WO2022269684A1 - Foam booster, premix solution including same, composition for polyurethane foam molding including these, and polyurethane foam with improved hydrophobicity - Google Patents

Foam booster, premix solution including same, composition for polyurethane foam molding including these, and polyurethane foam with improved hydrophobicity Download PDF

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Publication number
WO2022269684A1
WO2022269684A1 PCT/JP2021/023397 JP2021023397W WO2022269684A1 WO 2022269684 A1 WO2022269684 A1 WO 2022269684A1 JP 2021023397 W JP2021023397 W JP 2021023397W WO 2022269684 A1 WO2022269684 A1 WO 2022269684A1
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foam
polyether
group
polyurethane
formula
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PCT/JP2021/023397
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French (fr)
Japanese (ja)
Inventor
誠基 田村
裕之 稲垣
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ダウ・東レ株式会社
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Priority to PCT/JP2021/023397 priority Critical patent/WO2022269684A1/en
Publication of WO2022269684A1 publication Critical patent/WO2022269684A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00Manufacture of cellular products

Definitions

  • the present invention provides a silicone polyether having a specific structure for a water-blown polyurethane spray foam system comprising a) a specific polyether polyol, b) a polyisocyanate, c) a curing catalyst, and d) water as the primary blowing agent.
  • foam enhancers containing copolymers, etc. the foam enhancers have excellent hydrophobicity improving effects on polyurethane foams, particularly flexible polyurethane foams, obtained by the same system.
  • "foam” means a polyurethane foam unless otherwise specified.
  • Such a foamed polyurethane heat insulating layer is usually positioned between the outer wall of a house or the like and the inner wall of the room. Therefore, in cold seasons such as winter, when warm air containing moisture inside the room moves into the heat insulating layer, it may be cooled from the outer wall side and cause condensation. In addition to the concern that dew condensation may cause the generation of mold, it also leads to the deterioration of polyurethane.
  • such a foamed polyurethane heat insulating layer can be used as a sound absorbing layer that effectively absorbs the impact sound on the upper floor by positioning it between the upper floor and the lower ceiling of the house. This is because the foamed polyurethane is not a closed cell type but a continuous type based on an open cell structure, so sound easily enters the cells and is efficiently attenuated within the cells, resulting in high soundproofing. .
  • polyether-modified silicones can be designed with various structures and average molecular weights, and the EO wt. %, size, introduction of a lipophilic group to the silicone main chain, variation in the structure of the silicone main chain, the site of introduction of a modifying group, modification with two or more different polyether groups, etc. properties, affinity to urethane foam systems, etc. can be controlled. Therefore, polyether-modified silicones can be used in all polyurethane foam formulations such as rigid foams, semi-rigid foams, HR (high elasticity) foams (hereinafter sometimes simply referred to as "HR foams"), flexible foams, and microcellular foams. It has been known for a long time that it is useful as a surfactant (foam stabilizer) for controlling or stabilizing foam.To date, many varieties have been commercially manufactured and sold, greatly contributing to the development of the polyurethane foam industry. Contributing.
  • HR foams high elasticity foams
  • Patent Documents 1 to 10 disclose a silicone foam stabilizer modified with a polyether chain having a terminal hydroxyl group.
  • Patent Documents 3 to 10 disclose PO wt.
  • silicones modified with polyether chains with a large percentage and hydroxyl groups at the ends have been tried to apply to various foam formulations, but poor performance has been reported, such as being treated as a comparative example. There were many cases. Alternatively, in some cases, compositions containing the silicone were prepared, but performance was not confirmed by actual foaming evaluation. Also, there is no mention of spray foams in any of the prior art documents, and the foam formulations carried out and the foams obtained were completely different from the formulations for spraying and the foams obtained therefrom.
  • the number of parts of water used is usually 10 to 40 parts per 100 parts of polyol, which is extremely large, and is characterized by the fact that a low-density foam can be obtained.
  • the range of the number of parts to be added of water used in the formulations of various foam types in the prior art is only 1.0 to 6.5 parts, which is very different from the content of the present invention.
  • general-purpose foam stabilizers for flexible slab foam which are currently being diverted to residential thermal insulation spray foam systems, are suitable for increasing foam volume, but there is a need to lower the moisture permeability or water absorption of the foam. I have not been able to respond.
  • the present invention has been made to solve the above problems, and by using a large number of water addition parts and a small amount of foam stabilizer (foam enhancer), it is possible to form a large volume foam at a construction site or the like. It is particularly suitable for water-blown polyurethane spray foam systems, and has excellent compatibility with premix systems.
  • An object of the present invention is to provide a foam enhancer which has a fine cell structure and can remarkably improve the hydrophobicity of the resulting foam.
  • the foam is preferably flexible urethane foam.
  • the present invention provides premix solutions containing the suds booster and suitable for water-blown polyurethane spray foam systems, polyurethane foam-forming compositions containing the suds booster, and compositions obtained by using the suds booster. It is an object of the present invention to provide a polyurethane foam (particularly, a flexible polyurethane foam) which is particularly improved in hydrophobicity and uses thereof (heat insulating material/sound absorbing material, etc.).
  • the present invention provides a foam enhancer containing the silicone polyether copolymer. It is an object of the present invention to provide a method for improving the hydrophobicity of polyurethane foams, which is not limited to a particular spray foam system, and a method for improving the hydrophobicity.
  • a further object of the present invention is to provide a flexible polyurethane foam that satisfies such requirements for Low Emission/Low VOC and is obtained from the composition for forming a polyurethane spray foam.
  • each R independently represents a monovalent hydrocarbon group having 1 to 16 carbon atoms selected from alkyl, aryl and aralkyl groups
  • Each X is independently one or more of the formula: -C k H 2k O-(C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r
  • -Y represents the polyether group of Y is 100 mol % of H groups, or consists of 75 mol % or more of H groups and 25 mol % or less of other groups selected from C1-C4 alkyl or acetyl groups
  • m, n, k, p, q, and r are numbers satisfying the following conditions.
  • 12 ⁇ (m+n) ⁇ 230, 10 ⁇ m, 2 ⁇ n, n ⁇ m, 3 ⁇ k ⁇ 4, p, q, and r have a formula weight of the polyether group moiety represented by X in the range of 1400 to 4000, ⁇ sum of the formula weights of the oxypropylene group moiety represented by ( C3H6O )q and the oxybutylene group moiety represented by ( C4H8O )r ⁇ / ⁇ ( C2H4O )p
  • the sum of the formula weights of the oxyethylene group moieties represented by) ⁇ is the ratio value Z, It is a number that satisfies the condition (51/49) ⁇ Z ⁇ (95/5).
  • a foam enhancer containing a silicone polyether copolymer represented by the following, and have completed the present invention.
  • the suds booster is particularly suitable for use in water-blown polyurethane spray foam systems having specific configurations, and is not limited to specific spray foam systems, to significantly improve the hydrophobicity of polyurethane foams. can be done.
  • the present inventors have discovered premix liquids for water-blown polyurethane spray foam systems containing the above-described foam boosters, polyurethane foam-forming compositions containing them, and hydrophobically enhanced soft foams prepared therefrom.
  • the present inventors have found that the above problems can be satisfactorily solved by a polyurethane foam, a flexible polyurethane foam having Low Emission/Low VOC characteristics, or a heat insulating material/sound absorbing material, and have arrived at the present invention.
  • the number of parts to be added with water is large, and it is suitable for on-site foaming spray foam formulations such as building insulation applications using polyols for flexible urethane foam, excellent compatibility with premix systems, and can be used in small amounts
  • a foam enhancer capable of forming a large-volume foam suitable for building insulation, etc., having a fine cell structure, and significantly improving the hydrophobicity of the resulting foam. can be provided. Further, it is possible to provide a premix liquid for a polyurethane spray foam system and a composition for forming a polyurethane spray foam containing the foam enhancer.
  • a flexible polyurethane foam with improved hydrophobicity obtained from the composition for forming polyurethane spray foam and uses thereof, in particular, the flexible polyurethane foam having low emission/low VOC properties, heat insulation comprising these We can provide the material or sound absorbing material.
  • the foam enhancer of the present invention is excellent in quality and environmental compatibility, and can be manufactured at a lower cost than the foam stabilizer for flexible slab foam currently being diverted to water foam spray foam. is possible.
  • the present invention allows manufacturers of foam stabilizers to have the option of supplying high volumes to the market at lower prices than in the past, while manufacturers of premixes and foam systems We are able to provide end customers and markets with excellent premix liquids for polyurethane spray foam systems and polyurethane spray foam forming compositions, and both contribute to the sound development of society and industry and pursue appropriate profits. The degree of freedom that can be compatible with is increased.
  • silicone polyether copolymer which is the main component of the foam enhancer according to the present invention, will be described in detail.
  • the present invention is based on the unexpected discovery that the hydrophobicity of urethane foam is significantly improved by selecting the chemical structure of the silicone polyether copolymer, and that the silicone polyether copolymer has a specific composition.
  • the structure of the silicone polyether copolymer is one of the characteristic features of the present invention. .
  • silicone polyether copolymer is represented by the following general formula (1).
  • each X is independently represented by the formula: -C k H 2k O-(C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r -Y
  • Y is 100 mol % of H groups, or consists of 75 mol % or more of H groups and 25 mol % or less of other groups selected from C1-C4 alkyl or acetyl groups
  • m, n, k, p, q, and r are numbers satisfying the following conditions.
  • 12 ⁇ (m+n) ⁇ 230, 10 ⁇ m, 2 ⁇ n, n ⁇ m, 3 ⁇ k ⁇ 4, p, q, and r have a formula weight of the polyether group moiety represented by X in the range of 1400 to 4000, ⁇ sum of the formula weights of the oxypropylene group moiety represented by ( C3H6O )q and the oxybutylene group moiety represented by ( C4H8O )r ⁇ / ⁇ ( C2H4O )p
  • the sum of the formula weights of the oxyethylene group moieties represented by) ⁇ is the ratio value Z, It is a number that satisfies the condition (51/49) ⁇ Z ⁇ (95/5).
  • the formula weight is the sum of the product of the atomic weight and the number of atoms based on the chemical formula and composition formula. calculated based on the average chemical structure (structure identified by nuclear magnetic resonance spectroscopy with mainly 13C and 1H nuclides), the polyether group moiety represented by X, the oxypropylene group moiety, and the oxyethylene group The formula weights of the moieties and their sums.
  • each R is preferably independently selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, methyl, ethyl, n-propyl, n-butyl, i linear or branched alkyl groups such as -butyl, n-pentyl, i-pentyl, 2-methylbutyl, n-hexyl and n-octyl; phenyl; phenethyl or phenylisopropyl.
  • R is a methyl group.
  • X is a polyether group having a polyoxyalkylene structure bonded to silicon atoms, the formula: —C k H 2k O—(C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r —Y defined by
  • Y is a terminal group of a polyoxyalkylene structure, 100 mol% of which is an H group (hydrogen atom), or 75 mol% or more of an H group and 25 mol% or less of a C1-C4 alkyl or acetyl group. consists of the basis of Preferably, Y is 100 mol % hydrogen atoms.
  • polyether group portion represented by X, p, q, and r are the average number of oxyethylene units, oxypropylene units, and oxybutylene units that constitute the polyoxyalkylene structure, and
  • the formula weights of the oxypropylene group moiety represented by ⁇ (C 3 H 6 O) q and the formula weight of the oxybutylene group moiety represented by (C 4 H 8 O) r are within the range of 1400 to 4000.
  • the sum of the ratios ⁇ / ⁇ the sum of the formula weights of the oxyethylene group moieties represented by (C 2 H 4 O)p) ⁇ is It is a number that satisfies the condition (51/49) ⁇ Z ⁇ (95/5).
  • the ratio value Z exceeds (95/5), the oxypropylene group moiety represented by (C 3 H 6 O)q and the oxybutylene group represented by (C 4 H 8 O)r Hydrophobicity derived from the base portion becomes excessive, making it difficult for the silicone polyether copolymer to make the polyether polyol and a large amount of water compatible, which tends to cause poor stability of the premix liquid and poor foaming. Conversely, if the value of the ratio Z is less than (51/49), i.e.
  • the compatibility with the polyol for flexible urethane foam used in the on-site foaming spray foam formulation becomes insufficient, and it tends to be difficult to obtain a stable premix liquid, resulting in the failure to obtain the desired foam stabilizing effect. effect may not be achieved.
  • the polyether group portion represented by X may be a mixture of polyether chains having two or more different average chemical structures, but a polyether having terminal hydroxyl groups and composed only of an oxyethylene portion It does not contain any groups. Such highly polar hydrophilic groups are not suitable because they are less compatible with the polyol.
  • the X group does not contain oxybutylene units and has the formula: —C 3 H 6 O(C 2 H 4 O) p (C 3 H 6 O) q —H wherein the formula weight of the X group is in the range of 1500 to 2500, and the ratio Z satisfies the condition of (54/46) ⁇ Z ⁇ (80/20).
  • the oxyethylene units, oxypropylene units, and oxybutylene units contained in the polyether group X may have a block-type copolymer structure or a random-type copolymer structure. is more preferred.
  • alkylene group bonded to the silicon atom and having 3 to 4 carbon atoms and the alkylene portion constituting the oxypropylene unit or oxybutylene unit, even if it is a linear alkylene group, isopropylene group or isobutylene It may also be a branched isoalkylene group, such as a group.
  • m and n are degrees of polymerization of each siloxane unit of the side chain (Rake) type silicone polyether copolymer, and 12 ⁇ (m + n) ⁇ 230, 10 ⁇ m, 2 ⁇ n, a number in the range n ⁇ m.
  • the numbers are preferably in the range of 40 ⁇ m ⁇ 90 and 2 ⁇ n ⁇ 8.
  • the ratio of the lipophilic portion derived from the oxypropylene unit or the oxybutylene unit is high with respect to the formula weight of the entire polyether portion, Excellent compatibility with polyols for flexible urethane foam used in on-site spray foam formulations for thermal insulation. Therefore, it is advantageous in obtaining desirable foam-stabilizing effects such as expansion of convenience due to improved stability of the premix liquid and provision of a large foam volume and a fine cell structure.
  • the preferred silicone polyether copolymer described above does not solidify even at low temperatures, and has a low viscosity. It does not become too high, and the handleability after production is also improved. Furthermore, the use of the above preferred silicone polyether copolymer as a foam stabilizer for the spray foam can remarkably improve the hydrophobicity of the obtained urethane foam in addition to the foam enhancing effect.
  • Such a silicone polyether copolymer can be obtained by a known method of hydrosilylating a polyether compound having an alkenyl group at one end of the molecular chain and an organohydrogenpolysiloxane in the presence or absence of any solvent. Can be synthesized.
  • the silicone polyether copolymer according to the invention has the following general formula (1H): an organohydrogenpolysiloxane represented by ⁇ wherein R has the same definition as above, and m and n are the same numbers as above ⁇ ;
  • the oxyethylene units, oxypropylene units, and oxybutylene units contained in the polyether compound represented by the general formula (2) may have a block-type copolymer structure or a random-type copolymer structure. can be taken, but a random type structure is preferred.
  • the silicone polyether copolymer according to the present invention can also be obtained by reacting two or more different polyether compounds with the organohydrogenpolysiloxane. Structure of 0: Does not include polyether compounds in which the polyoxyalkylene portion is composed only of the polyoxyethylene portion.
  • the ratio of [substance amount of carbon-carbon double bonds in the polyether compound/substance amount of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane] is 1.0 to A range of 2.0 can be exemplified. That is, when synthesizing the silicone polyether copolymer according to the present invention, it is preferable to use an excessive amount of the polyether compound. More specifically, the above ratio is preferably in the range of 1.05 to 1.75, more preferably in the range of 1.20 to 1.60. The reason for this is that a portion of the terminal alkenyl groups of the polyether compound undergoes internal transfer during the hydrosilylation reaction and ceases to participate in the reaction.
  • silicone polyether copolymer is generally obtained as a mixture of the product silicone polyether copolymer and an unreacted polyether compound, and is represented by general formula (1) according to the present invention.
  • a foam enhancer having a hydrophobicity-improving effect containing a silicone polyether copolymer is constituted.
  • the foam enhancer containing the silicone polyether copolymer and having the effect of improving hydrophobicity is usually obtained as a transparent or almost transparent homogeneous liquid.
  • the polyether compound represented by the general formula (2) is produced by addition polymerization of ethylene oxide, propylene oxide, etc. in the presence of an alkali catalyst using an unsaturated alcohol such as allyl alcohol or allyl glycol as a starting material.
  • an unsaturated alcohol such as allyl alcohol or allyl glycol
  • it may contain diols at both ends as impurities. Therefore, such a double-ended diol compound, such as a PEG/PPG copolymer, may be further contained in the foam enhancer according to the present invention.
  • the progress of the reaction may be affected by trace impurities originally contained in the polyether compound or the organohydrogenpolysiloxane, by-products due to deterioration over time, and trace contaminants in the reactor. may be delayed.
  • appropriate measures such as adding a catalyst, raising the reaction temperature slightly higher than usual, extending the reaction time, or adding a reaction solvent for the purpose of improving the compatibility between the raw materials may be taken to prevent the reaction. It is desirable to control the process until the residual Si—H groups in the system are below the detection limit. Remaining Si—H groups may cause the generation of combustible hydrogen gas when the foam enhancer is blended into a premix system.
  • the residual amount of Si—H groups should be approximately 30 wt. ppm or less, and 10 wt. ppm or less, and 2.5 wt. ppm or less is particularly preferred.
  • the silicone polyether copolymer partially containing such a small amount of Si—H groups is not represented by the general formula (1) on the text, but industrially, it is considered to be substantially the same type. Included in the present invention.
  • reaction solvent is often not necessary, but when using a general organic solvent, aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as isopropyl alcohol; cyclohexane, n-heptane, methyl Selection from aliphatic saturated hydrocarbon solvents such as cyclohexane is preferred for industrial production.
  • aromatic hydrocarbon solvents such as toluene and xylene
  • alcohol solvents such as isopropyl alcohol
  • cyclohexane, n-heptane methyl
  • Selection from aliphatic saturated hydrocarbon solvents such as cyclohexane is preferred for industrial production.
  • these highly volatile reaction solvents need to be removed from the product system by stripping as soon as they have completed their role, such as the completion of the hydrosilylation reaction.
  • toluene and xylene belong to the so-called BTX solvents and have been widely used for the production of silicone polyether copolymers used as foam stabilizers
  • saturated hydrocarbon solvents having an average number of carbon atoms in the range of 6 to 11 include methylcyclohexane, n-heptane, heptane mixtures, heptane (commercial grade), isooctane, 2,2,4- trimethylpentane, octane mixture, ethylcyclohexane, dimethylcyclohexane, n-hexane, isohexane, hexane mixture, cyclohexane, 2-methylpentane, 2-methylheptane, 3-methylheptane, Isopar E (C7-C9 saturated hydrocarbon mixture), Isopar C (C7-C8 saturated hydrocarbon mixture), IP solvent 1016 (C6-C9 saturated hydrocarbon mixture), Isopar G (C10-C11 saturated hydrocarbon mixture) and the like.
  • C7 saturated hydrocarbons typified by methylcyclohexane, n-heptan
  • the foam booster according to the invention may additionally optionally comprise a diluent h') a polyalkylene glycol or derivative thereof which is liquid at 25°C.
  • a diluent h' a polyalkylene glycol or derivative thereof which is liquid at 25°C.
  • component h' a diluent h'
  • the viscosity and the like of the foam enhancer of the present invention can be adjusted without adversely affecting the function as a foam stabilizer or surfactant, and convenience during use and handling workability ( handling) can be improved.
  • component h') may be used in addition to the foam enhancer for the purpose of adjusting the hydroxyl value in the polyurethane foam-forming composition, that is, controlling various physical properties such as the crosslink density and strength of the polyurethane foam. .
  • the catalyst for the hydrosilylation reaction is not particularly limited as long as it can promote the hydrosilylation reaction.
  • a hydrosilylation reaction catalyst many metals and compounds have been known so far, and a suitable one can be selected from them and used for the production of the component e) according to the present invention.
  • Specific examples of hydrosilylation reaction catalysts include particulate platinum adsorbed on a silica fine powder or carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, Speyer's catalyst, olefin complex of chloroplatinic acid, chloride Coordination compounds of platinic acid and vinyl siloxanes, Karstadt catalysts, platinum black, palladium, and rhodium catalysts may be mentioned.
  • catalysts are dissolved or dispersed in toluene, xylene, ligand compounds of catalysts, alcohols, other suitable polar solvents, raw materials for reaction such as polyethers and diluents, etc., according to standard methods, and introduced into the reaction system. can do.
  • the amount of hydrosilylation reaction catalyst used is an effective amount, and is not particularly limited as long as it is an amount that promotes the synthesis reaction of the silicone polyether copolymer, which is the main component of the foam enhancer according to the present invention. Specifically, the sum (total 100% by mass), the amount of metal atoms in the catalyst is 0.5 to 100 ppm, preferably 3 to 30 ppm by mass of platinum metal atoms. If the content of the hydrosilylation reaction catalyst is less than the lower limit of the above range, the addition reaction may be insufficient. may have an adverse effect on transparency, such as coloring of
  • Conditions for the hydrosilylation reaction can be arbitrarily selected according to the type of raw materials and the presence or absence of a solvent.
  • the reaction can be completed by adding a small amount of an antioxidant such as tocopherol (vitamin E) and heating and stirring for a certain period of time at room temperature to 120°C, preferably 50 to 100°C, in an inert gas atmosphere such as nitrogen. .
  • the antioxidant may be added after hydrosilylation is completed.
  • the reaction time can be selected according to the reaction scale, amount of catalyst used and reaction temperature, and is generally in the range of several minutes to several hours.
  • the reaction may be carried out under reduced pressure for the purpose of improving quality and productivity, and not only a batch process but also a known semi-continuous or continuous production process can be applied.
  • the end point of the hydrosilylation reaction can be confirmed by the disappearance of Si—H bond absorption by infrared spectroscopy (IR) or the disappearance of hydrogen gas generation by the following alkaline decomposition gas generation method.
  • the amount of hydrogen gas generated can also be determined by analyzing silicon-bonded hydrogen atoms (Si—H) in the organohydrogenpolysiloxane, which is the reaction raw material, by the same method.
  • a solution obtained by dissolving a sample in toluene or IPA and a mixed solution of 28.5% by mass of caustic potash in ethanol/water are allowed to react at room temperature, and the generated hydrogen gas is collected in a collection tube. It is a method of measuring the volume.
  • the silicone polyether copolymer which is the main component of the foam enhancer according to the present invention, has a structure modified by a polyether group having a terminal hydroxyl group, a side reaction during the hydrosilylation reaction: dehydrogenation and Suppression of acetal formation is important.
  • a buffering agent represented by alkali metal carboxylates such as potassium acetate, potassium propionate and sodium acetate is added to the reaction system before the start of the main reaction.
  • reaction system may be added to the reaction system as solids (powder), dissolved or dispersed in a polar solvent such as methanol and then added to the reaction system, or may be added to the reaction system in advance by It is possible to exhibit the effect by dissolving or dispersing it in a polyether compound having an alkenyl group at its end. Generally, when these side reactions occur, the reaction system thickens, and in severe cases, gelation may occur. Use of a reaction solvent is effective in reducing such a situation.
  • the timing of adding the buffer is preferably before the start of the hydrosilylation reaction (main reaction).
  • the optimum amount of buffering agent to be added is the amount just enough to neutralize the amount of acid in the system, or a slight excess.
  • the foam enhancer according to the present invention may be gradually oxidized by oxygen in the air and deteriorate.
  • an antioxidant such as phenols, hydroquinones, benzoquinones, aromatic amines, or vitamins can be added to increase the oxidation stability, which is preferable.
  • an antioxidant for example, in addition to vitamin E described above, BHT (2,6-di-t-butyl-p-cresol), vitamin C, and the like may be used.
  • BHT 2,6-di-t-butyl-p-cresol
  • vitamin C and the like
  • the amount of the antioxidant used is in the range of 10 to 1000 ppm, preferably 50 to 500 ppm, based on the weight of component e).
  • the content of low-molecular-weight siloxane having 20 or less silicon atoms is preferably 5000 ppm (weight) or less, particularly preferably 2000 ppm (weight) or less. If this value exceeds 5,000 ppm, when the foam enhancer is used as a foam stabilizer for polyurethane foam, it may contaminate the surrounding members where the polyurethane foam is installed and cause contact failure in electrical and electronic devices. have a nature.
  • Such low-molecular-weight siloxanes include cyclic ones and straight-chain ones.
  • dimethylsiloxane and linear dimethylsiloxane oligomers represented by the formula CH3[(CH3)2SiO]mSi(CH3)3, where m is an integer from 1 to 10; Some methyl groups are partially substituted with other organic groups. More specific examples of such low-molecular-weight siloxanes include octamethyltetrasiloxane, decamethylpentacyclosiloxane, and both-terminal trimethylsiloxy group-blocked dimethylsiloxane oligomers. The content of such low-molecular-weight siloxane can be measured by analysis using, for example, a gas chromatography analyzer.
  • the method for reducing low-molecular-weight siloxane is not limited, it is usually done industrially by a stripping operation. Purification to remove low-molecular-weight siloxanes is desirable. Alternatively, the low-molecular-weight siloxane may be removed during the hydrosilylation reaction or after completion of the reaction.
  • the foam booster containing the above silicone polyether copolymer of the present invention is applied to a water-blown polyurethane spray foam system comprising a) to d) below.
  • polyisocyanates c) a curing catalyst,
  • Foaming agent that is water Sum of polyether polyol and other polyol components as component a) in the same system Range of 10 to 40 parts by mass per 100 parts by mass
  • the water-blown polyurethane spray foam system described above may contain at least one or more polyol components other than a') component a) polyether polyol.
  • the water-blown polyurethane spray foam system described above may optionally include f) a nonionic surfactant (silicone polyether covalent agent according to the present invention) as long as it does not impair the technical effects of the present invention. including organic surfactants and emulsifiers that do not correspond to polymers), g) flame retardants, h) other additives: for example, foam stabilizers for urethane foam other than the foam enhancer according to the present invention, diluents, Chain extenders, crosslinkers, secondary amounts of non-aqueous blowing agents, cell openers, fillers, reinforcing agents, pigments, dyes, colorants, antioxidants, antiozonants, UV stabilizers, antistatic agents, bactericides and antibacterials, and the like.
  • a nonionic surfactant silicone polyether covalent agent according to the present invention
  • polyether polyol Component a) used in the present invention is one or more polyether polyols having an average number of hydroxyl groups of 2 to 4, oxypropylene repeating units, and a number average molecular weight of 1,000 to 6,000.
  • Such polyols can be used for general flexible urethane foams such as flexible slab foams. Water or a polyhydric alcohol having an average of 2 to 4 hydroxyl groups in one molecule is used as a starting material, and an alkylene oxide is added to them. is produced by addition polymerization.
  • Alkylene oxides used in the production of polyoxyalkylene polyols usually have 2 to 4 carbon atoms, and propylene oxide and mixtures of propylene oxide and ethylene oxide are preferred. These polyols may be used alone or in combination of two or more.
  • mixtures of bifunctional and tri- to tetra-functional substances and/or mixtures of substances with different molecular weights or different chemical compositions can be used.
  • non-volatile, high-molecular-weight additives such as antioxidants and stabilizers
  • polyether polyols useful as component a) include Voranol-3010, Voranol 3137, V230-056 Polyol (Dow Chemical Company), ARCOL Polyol 16-56, ARCOL 200 Polyol 16-56 (Arco Chimecal Co.) , NIAX Polyol 16-56 (AC West Virginia Polyol Company), Desmophen PU20WB01, Desmophen 7186, Desmophen VPPU 20 WB 01 (BAYER), polypropylene glycol-based polyether polyol No.
  • polyether polyols with relatively low molecular weight and high functionality: polyhydric alcohols with an average number of hydroxyl groups of 3 to 8 and a number average molecular weight of 250 to 1000 Alkylene oxide adducts to polyvalent amines are also preferred.
  • saccharides such as sorbitol; sucrose; lactose; ⁇ -methylglucoside; ⁇ -hydroxyalkylglucoside; Adducts of ethylene oxide are mentioned.
  • carboxylic acids such as adipic acid and phthalic acid
  • polyhydric alcohols such as ethylene glycol, 1,4-butanediol and 1,6-hexanediol
  • polyester polyols produced by HR foams polyether polyols with a high content of primary hydroxyl groups and an average molecular weight of about 5000 to 7000, which are usually used for HR foams, and copolymerization of acrylonitrile, styrene, etc. in polyether polyols.
  • a polymer polyol or the like in which fine polymer particles are dispersed by means of a polymer may be appropriately selected and used in combination.
  • polyisocyanate As the polyisocyanate, it is preferable to select a non-volatile or non-volatile organic polyisocyanate, especially in the case of on-site foaming, considering the safety of workers and the surrounding environment on the premise that it will be used for spraying.
  • component b commercially advantageous materials are MDI (diphenylmethane diisocyanate), 4,4'-diphenylmethane diisocyanate, 4,2'-diphenylmethane diisocyanate, polymeric MDI (polymethylene polyphenyl polyisocyanate), crude MDI. .
  • isocyanate group-containing prepolymers MDI prepolymers prepared by reacting MDI with polyols, TDI prepolymers prepared by reacting TDI with polyols, and other aromatic or aliphatic polyisocyanates.
  • a derivative of the above polyisocyanate may be selected.
  • TDI toluene diisocyanate
  • the amount of polyisocyanate incorporated relative to the amount of other ingredients in the formulation is expressed by the "isocyanate index.”
  • “Isocyanate Index” is the actual amount of polyisocyanate used divided by the stoichiometric amount of polyisocyanate required to react with all active hydrogens in the reaction mixture multiplied by 100. .
  • the preferred range of the isocyanate index in component b) is generally in the range of 30 to 80, unlike the range in general polyurethane foams.
  • the polyisocyanate is MDI (diphenylmethane diisocyanate), polymeric MDI (polymethylene polyphenyl polyisocyanate), crude MDI, isocyanate, in the applied water blown polyurethane spray foam system.
  • a component selected from group-containing prepolymers and derivatives thereof, and the blowing agent (d)) of the same system is water as the main blowing agent, more preferably substantially only water, or other blowing agents Combinations containing no agents and only water are particularly preferred.
  • the isocyanate index of component b) is preferably in the range of 20-80, more preferably 30-70.
  • Urethane catalyst Metal catalysts and tertiary amines are generally used as catalysts for polyurethane resin production. and organic polyisocyanate to generate carbon dioxide gas, it is widely used in the formation of various types of urethane foam.
  • metal catalysts typified by tin catalysts, are mainly used in non-foaming urethane fields because they have high catalytic activity for promoting urethanization reactions and are excellent in practical use.
  • the tin-based catalyst is also used in combination with the amine-based catalyst.
  • nickel-based catalysts are mainly used in the formulation of mechanical froth foam.
  • the polyurethane spray foam system according to the present invention uses a large amount of water, it generates more heat of reaction than general flexible foams, and therefore has a high reaction rate. Therefore, it is usually sufficient to use an amine-based catalyst.
  • the amine-based catalyst may be used alone or in combination of two or more depending on the purpose of adjusting the reaction rate and foaming state.
  • amine-based catalysts examples include dimethylethanolamine, dimethylaminoethoxyethanol, triethylenediamine, bis(2-dimethylaminoethyl)ether, N,N,N',N'-tetramethylhexamethylenediamine, N ,N′,N′,N′′-Pentamethyldiethylenetriamine and other tertiary amine urethane catalysts, imidazole derivatives, slow-acting tertiary amine catalysts, general type tertiary amine catalysts, low-emission tertiary amine catalysts, non-emission tertiary Examples include amine catalysts and DABCO (registered trademark) catalysts from Air Products.From the viewpoint of imparting low emission characteristics to polyurethane foams, it is preferable to use reactive amine catalysts.If necessary, metal catalysts are used in combination.
  • Examples of these include nickel acetoacetonate, iron acetoacetonate, tin-based catalysts, bismuth-based catalysts, zinc-based catalysts, titanium-based catalysts, aluminum complexes, zirconium complexes, potassium octylate, potassium acetate. , sodium acetate, sodium octylate, metal oxide particles having solid acid points on the surface, quaternary ammonium carboxylic acid, etc.
  • the amount of component c) added is usually 1 to 1 to 100 parts by weight of the total polyol. 5 parts by weight.
  • the polyurethane spray foam system of the present invention produces a low density, lightweight, flexible urethane foam for insulation or sound absorption, typically expanded 100 times with water as the primary blowing agent (before foaming). If the density of the urethane mixed solution is assumed to be 1.0 g/cm3, the density of the foam after foaming is 0.01 g/cm3). Therefore, the number of parts of water added to 100 parts of the sum of polyether polyol and other polyol components as component a) in the system should be in the range of 10 to 40 parts, preferably in the range of 15 to 35 parts. within the range of 15 to 25 parts.
  • Purified water, pure water, distilled water, ion-exchanged water, tap water, tap water, and the like can be suitably used as water.
  • the blowing agent is preferably substantially only water from the standpoint of convenience and cost. is particularly preferred. If another expensive foaming agent is used in combination, gas will escape due to the open cell structure of the foam. It may be wasted in terms of effectiveness. Therefore, component d) is preferably water in an amount of 95% by mass or more, more preferably 99% by mass or more, and still more preferably 99 to 100% by mass, from the viewpoints of convenience and cost. It is one of the commercial and technical advantages of the foam enhancer according to the present invention that water, which can be easily and inexpensively procured at construction sites or the like, can be used as it is as a foaming agent.
  • flame-retardant foaming agents such as HFC-245fa and HFC-134a Hydrofluorocarbons , hydrofluoroolefins such as HFO and HCFO may be used in combination. If these expensive gases do not leak out of the filled mold with the foam, it helps improve insulation.
  • Component f) is one of the optional constituents of the polyurethane spray foam system of the present invention, whose primary purpose is to stabilize the premix liquid for the polyurethane spray foam system of the present invention.
  • the nonionic surfactant that is component f) is a nonionic organic surfactant or emulsifier that does not contain a silicon atom in its molecular structure. Polyether copolymers and foam enhancers containing them are excluded, and non-silicone surfactants or emulsifiers that do not have a silicon atom in their molecular structure (hereinafter referred to as "organic”) are particularly preferred. be.
  • component f addition of a nonionic organic surfactant capable of improving the clouding point of the system is effective in ensuring the storage stability of the premixed liquid over time and temperature.
  • the number of added moles of oxyethylene can usually be in the high range of 2 to 100, but from the viewpoint of water solubility, it is preferably 7 moles or more, and from the viewpoint of availability and ease of handling, it is preferably 30 moles or less.
  • Particularly preferred are POE(9-20) nonylphenyl ether and POE(9-20)octylphenyl ether.
  • the preferred amount of component f) used is 5 to 30 parts by weight per 100 parts by weight of the total amount of polyol. If the amount is less than 5 parts, the polyols having different polarities cannot be made compatible with each other or the polyol and water cannot be made compatible, making it difficult to obtain a homogeneous premix solution. opening) is less likely to occur, and foam shrinkage is more likely to occur.
  • the g) component is one of the arbitrary configurations of the polyurethane spray foam system according to the above, and the flame retardant used in the present invention is a flame retardant component other than the flame retardant polyol included in a') above, such as Phosphate esters such as trimethyl phosphate, triethyl phosphate, trischloroethyl phosphate and trischloropropyl phosphate.
  • the amount used is preferably 40 to 80 parts by weight per 100 parts by weight of the total polyol in a formulation that does not use a flame-retardant polyol. If it is less than 40 parts by weight, the flame retardant effect may be insufficient.
  • the amount of component g) used is preferably 20 to 40 parts by weight.
  • the flame retardant g) can also be mixed with the polyisocyanate component to form the urethane foam. These flame retardants reduce the viscosity of the urethane mixture and facilitate uniform foam formation by spraying. They also act as plasticizers for the polyurethane resin, improving the adhesion of the foam to the substrate. contribute.
  • h) component is a foam stabilizer for urethane foam other than the foam enhancer according to the present invention, a diluent, a chain extender, a cross-linking agent, a secondary amount of a non-aqueous foaming agent, a cell opening agent, a filler, a reinforcing agents, pigments, dyes, colorants, antioxidants, antiozonants, UV stabilizers, antistatic agents, bactericides and antibacterial agents, etc., which are known in the art and optional, and which are technically useful in the present invention. They may be included within the range of their normal content as long as the effect is not impaired.
  • the material is composed only of ingredients that do not cause release due to migration or volatilization from the foam, and the foam formulation is adjusted.
  • Compounding is important in formulating polyurethane foam-forming compositions.
  • a general foam stabilizer for flexible slab foam may be used in combination within a range that does not impair the effects of the present invention.
  • L-520 Si—O—C type silicone polyether copolymer
  • the optional h) component crosslinker or chain extender may contain a polyhydroxyl terminated compound having 2 to 8 hydroxyl groups per molecule and a molecular weight of 62-500.
  • Crosslinkers with 3 to 8 hydroxyl groups include glycerin, trimethylolpropane, pentaerythritol, mannitol, sorbitol, and the like.
  • Examples of useful chain extenders with two hydroxyl groups are dipropylene glycol, tripropylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, ethylene glycol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,2-propanediol, 1,3-propanediol and neopentyl glycol and the like.
  • Diethanolamine, monoethanolamine, and the like can also be used. These compounds may also be treated as diluents.
  • Other suitable diluents include polyalkylene glycols or derivatives thereof that are liquid at 25°C.
  • the optional h) component may also contain fillers, such as inorganic fillers or combinations of fillers. Fillers may be used for density modification, improving physical performance such as mechanical performance or sound absorption, flame retardancy or other benefits including improved economics such as calcium carbonate. or other fillers that reduce the cost of foam production, aluminum hydroxide or other flame retardant fillers, barium sulfate or other high density fillers used for sound absorption, glass or other fillers that further reduce foam density Contains microspheres of polymer-like material.
  • fillers may be used for density modification, improving physical performance such as mechanical performance or sound absorption, flame retardancy or other benefits including improved economics such as calcium carbonate. or other fillers that reduce the cost of foam production, aluminum hydroxide or other flame retardant fillers, barium sulfate or other high density fillers used for sound absorption, glass or other fillers that further reduce foam density Contains microspheres of polymer-like material.
  • High aspect ratio fillers or reinforcing agents used to modify the mechanical performance of foams, such as rigid or flexible modules include man-made fibers such as ground glass or graphite fibers; natural animal fibers such as wool or vegetable fibers such as cotton; artificial plate-like fibers such as ground glass; and natural mineral plate-like fillers such as mica. Including any pigments, dyes or colorants that may be added.
  • the present invention includes anti-ozonants, antioxidants; heat or thermo-oxygen decomposition inhibitors, UV stabilizers, UV absorbers, or the resulting foam heat, light when added to the foam-forming composition. and/or use of any other additive that avoids or inhibits chemical degradation is contemplated. Also contemplated for use herein are any of the known and conventional antistatic agents, disinfectants, antibacterial agents and gas fade inhibitors.
  • the premix liquid for the polyurethane spray foam system comprises: a) polyether polyol, c) urethane catalyst, d) water blowing agent: polyether polyol as component a) in said system and other It contains at least 10 to 40 parts by weight per 100 parts by weight of the total polyol components, and e) a foam enhancer having a hydrophobicity-enhancing effect containing the silicone polyether copolymer.
  • premix liquid for the polyurethane spray foam system according to the present invention preferably further contains f) a nonionic surfactant, particularly an organic nonionic surfactant.
  • Premix fluids for polyurethane spray foam systems according to the present invention may have a color derived from the substrate, but usually have the properties of clear homogeneous fluids.
  • composition for Forming Polyurethane Spray Foam comprises components a), b), c), d) and e), and optionally one selected from a′) and f) above. can contain one or more
  • the composition also further comprises g) a flame retardant and optionally h) other additives. The types and amounts of each component are as described for the polyurethane spray foam system.
  • the following component a) is "one type having an average number of hydroxyl groups in the molecule of 2 to 4, having a repeating unit composed of an oxypropylene group, and having a number average molecular weight within the range of 1000 to 6000. It satisfies the above polyether polyol requirements. Also, the concentration of the isocyanate groups in component b) below is 30.5 to 32.0 wt. % range.
  • Formula 1 a) Polypropylene glycol-based polyether polyol (Sanyo Kasei No.
  • the composition for forming polyurethane spray foam according to the present invention can be used particularly suitably for forming flexible polyurethane foams, and meets the current needs of the polyurethane industry, which requires strict VOC (volatile organic compound) control or emission control. It is possible. More specifically, the content of the low-molecular-weight siloxane having 20 or less silicon atoms in the foam enhancer can be easily suppressed to 5000 ppm (weight) or less, 2000 ppm (weight) or less, or 1000 ppm (weight) or less. Moreover, since the amount itself used as a foam enhancer is small, VOCs derived from these volatile siloxanes and their emissions can be almost completely suppressed in the finally obtained polyurethane foam.
  • VOC volatile organic compound
  • the content of these components in the foam enhancer exceeds 5000 ppm, when the foam enhancer is used as a foam stabilizer for a polyurethane foam, the surrounding members around the place where the polyurethane foam is installed will be contaminated, It is not preferable because it may cause contact failure of electric/electronic devices.
  • the flexible polyurethane foam obtained by curing the composition for forming polyurethane spray foam according to the present invention is not limited in its use, but is a building material cured by on-site foaming, in particular, a heat insulating material or a sound absorbing material. It can be suitably used as
  • the resulting foam has a fine cell structure and is suitable for applications such as heat insulation / sound absorption Moreover, compared with the use of conventional foam enhancers, the hydrophobicity of polyurethane foams (especially flexible polyurethane foams) can be significantly improved, which is a major advantage not found in the prior art, and In recent years, it can satisfy the requirements of Low Emission/Low VOC, which are of high importance especially in building applications.
  • the present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these.
  • the number average molecular weight other than the "formula weight" is a value obtained as a polystyrene equivalent by GPC (detector: refractometer) using a chloroform eluent.
  • the performance evaluation procedure of the foam enhancer according to the present invention is A: Premix compatibility test, B: Formation of urethane foam, C: Evaluation of volume / cell structure of urethane foam, D: Water absorption test of urethane foam I will explain in order.
  • A Premix compatibility test
  • a 1. Charge 50 g of a) polyether polyol and proportions of d) water, c) urethane catalyst, e) foam enhancer or comparative foam stabilizer to a 100 mL glass bottle.
  • A2. Homogenize the contents by stirring for 1 minute using a disk-shaped disper mixer with a saw blade.
  • A3. Cap the vial and let stand overnight at room temperature to allow bubbles to dissipate.
  • D Water absorption test of urethane foam
  • D1 The foam pieces obtained in C above are further chopped with an electric cutter to prepare rectangular parallelepiped test pieces of length 6.5 cm x width 6.5 cm x height 4 cm. Here, it is assumed that this test piece was sampled from the center of the foam containing the plastic cup prepared in B above.
  • D2. Measure and record the weight of the test piece.
  • D3. Prepare a water bath.
  • D4. The bottom half of the test piece is immersed in the water bath for 2 hours, then removed and weighed and recorded.
  • D5. Calculate and record the water absorption (% by weight) of the test piece.
  • Comparative foam stabilizer R4: M * D18D * 3M * , * -C3H6O(EO) 15 ( PO) 5 - CH3
  • the Me 3 SiO group (or Me 3 Si group) is "M”
  • the Me 2 SiO group is “D”
  • the Me 2 HSiO group is "M H
  • a MeHSiO group is denoted as “D H ”
  • units obtained by modifying one of the methyl groups in M and D with some substituent (* or **) are denoted as M * and D * , and the like.
  • (EO) represents an oxyethylene group
  • (PO) represents an oxypropylene group
  • Me represents a methyl group
  • Ac represents an acetyl group.
  • Example 1 Production of foam enhancer with identification number SI-1 An organohydrogen represented by the average composition formula MD 53 D H 3 M and having a concentration analysis value of hydrogen groups bonded to silicon atoms of 0.072% by mass. 139.68 g of genpolysiloxane raw material, represented by the average compositional formula CH 2 ⁇ CH—CH 2 —O(C 2 H 4 O) 9 (C 3 H 6 O) 22 —H, concentration analysis value of unsaturated groups is 0.45 mmol/g and the hydroxyl value analysis value is 28.4 mg-KOH/g. Heating was started while setting the temperature of the oil bath to 85°C. The allyl/SiH molar ratio in this reaction system was 1.4.
  • the IPA in the receiver was temporarily discarded, and the pressure in the system was gradually reduced to 30 mmHg while paying attention to bubbling and bumping. After that, the temperature of the liquid in the flask was maintained at 110 to 125° C. and the pressure was kept at 10 mmHg or less for 75 minutes to remove volatile matter. After that, the heating was stopped, the flask was allowed to cool to 95°C or less, and the pressure was restored.
  • Identification numbers SR-1 to SR-8 The identification numbers of the comparative samples and the average compositional formula of the main components are shown below. Although (EO) and (PO) are expressed in a block-bonded form for simplicity, it is actually a random addition structure.
  • the polyether terminal group Y of the silicone foam stabilizer has a structure mainly composed of H, when the value of the ratio Z is large (here, it has a PO-rich long polyether chain) It has been found that the foam has excellent compatibility with the premix system, has a large volume, has a good cell structure, and has a low water absorption rate. That is, it was found that the hydrophobicity of the urethane foam itself can be improved by selecting the specific chemical structure of the silicone polyether copolymer used as a foam stabilizer for urethane foam.
  • the polyether terminal group Y of the silicone foam stabilizer has a capped structure such as Me or Ac, it is characterized by excellent compatibility with the premix even if the value of the ratio Z is small. It is clear that the foam has a high water absorption rate and cannot meet the market needs.
  • the foam enhancers SI-1 to SI-4 of the present invention do not require capping of the hydroxyl group portion of the single-ended allyl polyether, which is the raw material, and therefore the soft slabs currently being diverted to spray foam systems It has the advantage of being cheaper to manufacture than foam stabilizers. Nevertheless, as shown in Table 4 above, it outperforms F3 in terms of overall performance balance. Therefore, the foam enhancer of the present invention greatly contributes to the sound development of society and industry.
  • the foam enhancers SI-1 to SI-3 of the present invention were analyzed for volatile cyclic siloxanes (D4 to D6) by the headspace GC method according to the following procedure. E1. About 1 g of sample was weighed into a 20 mL vial and sealed. E2. After heating the vial at 150° C. for 30 minutes, 1 mL of headspace was injected into GC using a headspace sampler and measured.
  • composition for forming a 100 times water expanded polyurethane thermal insulation spray foam suitable for use with the foam enhancer of the present invention.
  • component a) in the table below is "one type having an average number of hydroxyl groups in the molecule of 2 to 4, having a repeating unit consisting of an oxypropylene group, and having a number average molecular weight within the range of 1000 to 6000. It satisfies the above polyether polyol requirements. Also, the calculated isocyanate index for Formulation 2 and Formulation 3 in the table below is about 30.

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Abstract

[Problem] To provide a foam booster, etc., endowed with major advantages not found in the prior art such as having excellent stability, handling workability, and foamability of a premix liquid, having excellent cost and work efficiency in building applications, etc., having a fine cell structure of the foam obtained, that is suitable for applications such as insulating materials, and that can markedly improve the hydrophobicity of a polyurethane foam in comparison to conventional foam boosters. [Solution] Provided are: a foam booster containing a silicone polyether copolymer having a specific structure for a water-foamed polyurethane spray foam system including a) a specific polyether polyol, b) a polyisocyanate, c) a curing catalyst, and d) water, which is the major foaming agent; a premix solution including the same; a composition for polyurethane foam molding including these; and a polyurethane foam having improved hydrophobicity and the use thereof.

Description

泡増強剤、これを含むプレミックス溶液、これらを含むポリウレタン発泡体形成用組成物、および疎水性が改善されたポリウレタン発泡体Foam booster, premix solution containing same, composition for forming polyurethane foam containing same, and polyurethane foam with improved hydrophobicity
本発明は、a)特定のポリエーテルポリオール、b)ポリイソシアネート、c)硬化触媒、およびd)主要発泡剤である水 を含む水発泡型ポリウレタンスプレーフォームシステム用の特定の構造を有するシリコーンポリエーテル共重合体を含有する泡増強剤等に関し、当該泡増強剤は、同システムにより得られるポリウレタン発泡体、特に、軟質ポリウレタン発泡体に対して優れた疎水性改善効果を有する。以下の説明において、「フォーム」とは、特に異なる説明がない限り、ポリウレタンの発泡体を意味するものである。 The present invention provides a silicone polyether having a specific structure for a water-blown polyurethane spray foam system comprising a) a specific polyether polyol, b) a polyisocyanate, c) a curing catalyst, and d) water as the primary blowing agent. Regarding foam enhancers containing copolymers, etc., the foam enhancers have excellent hydrophobicity improving effects on polyurethane foams, particularly flexible polyurethane foams, obtained by the same system. In the following description, "foam" means a polyurethane foam unless otherwise specified.
従来から住宅や冷凍保温倉庫、タンク設備など各種建造物の断熱施工部分に、断熱層を現場発泡により施工する方法が行われている。近年は、更に低コスト化のニーズが強まり、発泡倍率の高い(すなわち水の使用部数の多い)低密度フォーム処方が広がってきた。こうした発泡ポリウレタンシステムの販売者は、cost-in-useの視点から同一使用量でより大きな体積のフォームを形成できる整泡剤を求める傾向にあり、現在、汎用の軟質スラブフォーム向け整泡剤の市販品が、住宅用の断熱スプレーフォームシステムにも適するとして利用されている。 BACKGROUND ART Conventionally, a method of constructing an insulation layer by on-site foaming has been carried out on the insulation construction parts of various buildings such as houses, refrigerated warehouses, and tank facilities. In recent years, the need for further cost reduction has increased, and low-density foam formulations with a high foaming ratio (that is, a large number of water-using parts) have spread. From a cost-in-use perspective, sellers of these foamed polyurethane systems are looking for foam stabilizers that can produce larger volumes of foam with the same dosage. Commercial products are also available as suitable for residential thermal insulation spray foam systems.
このような発泡ポリウレタン断熱層は、通常は住宅等の外壁と室内側の内壁との間に位置する。従って、冬季など寒い時期には、室内側の湿気を含んだ暖かい空気が断熱層の内部に移行した際、外壁側から冷やされて結露を生じる可能性がある。結露はカビ発生の原因となる懸念があることに加えてポリウレタンの劣化にもつながるため、透湿性或いは吸水性のより低い発泡ポリウレタンシステムの開発が望まれていた。なお、このような発泡ポリウレタン断熱層は、住宅の階上床と階下天井部との間に位置させることにより、階上での衝撃音を効果的に吸収する吸音層としても活用できる。これは、当該発泡ポリウレタンが独立気泡タイプではなく開放セル構造に基づく連通タイプであるため、音がセル内に進入し易くなって該セル内で効率良く減衰するため、防音性が高くなることによる。 Such a foamed polyurethane heat insulating layer is usually positioned between the outer wall of a house or the like and the inner wall of the room. Therefore, in cold seasons such as winter, when warm air containing moisture inside the room moves into the heat insulating layer, it may be cooled from the outer wall side and cause condensation. In addition to the concern that dew condensation may cause the generation of mold, it also leads to the deterioration of polyurethane. In addition, such a foamed polyurethane heat insulating layer can be used as a sound absorbing layer that effectively absorbs the impact sound on the upper floor by positioning it between the upper floor and the lower ceiling of the house. This is because the foamed polyurethane is not a closed cell type but a continuous type based on an open cell structure, so sound easily enters the cells and is efficiently attenuated within the cells, resulting in high soundproofing. .
一方、ポリエーテル変性シリコーンは、様々な構造や平均分子量の設計が可能であり、ポリエーテル部のEO wt.%やサイズ、シリコーン主鎖への親油基の導入、シリコーン主鎖構造のバリエーションや変性基の導入部位、異なる2以上のポリエーテル基による変性等によっても、界面活性能や発泡剤への適合性、ウレタンフォームシステムへの親和性等をコントロールする事ができる。従って、ポリエーテル変性シリコーンは、硬質フォーム、半硬質フォーム、HR(高弾性)フォーム(以下、単に「HRフォーム」ということがある)、軟質フォーム、マイクロセルラーフォーム等全てのポリウレタンフォーム処方で、気泡コントロール或いは気泡安定用の界面活性剤(整泡剤)として有用であることが古くから知られており、現在まで数多くの品種が商業的に製造・販売されており、ポリウレタンフォーム産業の発展に大きく貢献している。 On the other hand, polyether-modified silicones can be designed with various structures and average molecular weights, and the EO wt. %, size, introduction of a lipophilic group to the silicone main chain, variation in the structure of the silicone main chain, the site of introduction of a modifying group, modification with two or more different polyether groups, etc. properties, affinity to urethane foam systems, etc. can be controlled. Therefore, polyether-modified silicones can be used in all polyurethane foam formulations such as rigid foams, semi-rigid foams, HR (high elasticity) foams (hereinafter sometimes simply referred to as "HR foams"), flexible foams, and microcellular foams. It has been known for a long time that it is useful as a surfactant (foam stabilizer) for controlling or stabilizing foam.To date, many varieties have been commercially manufactured and sold, greatly contributing to the development of the polyurethane foam industry. Contributing.
しかしながら、水の添加部数の多い建造物断熱用の現場発泡スプレーフォームは、ポリウレタンフォーム産業の長い歴史の中では比較的新しい技術分野と考えられる。すなわち、本発明者らの調査した範囲では、ポリエーテル変性シリコーン整泡剤の化学構造、当該スプレーフォーム処方での整泡剤の性能、得られたフォーム特性との相関等について、これまで詳細な報告は為されていなかった(特許文献1~10)。具体的には、、特許文献1~2には、末端が水酸基であるポリエーテル鎖で変性されたシリコーン整泡剤は示されていなかった。特許文献3~10には、PO wt.%が大きく末端が水酸基であるポリエーテル鎖で変性されたシリコーンが幾つか例示され、様々なフォーム処方への適用が試行されていたが、比較例として扱われるなど、性能不良が報告されていた事例が多かった。或いは、当該シリコーンを含む組成物の調製は行われたが、現実の発泡評価による性能確認が行われなかった事例もあった。また、どの先行文献においてもスプレーフォームに関する言及は無く、実施されたフォーム処方や得られたフォームは、スプレー用処方・それにより得られるフォームとは全く異なっていた。例えば、水を主要な発泡剤とする100倍発泡スプレーフォーム処方では、水の使用部数がポリオール100部に対して通常10~40部と極めて多く、低密度フォームが得られるのが特徴であるが、先行文献の各種フォームタイプの処方で用いられた水の添加部数の範囲は1.0~6.5部に留まっており、本願発明とは内容が大きく異なる。また、現在、住宅用の断熱スプレーフォームシステムに転用されている軟質スラブフォーム向け汎用整泡剤は、フォーム体積を稼ぐのには適しているが、フォームの透湿性或いは吸水性を低くするニーズに応えることができていない。更には、これら先行文献において、ウレタンフォーム用整泡剤として利用されるポリエーテル変性シリコーンに関して特定の化学構造を選択することにより、ウレタンフォーム自体の疎水性を向上できるという本発明の知見について、一切の言及も試験も確認もされていない。 However, blow-in-place spray foam for high water add-on building insulation is considered a relatively new technical area in the long history of the polyurethane foam industry. That is, within the scope of the present inventors' investigation, the chemical structure of the polyether-modified silicone foam stabilizer, the performance of the foam stabilizer in the spray foam formulation, the correlation with the obtained foam properties, etc. have been detailed so far. No reports have been made (Patent Documents 1 to 10). Specifically, Patent Documents 1 and 2 do not disclose a silicone foam stabilizer modified with a polyether chain having a terminal hydroxyl group. Patent Documents 3 to 10 disclose PO wt. Some examples of silicones modified with polyether chains with a large percentage and hydroxyl groups at the ends have been tried to apply to various foam formulations, but poor performance has been reported, such as being treated as a comparative example. There were many cases. Alternatively, in some cases, compositions containing the silicone were prepared, but performance was not confirmed by actual foaming evaluation. Also, there is no mention of spray foams in any of the prior art documents, and the foam formulations carried out and the foams obtained were completely different from the formulations for spraying and the foams obtained therefrom. For example, in a 100-fold expansion spray foam formulation using water as the main foaming agent, the number of parts of water used is usually 10 to 40 parts per 100 parts of polyol, which is extremely large, and is characterized by the fact that a low-density foam can be obtained. , the range of the number of parts to be added of water used in the formulations of various foam types in the prior art is only 1.0 to 6.5 parts, which is very different from the content of the present invention. In addition, general-purpose foam stabilizers for flexible slab foam, which are currently being diverted to residential thermal insulation spray foam systems, are suitable for increasing foam volume, but there is a need to lower the moisture permeability or water absorption of the foam. I have not been able to respond. Furthermore, in these prior documents, there is no knowledge of the present invention that the hydrophobicity of the urethane foam itself can be improved by selecting a specific chemical structure for the polyether-modified silicone used as a foam stabilizer for urethane foam. is not mentioned, tested or confirmed.
以上の通り、特許文献1~10ではスプレーフォーム処方についての説明がなく、従って水の添加部数が多く、軟質ウレタンフォーム用ポリオールを利用することを特徴とする、建造物断熱用の現場発泡スプレーフォーム処方での検討も為されていなかった。従って、ポリエーテル変性シリコーン整泡剤の化学構造、当該スプレーフォーム処方での整泡剤の性能、得られたフォーム特性との相関等について何ら記載も示唆もなされていなかった。さらに、当該用途では、1)プレミクス系との相溶性、2)より大きなフォーム体積の付与、3)より微細な開放セル構造の付与、が一般に整泡剤に期待される性能と考えられるが、今般求められている4)フォーム自体の透湿性又は吸水性をより低くする(或いはフォームの疎水性を向上する)手法については、何ら記載も示唆もされていない。このため、当業者が、整泡剤の化学構造の選択によってウレタンフォームの疎水性を改善する有効なアプローチが既存技術には存在せず、その技術的効果も予測が困難であった。 As described above, in Patent Documents 1 to 10, there is no explanation about the spray foam formulation, so the number of parts added with water is large, and the on-site foaming spray foam for building insulation is characterized by using a polyol for flexible urethane foam. Prescription considerations were also not made. Therefore, neither the chemical structure of the polyether-modified silicone foam stabilizer, the performance of the foam stabilizer in the spray foam formulation, nor the correlation with the properties of the obtained foam, etc. have been provided. Furthermore, in this application, 1) compatibility with premix systems, 2) imparting a larger foam volume, and 3) imparting a finer open cell structure are generally considered to be performances expected of foam stabilizers. There is no description or suggestion of 4) the technique of lowering the moisture permeability or water absorbency of the foam itself (or improving the hydrophobicity of the foam), which is currently required. For this reason, it has been difficult for those skilled in the art to anticipate the technical effects of the existing technology, as there is no effective approach for improving the hydrophobicity of urethane foam by selecting the chemical structure of the foam stabilizer.
このような背景技術の下、上記の技術的課題を解決し、さらに、特定の原料/発泡/硬化システムを使用し、かつ、得られるポリウレタン発泡体が上記の要求事項を満たす技術が必要とされている。また、ポリウレタン発泡体の疎水性を有効に改善する技術が必要とされている。 Under such background art, there is a need for a technology that solves the above technical problems, uses a specific raw material/foaming/curing system, and provides a polyurethane foam that satisfies the above requirements. ing. There is also a need for techniques to effectively improve the hydrophobicity of polyurethane foams.
米国特許第3817822号明細書U.S. Pat. No. 3,817,822 米国特許第3398104号明細書U.S. Pat. No. 3,398,104 米国特許第3669913号明細書U.S. Pat. No. 3,669,913 米国特許第4478957号明細書U.S. Pat. No. 4,478,957 米国特許第4529743号明細書U.S. Pat. No. 4,529,743 特許第3135318号明細書(特開平5-117352号公報)Japanese Patent No. 3135318 (JP-A-5-117352) 米国特許第5489617号明細書U.S. Pat. No. 5,489,617 米国特許第6071977号明細書(特許第4366470号明細書)U.S. Pat. No. 6,071,977 (Patent No. 4,366,470) 米国特許第8436064号明細書(特許第5743544号明細書)US Patent No. 8436064 (Patent No. 5743544) 欧州特許出願公開3530703号公報(国際公開2018-074257号公報)European Patent Application Publication No. 3530703 (International Publication No. 2018-074257)
本発明は、上記課題を解決すべくなされたものであり、水の添加部数が多く、少量の整泡剤(泡増強剤)の使用により、建築現場等で大容積の発泡体を形成可能な、水発泡型ポリウレタンスプレーフォームシステムに特に適合しており、プレミックス系との相溶性に優れ、少量の使用で建造物断熱用途等に適した大容積の発泡体を形成でき、得られる発泡体が微細なセル構造を有し、かつ、得られる発泡体の疎水性を顕著に向上させることができる泡増強剤を提供することを目的とする。本課題において、当該発泡体は、特に、軟質ウレタンフォームであることが好ましい。 The present invention has been made to solve the above problems, and by using a large number of water addition parts and a small amount of foam stabilizer (foam enhancer), it is possible to form a large volume foam at a construction site or the like. It is particularly suitable for water-blown polyurethane spray foam systems, and has excellent compatibility with premix systems. An object of the present invention is to provide a foam enhancer which has a fine cell structure and can remarkably improve the hydrophobicity of the resulting foam. In the present subject, the foam is preferably flexible urethane foam.
さらに、本発明は、当該泡増強剤を含み、水発泡型ポリウレタンスプレーフォームシステムに適したプレミックス溶液、当該泡増強剤を含むポリウレタン発泡体形成用組成物、および当該泡増強剤の使用により得られ、特に疎水性が顕著に改善されたポリウレタン発泡体(特に、軟質ポリウレタンフォーム)およびその用途(断熱材/吸音材等)を提供する事を目的とする。 Further, the present invention provides premix solutions containing the suds booster and suitable for water-blown polyurethane spray foam systems, polyurethane foam-forming compositions containing the suds booster, and compositions obtained by using the suds booster. It is an object of the present invention to provide a polyurethane foam (particularly, a flexible polyurethane foam) which is particularly improved in hydrophobicity and uses thereof (heat insulating material/sound absorbing material, etc.).
さらに、本発明は、シリコーンポリエーテル共重合体の化学構造の選択によってウレタンフォームの疎水性が顕著に向上するという予期せぬ発見に基づき、当該シリコーンポリエーテル共重合体を含有する泡増強剤の使用による、特定のスプレーフォームシステムに限定されない、ポリウレタン発泡体の疎水性の改善方法、疎水性の向上方法を提供することを目的とする。 Furthermore, based on the unexpected discovery that the hydrophobicity of urethane foam is significantly improved by selecting the chemical structure of the silicone polyether copolymer, the present invention provides a foam enhancer containing the silicone polyether copolymer. It is an object of the present invention to provide a method for improving the hydrophobicity of polyurethane foams, which is not limited to a particular spray foam system, and a method for improving the hydrophobicity.
本発明は上記課題を解決するものであるが、さらに、本発明者らは、ポリウレタン発泡体形成組成物、およびこれにより調製されるポリウレタン発泡体について、新たな課題を発見した。すなわち、近年のポリウレタン発泡体(以下、「ウレタンフォーム」または「フォーム」と略称することがある)材料の市場ニーズとして、低排出性、すなわち、「Low Emission特性」の需要が高まっている。これは、ポリウレタン発泡体から発生乃至揮発する化学物質等の成分が量的に少ないことを特徴とする要求特性であり、具体的には、フォームから発生する揮発成分が少ない(=Low VOC(Volatile Organic Compound))、シックハウス・アレルギーなどを予防するため、経時でフォームから外部に放出される化学物質の量が少ない(=Low Emission Of Chemical Compound)、自動車の内部に使用されたフォームから揮発した成分が付着して窓ガラスなどに曇りを生じる現象が起こり難い(=Low Fogging)などの要求として表現されることがあるが、化学物質の種類や性質の相違を除けば、フォームに由来する排出成分が少ないという点において実質的な意味はほぼ同じである。 Although the present invention solves the above problems, the present inventors have also discovered new problems with polyurethane foam-forming compositions and polyurethane foams prepared therefrom. That is, as a recent market need for polyurethane foam (hereinafter sometimes abbreviated as "urethane foam" or "foam") material, demand for low emission properties, that is, "low emission characteristics" is increasing. This is a required property characterized by the amount of components such as chemical substances generated or volatilized from the polyurethane foam being quantitatively small. (Organic Compound)), to prevent sick house allergies, etc., the amount of chemical substances emitted from the foam to the outside over time is small (= Low Emission Of Chemical Compound), volatile components from the foam used inside the car It is sometimes expressed as a requirement that it is difficult for dust to adhere to the window glass and cause fogging (= Low Fogging). The substantive meaning is almost the same in that there is less
本発明は、このようなLow Emission/Low VOCの要求を充足し、且つ前記ポリウレタンスプレーフォーム形成用組成物から得られる、軟質のポリウレタンフォームを提供することを更なる目的とする。 A further object of the present invention is to provide a flexible polyurethane foam that satisfies such requirements for Low Emission/Low VOC and is obtained from the composition for forming a polyurethane spray foam.
鋭意検討の結果、本発明者らは、一般式(1):
Figure JPOXMLDOC01-appb-C000003
{式中、Rは各々独立にアルキル、アリール、アラルキル基から選択される炭素原子数1~16の1価の炭化水素基を表し、
Xは、各々独立に式:-C2kO-(CO)p(CO)q(CO)r-Yで示される1種類または2種類以上のポリエーテル基を表し、
Yは、100モル%がH基であるか、75モル%以上のH基と25モル%以下のC1~C4アルキル又はアセチル基から選ばれるその他の基からなり、
m、n、k、p、q 、r は以下の条件を満たす数である。
12≦(m+n)≦230、
10≦m、
2≦n、
n≦m、
3≦k≦4、
p、q、rは、Xで表されるポリエーテル基部分の式量が1400~4000の範囲内にあり、
{(CO)qで表されるオキシプロピレン基部分および(CO)rで表されるオキシブチレン基部分の式量の和}/{(CO)pで表されるオキシエチレン基部分の式量の和)}である比の値Zが、
(51/49)≦Z≦(95/5)の条件を満たす数である。
ただし、式中のXにおいて、1≦pかつq=r=0である構造を有するポリエーテル基は除く。}
で表されるシリコーンポリエーテル共重合体を含有する泡増強剤により、上記課題を解決できる事を見出し、本発明に到達した。当該泡増強剤は、特定の構成を有する水発泡型ポリウレタンスプレーフォームシステムにおける使用に、特に適しており、かつ、特定のスプレーフォームシステムに限定されない、ポリウレタン発泡体の疎水性を顕著に改善することができる。
As a result of intensive studies, the present inventors found general formula (1):
Figure JPOXMLDOC01-appb-C000003
{wherein each R independently represents a monovalent hydrocarbon group having 1 to 16 carbon atoms selected from alkyl, aryl and aralkyl groups,
Each X is independently one or more of the formula: -C k H 2k O-(C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r -Y represents the polyether group of
Y is 100 mol % of H groups, or consists of 75 mol % or more of H groups and 25 mol % or less of other groups selected from C1-C4 alkyl or acetyl groups;
m, n, k, p, q, and r are numbers satisfying the following conditions.
12≦(m+n)≦230,
10≦m,
2≦n,
n≦m,
3≤k≤4,
p, q, and r have a formula weight of the polyether group moiety represented by X in the range of 1400 to 4000,
{sum of the formula weights of the oxypropylene group moiety represented by ( C3H6O )q and the oxybutylene group moiety represented by ( C4H8O )r}/ { ( C2H4O )p The sum of the formula weights of the oxyethylene group moieties represented by)} is the ratio value Z,
It is a number that satisfies the condition (51/49)≤Z≤(95/5).
However, in X in the formula, a polyether group having a structure where 1≤p and q=r=0 is excluded. }
The inventors have found that the above problems can be solved by a foam enhancer containing a silicone polyether copolymer represented by the following, and have completed the present invention. The suds booster is particularly suitable for use in water-blown polyurethane spray foam systems having specific configurations, and is not limited to specific spray foam systems, to significantly improve the hydrophobicity of polyurethane foams. can be done.
さらに、本発明者らは、上記泡増強剤を含む水発泡型ポリウレタンスプレーフォームシステム用のプレミックス液、これらを含むポリウレタン発泡体形成用組成物、およびこれにより調製される疎水性の向上した軟質ポリウレタン発泡体、Low Emission/Low VOC特性を有する軟質ポリウレタンフォーム、あるいは断熱材/吸音材により、上記課題を好適に解決できることを見出し、本発明に到達した。 Furthermore, the present inventors have discovered premix liquids for water-blown polyurethane spray foam systems containing the above-described foam boosters, polyurethane foam-forming compositions containing them, and hydrophobically enhanced soft foams prepared therefrom. The present inventors have found that the above problems can be satisfactorily solved by a polyurethane foam, a flexible polyurethane foam having Low Emission/Low VOC characteristics, or a heat insulating material/sound absorbing material, and have arrived at the present invention.
本発明によれば、水の添加部数が多く、軟質ウレタンフォーム用ポリオールを用いる建造物断熱用途等に適した現場発泡スプレーフォーム処方向けの、プレミックス系との相溶性に優れ、少量の使用で建造物断熱用途等に適した大容積の発泡体を形成でき、得られる発泡体が微細なセル構造を有し、かつ、得られる発泡体の疎水性を顕著に向上させることができる泡増強剤を提供することができる。また、当該泡増強剤を含有するポリウレタンスプレーフォームシステム用のプレミクス液、ポリウレタンスプレーフォーム形成用組成物を提供する事ができる。 According to the present invention, the number of parts to be added with water is large, and it is suitable for on-site foaming spray foam formulations such as building insulation applications using polyols for flexible urethane foam, excellent compatibility with premix systems, and can be used in small amounts A foam enhancer capable of forming a large-volume foam suitable for building insulation, etc., having a fine cell structure, and significantly improving the hydrophobicity of the resulting foam. can be provided. Further, it is possible to provide a premix liquid for a polyurethane spray foam system and a composition for forming a polyurethane spray foam containing the foam enhancer.
また、本発明により、前記ポリウレタンスプレーフォーム形成用組成物から得られる疎水性の向上した軟質ポリウレタン発泡体およびその用途、特に、Low Emission/Low VOC特性を有する前記軟質ポリウレタン発泡体、これらからなる断熱材又は吸音材を提供する事ができる。 Further, according to the present invention, a flexible polyurethane foam with improved hydrophobicity obtained from the composition for forming polyurethane spray foam and uses thereof, in particular, the flexible polyurethane foam having low emission/low VOC properties, heat insulation comprising these We can provide the material or sound absorbing material.
さらに、本発明により、水発泡ポリウレタンスプレーフォーム以外のウレタンフォーム製造において、フォームの疎水性向上のために前記泡増強剤を利用し、ポリウレタン発泡体の疎水性を顕著に改善する方法を提供することができる。 Furthermore, according to the present invention, in the production of polyurethane foams other than water-blown polyurethane spray foams, there is provided a method for significantly improving the hydrophobicity of polyurethane foams by using the foam enhancer to improve the hydrophobicity of the foams. can be done.
なお、本発明の泡増強剤は、品質と環境適合性に優れていると共に、現在、水発泡スプレーフォーム向けに転用されている軟質スラブフォーム用整泡剤と比較して、低コストでの製造が可能である。従って、本発明により、整泡剤の製造業者は従来よりも低価格で大量に市場に供給する選択肢を持つことができ、一方でプレミクスやフォームシステムの製造業者はcost-in-useと特性に優れたポリウレタンスプレーフォームシステム用のプレミクス液、ポリウレタンスプレーフォーム形成用組成物とを末端顧客や市場に提供することができ、両者ともに、社会及び産業の健全な発展への貢献と適正な利潤の追求とを両立できる自由度が高まる。 In addition, the foam enhancer of the present invention is excellent in quality and environmental compatibility, and can be manufactured at a lower cost than the foam stabilizer for flexible slab foam currently being diverted to water foam spray foam. is possible. Thus, the present invention allows manufacturers of foam stabilizers to have the option of supplying high volumes to the market at lower prices than in the past, while manufacturers of premixes and foam systems We are able to provide end customers and markets with excellent premix liquids for polyurethane spray foam systems and polyurethane spray foam forming compositions, and both contribute to the sound development of society and industry and pursue appropriate profits. The degree of freedom that can be compatible with is increased.
[シリコーンポリエーテル共重合体、およびそれを含む泡増強剤]
まず、本発明にかかる泡増強剤の主要な成分である、シリコーンポリエーテル共重合体について詳細に説明する。前記の通り、本発明は、シリコーンポリエーテル共重合体の化学構造の選択によってウレタンフォームの疎水性が顕著に向上するという予期せぬ発見、および、当該シリコーンポリエーテル共重合体が、特定の構成を有する水発泡型ポリウレタンスプレーフォームシステムにおける使用に、特に適していることを見出したことに基づくものであり、シリコーンポリエーテル共重合体の構造は、本発明の特徴的な構成の一つである。
[Silicone polyether copolymer and foam enhancer containing the same]
First, the silicone polyether copolymer, which is the main component of the foam enhancer according to the present invention, will be described in detail. As described above, the present invention is based on the unexpected discovery that the hydrophobicity of urethane foam is significantly improved by selecting the chemical structure of the silicone polyether copolymer, and that the silicone polyether copolymer has a specific composition. The structure of the silicone polyether copolymer is one of the characteristic features of the present invention. .
より具体的には、本発明にかかるシリコーンポリエーテル共重合体は、下記の一般式(1)で表される。
一般式(1):
Figure JPOXMLDOC01-appb-C000004
More specifically, the silicone polyether copolymer according to the present invention is represented by the following general formula (1).
General formula (1):
Figure JPOXMLDOC01-appb-C000004
一般式(1)において、Xは、各々独立に式:-C2kO-(CO)p(CO)q(CO)r-Yで示される1種類または2種類以上のポリエーテル基を表し、
Yは、100モル%がH基であるか、75モル%以上のH基と25モル%以下のC1~C4アルキル又はアセチル基から選ばれるその他の基からなり、
m、n、k、p、q 、r は以下の条件を満たす数である。
12≦(m+n)≦230、
10≦m、
2≦n、
n≦m、
3≦k≦4、
p、q、rは、Xで表されるポリエーテル基部分の式量が1400~4000の範囲内にあり、
{(CO)qで表されるオキシプロピレン基部分および(CO)rで表されるオキシブチレン基部分の式量の和}/{(CO)pで表されるオキシエチレン基部分の式量の和)}である比の値Zが、
(51/49)≦Z≦(95/5)の条件を満たす数である。
ただし、式中のXにおいて、1≦pかつq=r=0である構造を有するポリエーテル基は含まない。すなわち、式中のXで表されるポリエーテル基部分は、2以上の異なる平均化学構造のポリエーテル鎖の混合体であってよいが、ポリオキシアルキレン部がポリオキシエチレン基のみから構成される基は含まない。後述する通り、本発明におけるポリエーテル部分のオキシエチレン単位由来の部分の割合が高いと、本発明の技術的効果を発揮できないためである。
In general formula (1), each X is independently represented by the formula: -C k H 2k O-(C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r -Y Represents one or more polyether groups,
Y is 100 mol % of H groups, or consists of 75 mol % or more of H groups and 25 mol % or less of other groups selected from C1-C4 alkyl or acetyl groups;
m, n, k, p, q, and r are numbers satisfying the following conditions.
12≦(m+n)≦230,
10≦m,
2≦n,
n≦m,
3≤k≤4,
p, q, and r have a formula weight of the polyether group moiety represented by X in the range of 1400 to 4000,
{sum of the formula weights of the oxypropylene group moiety represented by ( C3H6O )q and the oxybutylene group moiety represented by ( C4H8O )r}/ { ( C2H4O )p The sum of the formula weights of the oxyethylene group moieties represented by)} is the ratio value Z,
It is a number that satisfies the condition (51/49)≤Z≤(95/5).
However, X in the formula does not include a polyether group having a structure where 1≤p and q=r=0. That is, the polyether group portion represented by X in the formula may be a mixture of polyether chains having two or more different average chemical structures, but the polyoxyalkylene portion is composed only of polyoxyethylene groups. It does not contain bases. This is because, as will be described later, the technical effects of the present invention cannot be exhibited if the proportion of the portion derived from oxyethylene units in the polyether portion in the present invention is high.
なお、式量とは化学式や組成式に基づいて原子量と原子数の積の総和を求めた値であるが、ここでは、シリコーンポリエーテル共重合体の反応原料である不飽和基含有ポリエーテル化合物の平均化学構造(主に13Cおよび1Hを核種とする核磁気共鳴分析により同定される構造)に基づいて計算される、Xで表されるポリエーテル基部分、オキシプロピレン基部分、およびオキシエチレン基部分の式量およびそれらの和である。 The formula weight is the sum of the product of the atomic weight and the number of atoms based on the chemical formula and composition formula. calculated based on the average chemical structure (structure identified by nuclear magnetic resonance spectroscopy with mainly 13C and 1H nuclides), the polyether group moiety represented by X, the oxypropylene group moiety, and the oxyethylene group The formula weights of the moieties and their sums.
上記の一般式(1)において、Rは好適には、各々独立に炭素原子数1~10のアルキル基、アリール基、アラルキル基から選択され、メチル、エチル、n-プロピル、n-ブチル、i-ブチル、n-ペンチル、i-ペンチル、2-メチルブチル、n-ヘキシル、n-オクチル等の直鎖状又は分岐状のアルキル基;フェニル基;フェネチル基或いはフェニルイソプロピル基などが例示される。工業的に特に好適には、Rはメチル基である。 In the above general formula (1), each R is preferably independently selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, methyl, ethyl, n-propyl, n-butyl, i linear or branched alkyl groups such as -butyl, n-pentyl, i-pentyl, 2-methylbutyl, n-hexyl and n-octyl; phenyl; phenethyl or phenylisopropyl. Industrially particularly preferred, R is a methyl group.
一般式(1)において、Xはケイ素原子に結合したポリオキシアルキレン構造を有するポリエーテル基であり、式:
-C2kO-(CO)p(CO)q(CO)r-Y
で定義される。ここで、kはケイ素原子に結合するアルキレン基の炭素原子数であり、工業的実用性の面から3≦k≦4であり、k=3がより好ましい。
In the general formula (1), X is a polyether group having a polyoxyalkylene structure bonded to silicon atoms, the formula:
—C k H 2k O—(C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r —Y
defined by Here, k is the number of carbon atoms of the alkylene group bonded to the silicon atom, and from the viewpoint of industrial practicality, 3≦k≦4, more preferably k=3.
Yはポリオキシアルキレン構造の末端基であり、100モル%がH基(水素原子)であるか、75モル%以上のH基と25モル%以下のC1~C4アルキル又はアセチル基から選ばれるその他の基からなる。好適には、Yは100モル%が水素原子である。 Y is a terminal group of a polyoxyalkylene structure, 100 mol% of which is an H group (hydrogen atom), or 75 mol% or more of an H group and 25 mol% or less of a C1-C4 alkyl or acetyl group. consists of the basis of Preferably, Y is 100 mol % hydrogen atoms.
前記のXで表されるポリエーテル基部分において、p、q、rは、ポリオキシアルキレン構造を構成するオキシエチレン単位、オキシプロピレン単位、およびオキシブチレン単位の平均の個数であり、前記X基の式量が1400~4000の範囲内にあり、且つ{(CO)qで表されるオキシプロピレン基部分および(CO)rで表されるオキシブチレン基部分の式量の和}/{(CO)pで表されるオキシエチレン基部分の式量の和)}である比の値Zが、
(51/49)≦Z≦(95/5)の条件を満たす数である。
In the polyether group portion represented by X, p, q, and r are the average number of oxyethylene units, oxypropylene units, and oxybutylene units that constitute the polyoxyalkylene structure, and The formula weights of the oxypropylene group moiety represented by {(C 3 H 6 O) q and the formula weight of the oxybutylene group moiety represented by (C 4 H 8 O) r are within the range of 1400 to 4000. The sum of the ratios}/{the sum of the formula weights of the oxyethylene group moieties represented by (C 2 H 4 O)p)} is
It is a number that satisfies the condition (51/49)≤Z≤(95/5).
ここで、比の値Zが(95/5)を超える値の場合、(CO)qで表されるオキシプロピレン基部分および(CO)rで表されるオキシブチレン基部分に由来する疎水性が過剰となり、シリコーンポリエーテル共重合体によりポリエーテルポリオールと多量の水とを親和させることが困難となり、プレミクス液の安定性不良やフォーム不良を生じやすい傾向にある。逆に、比の値Zが(51/49)未満、すなわち、オキシエチレン単位数が、オキシプロピレン単位およびオキシブチレン単位の和に対して等しいか、より高い比率となる場合、建造物断熱用の現場発泡スプレーフォーム処方で利用される軟質ウレタンフォーム用ポリオールとの相溶性が不十分となり、安定なプレミクス液を得ることが困難となり易く、望ましい整泡効果も得られない結果となり、本発明の技術的効果が達成できなくなる場合がある。なお、Xで表されるポリエーテル基部分は、2以上の異なる平均化学構造のポリエーテル鎖の混合体であってよいが、末端に水酸基を有し且つオキシエチレン部のみから構成されるポリエーテル基を含有することは無い。このような高極性の親水基は前記ポリオールとの相溶性が更に悪いため、不適である。 Here, when the ratio value Z exceeds (95/5), the oxypropylene group moiety represented by (C 3 H 6 O)q and the oxybutylene group represented by (C 4 H 8 O)r Hydrophobicity derived from the base portion becomes excessive, making it difficult for the silicone polyether copolymer to make the polyether polyol and a large amount of water compatible, which tends to cause poor stability of the premix liquid and poor foaming. Conversely, if the value of the ratio Z is less than (51/49), i.e. the number of oxyethylene units is equal or higher than the sum of the oxypropylene and oxybutylene units, then the The compatibility with the polyol for flexible urethane foam used in the on-site foaming spray foam formulation becomes insufficient, and it tends to be difficult to obtain a stable premix liquid, resulting in the failure to obtain the desired foam stabilizing effect. effect may not be achieved. The polyether group portion represented by X may be a mixture of polyether chains having two or more different average chemical structures, but a polyether having terminal hydroxyl groups and composed only of an oxyethylene portion It does not contain any groups. Such highly polar hydrophilic groups are not suitable because they are less compatible with the polyol.
より好適には、X基はオキシブチレン単位を含まず、式:
-CO(CO)p(CO)q-H
で表され、X基の式量が1500~2500の範囲内にあり、前記の比Zが(54/46)≦Z≦(80/20)の条件を満たすものである。
More preferably, the X group does not contain oxybutylene units and has the formula:
—C 3 H 6 O(C 2 H 4 O) p (C 3 H 6 O) q —H
wherein the formula weight of the X group is in the range of 1500 to 2500, and the ratio Z satisfies the condition of (54/46)≦Z≦(80/20).
なお、ポリエーテル基Xに含まれるオキシエチレン単位、オキシプロピレン単位、およびオキシブチレン単位は、ブロック型の共重合体構造をとっても良いしランダム型の共重合体構造をとっても良いが、ランダム型の構造がより好適である。 The oxyethylene units, oxypropylene units, and oxybutylene units contained in the polyether group X may have a block-type copolymer structure or a random-type copolymer structure. is more preferred.
なお、ケイ素原子に結合するアルキレン基であって炭素原子数3~4のもの、オキシプロピレン単位またはオキシブチレン単位を構成するアルキレン部分については、直鎖アルキレン基であっても、イソプロピレン基またはイソブチレン基のような、分岐したイソアルキレン基であってもよい。 As for the alkylene group bonded to the silicon atom and having 3 to 4 carbon atoms, and the alkylene portion constituting the oxypropylene unit or oxybutylene unit, even if it is a linear alkylene group, isopropylene group or isobutylene It may also be a branched isoalkylene group, such as a group.
上記の一般式(1)において、m,nは、側鎖(Rake)型シリコーンポリエーテル共重合体の各シロキサン単位の重合度であり、12≦(m+n)≦230、10≦m、2≦n、n≦mの範囲の数である。特に、40≦m≦90,2≦n≦8の範囲の数であることが好ましい。 In the general formula (1) above, m and n are degrees of polymerization of each siloxane unit of the side chain (Rake) type silicone polyether copolymer, and 12 ≤ (m + n) ≤ 230, 10 ≤ m, 2 ≤ n, a number in the range n≦m. In particular, the numbers are preferably in the range of 40≦m≦90 and 2≦n≦8.
本発明に係るシリコーンポリエーテル共重合体は、上記の構造(特に、好適な構造)の選択により、
i)軟質ウレタンフォーム用ポリオールとの相溶性に優れ、安定したプレミックス溶液を形成できる
ii)発泡性に優れ、建造物の製造現場において、少量の使用であっても大容積の発泡体(=フォーム体積)を形成できるため、建造物用途等におけるコスト面、作業効率に優れる
iii)得られる発泡体が微細なセル構造を有し、断熱材/吸音材等の用途に適合している
iv)従来の泡増強剤に比して、ポリウレタン発泡体(特に、軟質ポリウレタンフォーム)の疎水性を顕著に改善可能である
という、従来技術にはない主要な利点を兼ね備え、かつ、近年、特に建造物用途における重要度が高い、Low Emission/Low VOCの要求を充足できるものである。
The silicone polyether copolymer according to the present invention has a
i) Excellent compatibility with polyols for flexible urethane foam, and can form a stable premix solution
ii) It has excellent foamability and can form a large-volume foam (= foam volume) at a building manufacturing site even if it is used in a small amount, so it is excellent in terms of cost and work efficiency in building applications.
iii) The resulting foam has a fine cell structure and is suitable for use as a heat insulator/sound absorber.
iv) Combined with the major advantage not found in the prior art of being able to significantly improve the hydrophobicity of polyurethane foams (especially flexible polyurethane foams) compared to conventional foam enhancers, and It satisfies the requirements of Low Emission/Low VOC, which are of high importance in building applications.
具体的には、上記の好適なシリコーンポリエーテル共重合体にあっては、ポリエーテル部全体の式量に対して、オキシプロピレン単位或いはオキシブチレン単位由来の親油部分の割合が高いため、建造物断熱用の現場発泡スプレーフォーム処方で利用される軟質ウレタンフォーム用ポリオールとの相溶性に優れる。従って、プレミックス液の安定性向上による利便性拡大、大きなフォーム体積や微細セル構造の付与などの望ましい整泡効果を得る上で有利となる。 Specifically, in the preferred silicone polyether copolymer described above, since the ratio of the lipophilic portion derived from the oxypropylene unit or the oxybutylene unit is high with respect to the formula weight of the entire polyether portion, Excellent compatibility with polyols for flexible urethane foam used in on-site spray foam formulations for thermal insulation. Therefore, it is advantageous in obtaining desirable foam-stabilizing effects such as expansion of convenience due to improved stability of the premix liquid and provision of a large foam volume and a fine cell structure.
また、上記の好適なシリコーンポリエーテル共重合体は、ポリエーテル部全体の式量に対して、オキシエチレン単位由来の部分の割合が低いことから、低温下でも固化を起こすことがなく、粘度もあまり高くなり過ぎず、製造後のハンドリング性も改善される。更に、上記の好適なシリコーンポリエーテル共重合体を前記スプレーフォームの整泡剤として使用すると、泡増強効果に加えて得られたウレタンフォームの疎水性を顕著に向上することができる。 In addition, since the proportion of the portion derived from oxyethylene units is low with respect to the formula weight of the entire polyether portion, the preferred silicone polyether copolymer described above does not solidify even at low temperatures, and has a low viscosity. It does not become too high, and the handleability after production is also improved. Furthermore, the use of the above preferred silicone polyether copolymer as a foam stabilizer for the spray foam can remarkably improve the hydrophobicity of the obtained urethane foam in addition to the foam enhancing effect.
[シリコーンポリエーテル共重合体の合成]
このようなシリコーンポリエーテル共重合体は、分子鎖の片末端にアルケニル基を有するポリエーテル化合物とオルガノハイドロジェンポリシロキサンを任意の溶媒の存在下または不存在下でヒドロシリル化反応させる公知の方法により合成することができる。
[Synthesis of silicone polyether copolymer]
Such a silicone polyether copolymer can be obtained by a known method of hydrosilylating a polyether compound having an alkenyl group at one end of the molecular chain and an organohydrogenpolysiloxane in the presence or absence of any solvent. Can be synthesized.
好適には、本発明にかかるシリコーンポリエーテル共重合体は、下記一般式(1H):
Figure JPOXMLDOC01-appb-C000005
{式中、Rは前記と同様の定義であり、m,nは前記と同様の数である}で表されるオルガノハイドロジェンポリシロキサン、
下記一般式(2):
2k-1O-(CO)p(CO)q(CO)r-Y
{式中、k、p、q及びrは前記と同様の数であり、Yは前記と同様の定義であり、C2k-1は炭素-炭素二重結合を有する直鎖または分岐鎖状のアルケニル基である}で示される分子鎖の片末端にアルケニル基を有するポリエーテル化合物とのヒドロシリル化反応により得られた、シリコーンポリエーテル共重合体である。
Preferably, the silicone polyether copolymer according to the invention has the following general formula (1H):
Figure JPOXMLDOC01-appb-C000005
an organohydrogenpolysiloxane represented by {wherein R has the same definition as above, and m and n are the same numbers as above};
The following general formula (2):
C k H 2k-1 O—(C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r —Y
{Wherein, k, p, q and r are the same numbers as above, Y is the same definition as above, and C k H 2k-1 is a straight or branched chain having a carbon-carbon double bond It is a silicone polyether copolymer obtained by a hydrosilylation reaction with a polyether compound having an alkenyl group at one end of the molecular chain represented by }.
この際、一般式(2)で表されるポリエーテル化合物に含まれるオキシエチレン単位、オキシプロピレン単位、およびオキシブチレン単位は、ブロック型の共重合体構造をとっても良いしランダム型の共重合体構造をとっても良いが、ランダム型の構造が好適である。また、2種類以上の異なる前記ポリエーテル化合物を、前記オルガノハイドロジェンポリシロキサンと反応させることにより、本発明にかかるシリコーンポリエーテル共重合体を得ることもできるが、1≦p且つq=r=0の構造体:すなわちポリオキシアルキレン部がポリオキシエチレン部のみから構成されるポリエーテル化合物は含まない。この理由としては、末端に水酸基を有し且つオキシエチレン部のみから構成されるポリエーテル基は極性が強過ぎるため、建造物断熱用の現場発泡スプレーフォーム処方で利用される軟質ウレタンフォーム用ポリオールとの相溶性を阻害する結果、安定なプレミクス液を得ることが困難となり易く、望ましい整泡効果も損なわれるためである。 At this time, the oxyethylene units, oxypropylene units, and oxybutylene units contained in the polyether compound represented by the general formula (2) may have a block-type copolymer structure or a random-type copolymer structure. can be taken, but a random type structure is preferred. The silicone polyether copolymer according to the present invention can also be obtained by reacting two or more different polyether compounds with the organohydrogenpolysiloxane. Structure of 0: Does not include polyether compounds in which the polyoxyalkylene portion is composed only of the polyoxyethylene portion. The reason for this is that polyether groups having terminal hydroxyl groups and consisting only of oxyethylene moieties have too strong a polarity, so that polyols for flexible urethane foams used in on-site expansion spray foam formulations for building insulation cannot be used. This is because, as a result of hindering the compatibility of , it is likely to be difficult to obtain a stable premix liquid, and the desirable foam-stabilizing effect is also impaired.
上記のヒドロシリル化反応を行う際に、[前記ポリエーテル化合物中の炭素-炭素二重結合の物質量/前記オルガノハイドロジェンポリシロキサン中の珪素結合水素原子の物質量]の比は1.0~2.0となる範囲が例示できる。すなわち、本発明に係るシリコーンポリエーテル共重合体を合成する場合には、ポリエーテル化合物を過剰量使用することが好ましい。より具体的には、上記の比が、1.05~1.75となる範囲が好ましく、1.20~1.60となる範囲がより好ましい。この理由は、前記ポリエーテル化合物の末端アルケニル基は、一般にヒドロシリル化反応中に一部が内部転移を起こし反応に関与しなくなるため、珪素結合水素原子を完全に消費するには、アルケニル基のモル比を過剰としておく必要があるためである。従って、かかるシリコーンポリエーテル共重合体は、一般に、生成物であるシリコーンポリエーテル共重合体と未反応のポリエーテル化合物との混合物として得られ、本発明に係る一般式(1)で表されるシリコーンポリエーテル共重合体を含有する疎水性向上効果を有する泡増強剤を構成する。 When carrying out the above hydrosilylation reaction, the ratio of [substance amount of carbon-carbon double bonds in the polyether compound/substance amount of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane] is 1.0 to A range of 2.0 can be exemplified. That is, when synthesizing the silicone polyether copolymer according to the present invention, it is preferable to use an excessive amount of the polyether compound. More specifically, the above ratio is preferably in the range of 1.05 to 1.75, more preferably in the range of 1.20 to 1.60. The reason for this is that a portion of the terminal alkenyl groups of the polyether compound undergoes internal transfer during the hydrosilylation reaction and ceases to participate in the reaction. This is because it is necessary to keep the ratio excessive. Therefore, such a silicone polyether copolymer is generally obtained as a mixture of the product silicone polyether copolymer and an unreacted polyether compound, and is represented by general formula (1) according to the present invention. A foam enhancer having a hydrophobicity-improving effect containing a silicone polyether copolymer is constituted.
なお、これらの成分は互いに相溶性に優れるため、前記シリコーンポリエーテル共重合体を含有する疎水性向上効果を有する泡増強剤は、通常、透明乃至ほぼ透明な均一液体として得られる。なお、一般式(2)で表されるポリエーテル化合物は、工業的にはアリルアルコールやアリルグリコール等の不飽和アルコールを出発物質とし、アルカリ触媒存在下にエチレンオキシドとプロピレンオキシド等を付加重合することにより製造されるのが通常であるが、反応系からの水分除去のレベルに応じ、不純物としての両末端ジオール体を含む場合がある。従って、このような両末端ジオール体:例えばPEG/PPG共重合体が、本発明に係る泡増強剤に更に含有されていてもよい。 Since these components are highly compatible with each other, the foam enhancer containing the silicone polyether copolymer and having the effect of improving hydrophobicity is usually obtained as a transparent or almost transparent homogeneous liquid. Industrially, the polyether compound represented by the general formula (2) is produced by addition polymerization of ethylene oxide, propylene oxide, etc. in the presence of an alkali catalyst using an unsaturated alcohol such as allyl alcohol or allyl glycol as a starting material. However, depending on the level of water removal from the reaction system, it may contain diols at both ends as impurities. Therefore, such a double-ended diol compound, such as a PEG/PPG copolymer, may be further contained in the foam enhancer according to the present invention.
上記のヒドロシリル化反応を行う際に、前記ポリエーテル化合物或いは前記オルガノハイドロジェンポリシロキサンに元々含まれる微量不純物や経時劣化による副生成物、反応装置内の微量汚染物などの影響により、反応の進行が遅くなる場合があり得る。このような場合、触媒の追加、反応温度を通常よりも若干高くする、反応時間を延長する、あるいは原料間の相溶性を向上させる目的で反応溶媒を追加するなどの適切な措置を講じ、反応系の残存Si-H基が検出限界以下となるまで工程を管理することが望ましい。Si-H基の残存は、前記泡増強剤をプレミクス系に配合した際、可燃性水素ガスの発生をもたらす恐れがあること、またある量を超えるSi-H基の残存は、一般にウレタンフォーム用整泡剤として使用されるシリコーンポリエーテル共重合体の整泡性能を劣化させることが知られていることから、Si-H基の残存量は、前記泡増強剤の概ね30wt.ppm以下であることが好ましく、10wt.ppm以下であることが更に好ましく、2.5wt.ppm以下であることが特に好ましい。なお、こうした微量Si-H基を一部に含有するシリコーンポリエーテル共重合体は、文面上は前記一般式(1)によっては表現されていないが、工業上は実質的に同種のものとして、本発明に包含される。 When performing the above hydrosilylation reaction, the progress of the reaction may be affected by trace impurities originally contained in the polyether compound or the organohydrogenpolysiloxane, by-products due to deterioration over time, and trace contaminants in the reactor. may be delayed. In such a case, appropriate measures such as adding a catalyst, raising the reaction temperature slightly higher than usual, extending the reaction time, or adding a reaction solvent for the purpose of improving the compatibility between the raw materials may be taken to prevent the reaction. It is desirable to control the process until the residual Si—H groups in the system are below the detection limit. Remaining Si—H groups may cause the generation of combustible hydrogen gas when the foam enhancer is blended into a premix system. Since it is known to deteriorate the foam stabilizing performance of silicone polyether copolymers used as foam stabilizing agents, the residual amount of Si—H groups should be approximately 30 wt. ppm or less, and 10 wt. ppm or less, and 2.5 wt. ppm or less is particularly preferred. Incidentally, the silicone polyether copolymer partially containing such a small amount of Si—H groups is not represented by the general formula (1) on the text, but industrially, it is considered to be substantially the same type. Included in the present invention.
ここで、反応溶媒は必要ない場合も多いが、一般的な有機溶媒を使用する場合、トルエン、キシレンなどの芳香族炭化水素系溶剤やイソプロピルアルコールなどのアルコール系溶剤;シクロヘキサン、n-ヘプタン、メチルシクロヘキサンなどの脂肪族飽和炭化水素系溶剤から選択することが、工業生産上は好ましい。一般に、これら高揮発性反応溶媒は、ヒドロシリル化反応が終了するなどその役目を終え次第、ストリピング処理によって生成系から除去する必要がある。この中で、トルエンとキシレンは所謂BTX溶媒に属し、かねてより整泡剤として利用されるシリコーンポリエーテル共重合体の製造に広く使用されてきたが、当該BTX溶媒を不含とすることが特に生産機スケールにおいては困難であるため、厳しいBTX管理を要求される現在のポリウレタン産業界のニーズに応えることはできない。そのため、必要な場合にはイソプロピルアルコール又は平均炭素原子数が6~11の範囲にある飽和炭化水素溶媒の中から、コストや安全性、生産時の利便性等を考慮し、適当なものを選択して使用することが望ましい。 Here, a reaction solvent is often not necessary, but when using a general organic solvent, aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as isopropyl alcohol; cyclohexane, n-heptane, methyl Selection from aliphatic saturated hydrocarbon solvents such as cyclohexane is preferred for industrial production. In general, these highly volatile reaction solvents need to be removed from the product system by stripping as soon as they have completed their role, such as the completion of the hydrosilylation reaction. Among them, toluene and xylene belong to the so-called BTX solvents and have been widely used for the production of silicone polyether copolymers used as foam stabilizers. Since it is difficult on a production machine scale, it cannot meet the needs of the current polyurethane industry, which requires strict BTX management. Therefore, if necessary, select an appropriate one from isopropyl alcohol or a saturated hydrocarbon solvent with an average number of carbon atoms in the range of 6 to 11, considering cost, safety, convenience during production, etc. It is desirable to use
このような平均炭素原子数が6~11の範囲にある飽和炭化水素溶媒の具体例としては、メチルシクロヘキサン、n-ヘプタン、ヘプタン混合物、ヘプタン(商業用グレード)、イソオクタン、2,2,4-トリメチルペンタン、オクタン混合物、エチルシクロヘキサン、ジメチルシクロヘキサン、n-ヘキサン、イソヘキサン、ヘキサン混合物、シクロヘキサン、2-メチルペンタン、2-メチルヘプタン、3-メチルヘプタン、Isopar E(C7-C9飽和炭化水素混合物)、Isopar C(C7-C8飽和炭化水素混合物)、IP solvent 1016(C6-C9飽和炭化水素混合物),Isopar G(C10-C11飽和炭化水素混合物)などが挙げられる。この中では、メチルシクロヘキサン、n-ヘプタン、ヘプタン混合物、ヘプタン(商業用グレード)に代表されるC7飽和炭化水素が好ましい。 Specific examples of such saturated hydrocarbon solvents having an average number of carbon atoms in the range of 6 to 11 include methylcyclohexane, n-heptane, heptane mixtures, heptane (commercial grade), isooctane, 2,2,4- trimethylpentane, octane mixture, ethylcyclohexane, dimethylcyclohexane, n-hexane, isohexane, hexane mixture, cyclohexane, 2-methylpentane, 2-methylheptane, 3-methylheptane, Isopar E (C7-C9 saturated hydrocarbon mixture), Isopar C (C7-C8 saturated hydrocarbon mixture), IP solvent 1016 (C6-C9 saturated hydrocarbon mixture), Isopar G (C10-C11 saturated hydrocarbon mixture) and the like. Among these, C7 saturated hydrocarbons typified by methylcyclohexane, n-heptane, heptane mixtures, and heptane (commercial grade) are preferred.
本発明にかかる泡増強剤は、さらに、任意で希釈剤h´)25℃で液状のポリアルキレングリコールまたはその誘導体を含んでもよい。かかる成分h´)を用いることで、整泡剤または界面活性剤としての機能に悪影響を及ぼすことなく、本発明の泡増強剤の粘度等を調整し、使用時の利便性、取扱作業性(ハンドリング)を改善できる場合がある。また、成分h´)は、ポリウレタン発泡体形成組成物における水酸基価の調整、すなわちポリウレタン発泡体の架橋密度や強度など各種物性コントロールの目的で、前記泡増強剤に追加して使用できる場合がある。 The foam booster according to the invention may additionally optionally comprise a diluent h') a polyalkylene glycol or derivative thereof which is liquid at 25°C. By using such component h'), the viscosity and the like of the foam enhancer of the present invention can be adjusted without adversely affecting the function as a foam stabilizer or surfactant, and convenience during use and handling workability ( handling) can be improved. In addition, component h') may be used in addition to the foam enhancer for the purpose of adjusting the hydroxyl value in the polyurethane foam-forming composition, that is, controlling various physical properties such as the crosslink density and strength of the polyurethane foam. .
ヒドロシリル化反応用の触媒は、ヒドロシリル化反応を促進することができる限り特定のものに限定されない。ヒドロシリル化反応触媒として、これまでに多くの金属及び化合物が知られており、それらの中から適宜選択して本発明にかかる成分e)の製造に用いることができる。ヒドロシリル化反応触媒の例として、具体的には、シリカ微粉末又は炭素粉末担体上に吸着させた微粒子状白金、塩化白金酸、アルコール変性塩化白金酸、スパイヤー触媒、塩化白金酸のオレフィン錯体、塩化白金酸とビニルシロキサンの配位化合物、カールシュタット触媒、白金黒、パラジウム、及びロジウム触媒を挙げることができる。これらの触媒は、定法に従ってトルエン、キシレン、触媒の配位子化合物、アルコール類、他の適当な極性溶媒、反応用原料であるポリエーテルや希釈剤等に溶解或は分散させて反応系に投入することができる。 The catalyst for the hydrosilylation reaction is not particularly limited as long as it can promote the hydrosilylation reaction. As a hydrosilylation reaction catalyst, many metals and compounds have been known so far, and a suitable one can be selected from them and used for the production of the component e) according to the present invention. Specific examples of hydrosilylation reaction catalysts include particulate platinum adsorbed on a silica fine powder or carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, Speyer's catalyst, olefin complex of chloroplatinic acid, chloride Coordination compounds of platinic acid and vinyl siloxanes, Karstadt catalysts, platinum black, palladium, and rhodium catalysts may be mentioned. These catalysts are dissolved or dispersed in toluene, xylene, ligand compounds of catalysts, alcohols, other suitable polar solvents, raw materials for reaction such as polyethers and diluents, etc., according to standard methods, and introduced into the reaction system. can do.
ヒドロシリル化反応用触媒の使用量は、有効量であり、本発明にかかる泡増強剤の主成分であるシリコーンポリエーテル共重合体の合成反応を促進する量であれば特に限定されない。具体的には、前記一般式(1H)で表されるオルガノハイドロジェンポリシロキサンと前記一般式(2)で表される、分子鎖の片方の末端にアルケニル基を有するポリエーテル化合物の和(全体を100質量%とする)に対して、この触媒中の金属原子が質量単位で0.5~100ppm、好適には白金金属原子が、3~30ppmの範囲内となる量である。ヒドロシリル化反応用触媒の含有量が上記範囲の下限未満であると、付加反応が不十分となる場合があり、上記範囲の上限を超えると、不経済であり、かつ、得られる本発明組成物の着色等、透明性に悪影響を及ぼす場合がある。 The amount of hydrosilylation reaction catalyst used is an effective amount, and is not particularly limited as long as it is an amount that promotes the synthesis reaction of the silicone polyether copolymer, which is the main component of the foam enhancer according to the present invention. Specifically, the sum (total 100% by mass), the amount of metal atoms in the catalyst is 0.5 to 100 ppm, preferably 3 to 30 ppm by mass of platinum metal atoms. If the content of the hydrosilylation reaction catalyst is less than the lower limit of the above range, the addition reaction may be insufficient. may have an adverse effect on transparency, such as coloring of
ヒドロシリル化反応の条件は、原料の種類や及び溶媒の有無に応じ、任意に選択することができる。例えば、トコフェロール(ビタミンE)等の抗酸化剤を少量添加し、窒素等の不活性ガス雰囲気下で室温~120℃、好適には50~100℃で一定時間加熱攪拌することにより反応を完結できる。なお、抗酸化剤はヒドロシリル化の終了後に添加しても良い。反応時間は、反応スケール、触媒の使用量および反応温度に応じて選択可能であり、数分~数時間の範囲であることが一般的である。また、反応は、品質改善や生産性の向上等を目的として減圧下で行ってもよいし、バッチプロセスだけでなく公知の半連続乃至は連続生産プロセスも適用可能である。 Conditions for the hydrosilylation reaction can be arbitrarily selected according to the type of raw materials and the presence or absence of a solvent. For example, the reaction can be completed by adding a small amount of an antioxidant such as tocopherol (vitamin E) and heating and stirring for a certain period of time at room temperature to 120°C, preferably 50 to 100°C, in an inert gas atmosphere such as nitrogen. . The antioxidant may be added after hydrosilylation is completed. The reaction time can be selected according to the reaction scale, amount of catalyst used and reaction temperature, and is generally in the range of several minutes to several hours. In addition, the reaction may be carried out under reduced pressure for the purpose of improving quality and productivity, and not only a batch process but also a known semi-continuous or continuous production process can be applied.
なお、ヒドロシリル化反応の終点は、赤外線分光法(IR)によるSi-H結合吸収の消失あるいは以下のアルカリ分解ガス発生法により、水素ガス発生がなくなったことで確認することができる。なお反応原料であるオルガノハイドロジェンポリシロキサン中のケイ素原子結合水素原子(Si-H)を、同方法により分析することで、水素ガス発生量を特定することもできる。 The end point of the hydrosilylation reaction can be confirmed by the disappearance of Si—H bond absorption by infrared spectroscopy (IR) or the disappearance of hydrogen gas generation by the following alkaline decomposition gas generation method. The amount of hydrogen gas generated can also be determined by analyzing silicon-bonded hydrogen atoms (Si—H) in the organohydrogenpolysiloxane, which is the reaction raw material, by the same method.
なお、アルカリ分解ガス発生法とは、試料をトルエン又はIPAに溶解した溶液と、28.5質量%苛性カリのエタノール/水混合溶液を室温で反応させ、発生する水素ガスを捕集管に集めてその体積を測定する方法である。 In the alkali decomposition gas generation method, a solution obtained by dissolving a sample in toluene or IPA and a mixed solution of 28.5% by mass of caustic potash in ethanol/water are allowed to react at room temperature, and the generated hydrogen gas is collected in a collection tube. It is a method of measuring the volume.
また、本発明にかかる泡増強剤の主成分であるシリコーンポリエーテル共重合体は、末端水酸基を有するポリエーテル基により変性された構造であるため、ヒドロシリル化反応中の副反応:脱水素反応とアセタール形成の抑制が重要である。触媒として塩化白金酸又はその溶液を使用する場合には、主反応の開始前に酢酸カリウム、プロピオン酸カリウム、酢酸ナトリウム等のカルボン酸アルカリ金属塩に代表される緩衝剤を適量、反応系に添加しておくとよい。これらは、固体(粉末)のまま反応系に添加すること、メタノール等の極性溶媒に溶解又は分散させてから反応系に添加すること、予め一般式(2)で表される分子鎖の片方の末端にアルケニル基を有するポリエーテル化合物中に溶解又は分散させておくこと等により効果を発揮させること、何れもが可能である。一般に、これらの副反応が生ずると反応系が増粘し、ひどい場合にはゲル化に至る場合もある。このような事態を軽減する上で、反応溶媒の使用が有効である。緩衝剤の添加タイミングは、ヒドロシリル化反応(主反応)の開始前が望ましいが、主反応終了後の添加であっても、後工程のストリピング中や製造後のアセタール形成反応の抑制に対し、ある程度の効果がある。但し、緩衝剤の添加量が多すぎると主反応の進行が遅くなる、或いはストリピング工程中でシリコーン主鎖切断に始まる別の副反応を誘発し易くなるため、注意が必要である。緩衝剤の最適な添加量は、系内の酸の量を丁度中和できる量か、それよりも若干過剰量である。 In addition, since the silicone polyether copolymer, which is the main component of the foam enhancer according to the present invention, has a structure modified by a polyether group having a terminal hydroxyl group, a side reaction during the hydrosilylation reaction: dehydrogenation and Suppression of acetal formation is important. When chloroplatinic acid or a solution thereof is used as a catalyst, an appropriate amount of a buffering agent represented by alkali metal carboxylates such as potassium acetate, potassium propionate and sodium acetate is added to the reaction system before the start of the main reaction. It is better to keep These may be added to the reaction system as solids (powder), dissolved or dispersed in a polar solvent such as methanol and then added to the reaction system, or may be added to the reaction system in advance by It is possible to exhibit the effect by dissolving or dispersing it in a polyether compound having an alkenyl group at its end. Generally, when these side reactions occur, the reaction system thickens, and in severe cases, gelation may occur. Use of a reaction solvent is effective in reducing such a situation. The timing of adding the buffer is preferably before the start of the hydrosilylation reaction (main reaction). has the effect of However, if the amount of buffering agent added is too large, the progress of the main reaction will be slowed down, or other side reactions that start with the cleavage of the silicone main chain during the stripping process will easily occur, so care must be taken. The optimum amount of buffering agent to be added is the amount just enough to neutralize the amount of acid in the system, or a slight excess.
本発明にかかる泡増強剤は、空気中の酸素により徐々に酸化され、変質する場合がある。これを防止するためフェノール類、ヒドロキノン類、ベンゾキノン類、芳香族アミン類、又はビタミン類等の酸化防止剤を入れ、酸化安定性を増加させることができ、かつ好ましい。このような酸化防止剤として、例えば、前述のビタミンEの他、BHT(2,6-ジ-t-ブチル-p-クレゾール)、ビタミンCなどを用いてもよい。但し、ポリウレタンフォームからのEmissionを低減させる観点からは、ビタミンEやその他の高分子量タイプの酸化防止剤を選択することが重要である。このとき、使用する酸化防止剤の添加量は、その質量において成分e)に対し10~1000ppm、好ましくは50~500ppmとなる範囲である。 The foam enhancer according to the present invention may be gradually oxidized by oxygen in the air and deteriorate. In order to prevent this, an antioxidant such as phenols, hydroquinones, benzoquinones, aromatic amines, or vitamins can be added to increase the oxidation stability, which is preferable. As such an antioxidant, for example, in addition to vitamin E described above, BHT (2,6-di-t-butyl-p-cresol), vitamin C, and the like may be used. However, from the viewpoint of reducing Emission from polyurethane foam, it is important to select vitamin E and other high-molecular-weight antioxidants. At this time, the amount of the antioxidant used is in the range of 10 to 1000 ppm, preferably 50 to 500 ppm, based on the weight of component e).
[低分子シロキサンの低減]
本発明にかかる泡増強剤は、ケイ素原子数が20以下の低分子シロキサンの含有量が5000ppm(重量)以下であることが好ましく、2000ppm(重量)以下が特に好ましい。この値が5000ppmを超えると、前記泡増強剤をポリウレタン発泡体用の整泡剤として用いた場合、ポリウレタンフォームが設置された場所の周辺部材を汚染し、電気・電子装置の接点障害を引き起こす可能性がある。かかる低分子シロキサンとしては、環状のものと直鎖状のものがあり、例えば、式、[(CH3)2SiO]n(式中、nは3~10の整数である。)で表される環状ジメチルシロキサン、および式、CH3[(CH3)2SiO]mSi(CH3)3(式中、mは1~10の整数である。)で表される直鎖状ジメチルシロキサンオリゴマーがあり、また、これらのメチル基の一部が他の有機基で置換されたものがある。かかる低分子シロキサンのより具体的な例としては、オクタメチルテトラシロキサン、デカメチルペンタシクロシロキサン、両末端トリメチルシロキシ基封鎖ジメチルシロキサンオリゴマーが例示される。かかる低分子シロキサンの含有量は、例えば、ガスクロマトグラフィ分析装置を用いて、分析することにより測定できる。低分子シロキサンの低減の方法は限定されないが、工業的には通常ストリピング操作によりこれを行うため、本発明にかかるシリコーンポリエーテル共重合体/泡増強剤の原料であるオルガノハイドロジェンポリシロキサンを予め精製し、低分子シロキサンを除去しておくことが望ましい。或は、ヒドロシリル化反応中、乃至は反応終了後に低分子シロキサンを除去してもよい。
[Reduction of low-molecular-weight siloxane]
In the foam enhancer according to the present invention, the content of low-molecular-weight siloxane having 20 or less silicon atoms is preferably 5000 ppm (weight) or less, particularly preferably 2000 ppm (weight) or less. If this value exceeds 5,000 ppm, when the foam enhancer is used as a foam stabilizer for polyurethane foam, it may contaminate the surrounding members where the polyurethane foam is installed and cause contact failure in electrical and electronic devices. have a nature. Such low-molecular-weight siloxanes include cyclic ones and straight-chain ones. dimethylsiloxane and linear dimethylsiloxane oligomers represented by the formula CH3[(CH3)2SiO]mSi(CH3)3, where m is an integer from 1 to 10; Some methyl groups are partially substituted with other organic groups. More specific examples of such low-molecular-weight siloxanes include octamethyltetrasiloxane, decamethylpentacyclosiloxane, and both-terminal trimethylsiloxy group-blocked dimethylsiloxane oligomers. The content of such low-molecular-weight siloxane can be measured by analysis using, for example, a gas chromatography analyzer. Although the method for reducing low-molecular-weight siloxane is not limited, it is usually done industrially by a stripping operation. Purification to remove low-molecular-weight siloxanes is desirable. Alternatively, the low-molecular-weight siloxane may be removed during the hydrosilylation reaction or after completion of the reaction.
[水発泡型ポリウレタンスプレーフォームシステム]
本発明の上記のシリコーンポリエーテル共重合体を含有する泡増強剤は、以下のa)~d)を含む水発泡型ポリウレタンスプレーフォームシステムに適用される。
a)分子内の平均水酸基数が2~4であり、オキシプロピレン基からなる繰り返し単位を有し、数平均分子量が1000~6000の範囲内にある、1種類以上のポリエーテルポリオール、
b)ポリイソシアネート、
c)硬化触媒、
d)水である発泡剤 同システム中の成分a)であるポリエーテルポリオールおよびその他のポリオール成分の和 100質量部に対して10~40質量部の範囲
[Water-blown polyurethane spray foam system]
The foam booster containing the above silicone polyether copolymer of the present invention is applied to a water-blown polyurethane spray foam system comprising a) to d) below.
a) one or more polyether polyols having an average number of hydroxyl groups in the molecule of 2 to 4, having repeating units composed of oxypropylene groups, and having a number average molecular weight in the range of 1000 to 6000;
b) polyisocyanates,
c) a curing catalyst,
d) Foaming agent that is water Sum of polyether polyol and other polyol components as component a) in the same system Range of 10 to 40 parts by mass per 100 parts by mass
さらに、上記の水発泡型ポリウレタンスプレーフォームシステムは、a´) 成分a)であるポリエーテルポリオール以外の、少なくとも1つ以上のポリオール成分 を含有してもよい。なお、この場合、d)水である発泡剤は、前記の成分a)および成分a´)との和(=合計量)100質量部に対して10~40質量部の添加部数である。 Furthermore, the water-blown polyurethane spray foam system described above may contain at least one or more polyol components other than a') component a) polyether polyol. In this case, d) the blowing agent, which is water, is added in an amount of 10 to 40 parts by mass per 100 parts by mass of the sum (=total amount) of component a) and component a').
さらに、上記の水発泡型ポリウレタンスプレーフォームシステムは、その実用上、本発明の技術的効果を損なわない範囲で、任意選択により、f) ノニオン性の界面活性剤(本発明に係るシリコーンポリエーテル共重合体に該当しない、有機系界面活性剤および乳化剤を含む)、g)難燃剤、h)その他の添加剤:例えば、本発明に係る泡増強剤以外のウレタンフォーム用整泡剤、希釈剤、鎖伸長剤、架橋剤、副次的な量の非水発泡剤、セル開放剤、充填剤、強化剤、顔料、染料、着色剤、抗酸化剤、抗オゾン剤、紫外線安定化剤、静電気防止剤、殺菌剤および抗菌剤等を含んでもよい。以下、これらの成分について解説する。 Furthermore, the water-blown polyurethane spray foam system described above may optionally include f) a nonionic surfactant (silicone polyether covalent agent according to the present invention) as long as it does not impair the technical effects of the present invention. including organic surfactants and emulsifiers that do not correspond to polymers), g) flame retardants, h) other additives: for example, foam stabilizers for urethane foam other than the foam enhancer according to the present invention, diluents, Chain extenders, crosslinkers, secondary amounts of non-aqueous blowing agents, cell openers, fillers, reinforcing agents, pigments, dyes, colorants, antioxidants, antiozonants, UV stabilizers, antistatic agents, bactericides and antibacterials, and the like. These components are explained below.
[a)ポリエーテルポリオール]
本発明で使用されるa)成分は、平均の水酸基数が2~4でオキシプロピレン繰り返し単位を有し、数平均分子量が1000~6000のポリエーテルポリオールの1種以上である。このようなポリオールは、軟質スラブフォームなど一般的な軟質ウレタンフォームに利用できるものであり、水や1分子中に平均で2~4の水酸基を有する多価アルコールを出発原料として、それらにアルキレンオキシドを付加重合して製造されている。例えば、水;エチレングリコール;ジエチレングリコール;プロピレングリコール;ジプロピレングリコール;ブチレングリコール;ペンタンジオール;ヘキサンジオール;ネオペンチルグリコール;グリセリン;トリメチロールプロパン;アンモニア;トリエタノールアミン;トリイソプロパノールアミン;ペンタエリスリトール;ジグリセリン;エチレンジアミン;芳香族ジアミンなどのアルキレンオキシド付加物を含むポリオキシアルキレンポリオールが挙げられる。ポリオキシアルキレンポリオールの製造に用いるアルキレンオキシドは、普通炭素数が2~4であり、プロピレンオキシド及びプロピレンオキシドとエチレンオキシドの混合物が好適である。これらのポリオールは、一種単独で用いても二種以上を併用してもよい。例えば、2官能性物質と3~4官能性物質との混合物および(または)分子量の異なるあるいは化学組成の異なる物質が混合使用できる。なお、ポリウレタンフォームにLow Emission特性を付与する観点からは、ポリオールに含まれる添加剤(例えば酸化防止剤や安定剤)は揮発性のない高分子量タイプを選択することが重要である。
[a) polyether polyol]
Component a) used in the present invention is one or more polyether polyols having an average number of hydroxyl groups of 2 to 4, oxypropylene repeating units, and a number average molecular weight of 1,000 to 6,000. Such polyols can be used for general flexible urethane foams such as flexible slab foams. Water or a polyhydric alcohol having an average of 2 to 4 hydroxyl groups in one molecule is used as a starting material, and an alkylene oxide is added to them. is produced by addition polymerization. Diethylene glycol; Propylene glycol; Dipropylene glycol; Butylene glycol; Pentanediol; Hexanediol; Neopentyl glycol; Glycerin; ethylene diamine; polyoxyalkylene polyols including alkylene oxide adducts such as aromatic diamines. Alkylene oxides used in the production of polyoxyalkylene polyols usually have 2 to 4 carbon atoms, and propylene oxide and mixtures of propylene oxide and ethylene oxide are preferred. These polyols may be used alone or in combination of two or more. For example, mixtures of bifunctional and tri- to tetra-functional substances and/or mixtures of substances with different molecular weights or different chemical compositions can be used. From the viewpoint of imparting low emission properties to the polyurethane foam, it is important to select non-volatile, high-molecular-weight additives (such as antioxidants and stabilizers) contained in the polyol.
a)成分として、有用なポリエーテルポリオールの具体例として、Voranol-3010、Voranol 3137、V230-056 Polyol(Dow Chemical Company)、ARCOLポリオール16-56、ARCOL 200 Polyol 16-56(Arco Chimecal Co.)、NIAX Polyol 16-56(A C West  Virginia  Polyo l  Company)、Desmophen PU20WB01、Desmophen 7186、Desmophen VPPU 20 WB 01(BAYER),ポリプロピレングリコール系ポリエーテルポリオー ル No.33(三洋化成工業株式会社)、10%の内部EOを含む3500分子量のEO/POトリオール、グリセリンを出発原料として、EO/PO=16/84(重量比)で付加重合した水酸基価56のポリエーテルポリオール、ポリオキシアルキレントリオール{EO/PO=12/88(重量比),水酸基価48}、グリセリンを出発原料として、EO/PO=14/86(重量比)で付加重合した水酸基価46のポリエーテルポリオール、グリセリンを出発原料として、EO/PO=16/84(重量比)で付加重合した水酸基価46のポリエーテルポリオール、グリセリンのPO/EO付加物(水酸基価33)などが挙げられる。 Specific examples of polyether polyols useful as component a) include Voranol-3010, Voranol 3137, V230-056 Polyol (Dow Chemical Company), ARCOL Polyol 16-56, ARCOL 200 Polyol 16-56 (Arco Chimecal Co.) , NIAX Polyol 16-56 (AC West Virginia Polyol Company), Desmophen PU20WB01, Desmophen 7186, Desmophen VPPU 20 WB 01 (BAYER), polypropylene glycol-based polyether polyol No. 33 (Sanyo Chemical Industries, Ltd.), an EO/PO triol with a molecular weight of 3,500 containing 10% internal EO, glycerin as a starting material, EO/PO = 16/84 (weight ratio) addition-polymerized poly with a hydroxyl value of 56 Ether polyol, polyoxyalkylene triol {EO/PO=12/88 (weight ratio), hydroxyl value 48}, glycerin as a starting material, hydroxyl value 46 obtained by addition polymerization at EO/PO=14/86 (weight ratio) A polyether polyol having a hydroxyl value of 46 obtained by addition polymerization of EO/PO=16/84 (weight ratio) using polyether polyol and glycerin as a starting material, and a PO/EO adduct of glycerin (hydroxy value of 33).
[a´)前記a)以外のポリオール]
本発明で必要に応じて前記a)成分と併用できるポリオールとして好適な例として、難燃性に優れたハロゲン化ポリエーテルポリオール類や臭素化ポリオール類(ジブロモネオペンチルグリコール、臭素化ペンタエリスリトール、エピクロロヒドリンと臭素化ポリオールの重合ポリオールなど)が挙げられる。硬化反応速度の向上やセルサイズ調整などの目的で、比較的低分子量且つ高官能性のポリエーテルポリオール:平均の水酸基数が3~8で数平均分子量が250~1000である、多価アルコールや多価アミンへのアルキレンオキシド付加物も好ましい。例えば、ソルビトール;シュークロース;ラクトーズ;α-メチルグルコシド;α-ヒドロキシアルキルグルコシドなどの糖類やジエチレントリアミン;グリセリン;トリメチロールプロパン;トリエタノールアミン;ペンタエリスリトール;エチレンジアミン;芳香族ジアミンへのプロピレンオキシド及び/またはエチレンオキシドの付加物が挙げられる。
[a') polyol other than the above a)]
Preferred examples of polyols that can be used in combination with component a) in the present invention include halogenated polyether polyols and brominated polyols (dibromoneopentyl glycol, brominated pentaerythritol, epi polymerized polyols of chlorohydrins and brominated polyols). For the purpose of improving the curing reaction speed and adjusting the cell size, polyether polyols with relatively low molecular weight and high functionality: polyhydric alcohols with an average number of hydroxyl groups of 3 to 8 and a number average molecular weight of 250 to 1000 Alkylene oxide adducts to polyvalent amines are also preferred. saccharides such as sorbitol; sucrose; lactose; α-methylglucoside; α-hydroxyalkylglucoside; Adducts of ethylene oxide are mentioned.
この他、本発明の効果を損なわない範囲であれば、アジピン酸やフタル酸などのカルボン酸とエチレングリコール、1,4-ブタンジオール、1,6-ヘキサンジオール等の多価アルコールを脱水縮合して製造されるポリエステルポリオールや、HRフォーム用に通常は利用される一級水酸基の含有率が高く平均分子量が5000~7000程度のポリエーテルポリオール、ポリエーテルポリオール中でアクリロニトリルやスチレンなどを共重合させることによりポリマー微粒子を分散させたポリマーポリオール等を適宜、選択し併用してよい。 In addition, carboxylic acids such as adipic acid and phthalic acid and polyhydric alcohols such as ethylene glycol, 1,4-butanediol and 1,6-hexanediol can be dehydrated and condensed as long as the effects of the present invention are not impaired. polyester polyols produced by HR foams, polyether polyols with a high content of primary hydroxyl groups and an average molecular weight of about 5000 to 7000, which are usually used for HR foams, and copolymerization of acrylonitrile, styrene, etc. in polyether polyols. A polymer polyol or the like in which fine polymer particles are dispersed by means of a polymer may be appropriately selected and used in combination.
[b)ポリイソシアネート]
ポリイソシアネートとしては、スプレー用途で利用するという前提から作業者や周辺環境の安全性を考慮し、特に現場発泡の場合には、難揮発性あるいは不揮発性の有機ポリイソシアネートを選択するのが好ましい。
[b) Polyisocyanate]
As the polyisocyanate, it is preferable to select a non-volatile or non-volatile organic polyisocyanate, especially in the case of on-site foaming, considering the safety of workers and the surrounding environment on the premise that it will be used for spraying.
b)成分として、商業上も有利な材料は、MDI(ジフェニルメタンジイソシアネート)、4,4′-ジフェニルメタンジイソシアネート、4,2′-ジフェニルメタンジイソシアネート、ポリメリックMDI(ポリメチレンポリフェニルポリイソシアネート),クルードMDIである。この他、イソシアナート基含有プレポリマーとして、MDIとポリオールとの反応より作製されるMDIのプレポリマー、TDIとポリオールの反応より作製されるTDIのプレポリマー、他の芳香族もしくは脂肪族ポリイソシアナートとポリオールとの反応により作製されるプレポリマー、ウレトンイミン修飾ポリイソシアナートとそれらのプレポリマーなども使用できる。なお、b)成分として、前記のポリイソシアネートの誘導体を選択してもよい。 As component b), commercially advantageous materials are MDI (diphenylmethane diisocyanate), 4,4'-diphenylmethane diisocyanate, 4,2'-diphenylmethane diisocyanate, polymeric MDI (polymethylene polyphenyl polyisocyanate), crude MDI. . In addition, as isocyanate group-containing prepolymers, MDI prepolymers prepared by reacting MDI with polyols, TDI prepolymers prepared by reacting TDI with polyols, and other aromatic or aliphatic polyisocyanates. Also usable are prepolymers prepared by the reaction of polyols with uretonimine-modified polyisocyanates and their prepolymers. As component b), a derivative of the above polyisocyanate may be selected.
ポリウレタンフォームにLow Emission特性を付与する観点からも、前述のような難揮発性あるいは不揮発性の有機ポリイソシアネートを選択するのが好ましい。他方、工場内で断熱パネルなどの型にフォームを自動化作業設備によりスプレー注入~加熱硬化まで行う場合には、局所排気装置など作業環境の安全性を確保したうえで、上記の難揮発性あるいは不揮発性の有機ポリイソシアネートの他、トルエンジイソシアナート(TDI)を使用できる場合もある。TDIには2,4および2,6異性体の2種類があり、通常は2,4体/2,6体=80/20の混合物が流通しているので、これを使用してもよい。処方中における他の材料の量に対するポリイソシアネートの配合量は「イソシアネート指数」によって表される。「イソシアネート指数」とは、ポリイソシアネートの実際の使用量を、反応混合物中の全活性水素との反応に必要とされるポリイソシアネートの化学量論量で除して、100を乗じた値である。 From the viewpoint of imparting low emission properties to the polyurethane foam, it is preferable to select the nonvolatile or nonvolatile organic polyisocyanate as described above. On the other hand, when foam is sprayed into a mold such as a heat insulating panel in a factory and then heated and cured using automated work equipment, after ensuring the safety of the work environment such as a local exhaust system, the above non-volatile or non-volatile In some cases, toluene diisocyanate (TDI) can be used, as well as organic polyisocyanates. There are two types of TDI, 2,4 and 2,6 isomers, and a mixture of 2,4 isomers/2,6 isomers=80/20 is usually distributed, so this may be used. The amount of polyisocyanate incorporated relative to the amount of other ingredients in the formulation is expressed by the "isocyanate index." "Isocyanate Index" is the actual amount of polyisocyanate used divided by the stoichiometric amount of polyisocyanate required to react with all active hydrogens in the reaction mixture multiplied by 100. .
本発明に係るポリウレタンスプレーフォームシステムでは水の使用量が多いため、b)成分における、イソシアネート指数の好適な範囲は一般的なポリウレタンフォームにおける範囲とは異なり、概ね30~80の範囲内である。 Since the polyurethane spray foam system according to the present invention uses a large amount of water, the preferred range of the isocyanate index in component b) is generally in the range of 30 to 80, unlike the range in general polyurethane foams.
本発明における泡増強剤の使用の見地から、適用される水発泡型ポリウレタンスプレーフォームシステムにおいて、ポリイソシアネートが、MDI(ジフェニルメタンジイソシアネート)、ポリメリックMDI(ポリメチレンポリフェニルポリイソシアネート),クルードMDI,イソシアナート基含有プレポリマー、およびこれらの誘導体から選ばれる成分であり、かつ、同システムの発泡剤(d))が水を主要な発泡剤とし、より好適には実質的に水のみ、または他の発泡剤を含まず、水のみである組み合わせが特に好ましい。また、その場合、b)成分のイソシアネート指数が20~80、より好適には30~70の範囲にあることがより好ましい。 From the point of view of the use of the foam booster in the present invention, the polyisocyanate is MDI (diphenylmethane diisocyanate), polymeric MDI (polymethylene polyphenyl polyisocyanate), crude MDI, isocyanate, in the applied water blown polyurethane spray foam system. a component selected from group-containing prepolymers and derivatives thereof, and the blowing agent (d)) of the same system is water as the main blowing agent, more preferably substantially only water, or other blowing agents Combinations containing no agents and only water are particularly preferred. In that case, the isocyanate index of component b) is preferably in the range of 20-80, more preferably 30-70.
[c)ウレタン触媒]
ポリウレタン樹脂製造用の触媒としては、一般に金属触媒や第3級アミン類が使用されているが、第3級アミン類は、ポリオールと有機ポリイソシアネートからウレタン結合を生成する反応を促進すると同時に、水と有機ポリイソシアネートとの反応を促進し、炭酸ガスを発生させる作用も有しているため、様々なタイプのウレタンフォーム形成に幅広く使用される。一方、スズ触媒に代表される金属触媒は、主にウレタン化反応促進の触媒活性が高く実用性に優れるため、非発泡ウレタン分野で使用されるケースの方が多いが、一般的な軟質スラブフォームの処方でも、スズ系触媒はアミン系触媒と併用して使用される。また、メカニカルフロスフォームの処方では主にニッケル系触媒が使用される。
[c) Urethane catalyst]
Metal catalysts and tertiary amines are generally used as catalysts for polyurethane resin production. and organic polyisocyanate to generate carbon dioxide gas, it is widely used in the formation of various types of urethane foam. On the other hand, metal catalysts, typified by tin catalysts, are mainly used in non-foaming urethane fields because they have high catalytic activity for promoting urethanization reactions and are excellent in practical use. In the formulation of , the tin-based catalyst is also used in combination with the amine-based catalyst. In addition, nickel-based catalysts are mainly used in the formulation of mechanical froth foam.
本発明に係るポリウレタンスプレーフォームシステムは、水の使用量が多いことから一般的な軟質フォームに比べ反応熱の発生が多く、従って反応速度も大きい。そのため、通常はアミン系触媒を利用すれば充分である。アミン系触媒は、反応速度や発泡状態の調整の目的等により1種又は2種以上を組み合わせて使用してもよい。このようなアミン系触媒の例としては、ジメチルエタノールアミン、ジメチルアミノエトキシエタノール、トリエチレンジアミン、ビス(2-ジメチルアミノエチル)エーテル、N,N,N′,N′-テトラメチルヘキサメチレンジアミン、N,N′,N′,N″-ペンタメチルジエチレントリアミン等の第3級アミンウレタン触媒、イミダゾール誘導体、遅効性三級アミン触媒、一般型三級アミン触媒、低エミッション三級アミン触媒、ノンエミッション三級アミン触媒、およびAir ProductsからのDABCO(登録商標)触媒が挙げられる。ポリウレタンフォームにLow Emission特性を付与する観点からは、反応型アミン触媒の活用が好ましい。なお、必要に応じて金属触媒を併用しても構わない。これらの例としては、ニッケルアセトアセトナート、鉄アセトアセトナート、スズ系触媒、ビスマス系触媒、亜鉛系触媒、チタニウム系触媒、アルミニウム錯体、ジルコニウム錯体、オクチル酸カリウム、酢酸カリウム、酢酸ナトリウム、オクチル酸ナトリウム、表面に固体酸点を有する金属酸化物粒子、カルボン酸四級アンモニウム塩などが挙げられる。c)成分の添加量は、通常ポリオール合計100重量部に対して1~5重量部である。 Since the polyurethane spray foam system according to the present invention uses a large amount of water, it generates more heat of reaction than general flexible foams, and therefore has a high reaction rate. Therefore, it is usually sufficient to use an amine-based catalyst. The amine-based catalyst may be used alone or in combination of two or more depending on the purpose of adjusting the reaction rate and foaming state. Examples of such amine-based catalysts include dimethylethanolamine, dimethylaminoethoxyethanol, triethylenediamine, bis(2-dimethylaminoethyl)ether, N,N,N',N'-tetramethylhexamethylenediamine, N ,N′,N′,N″-Pentamethyldiethylenetriamine and other tertiary amine urethane catalysts, imidazole derivatives, slow-acting tertiary amine catalysts, general type tertiary amine catalysts, low-emission tertiary amine catalysts, non-emission tertiary Examples include amine catalysts and DABCO (registered trademark) catalysts from Air Products.From the viewpoint of imparting low emission characteristics to polyurethane foams, it is preferable to use reactive amine catalysts.If necessary, metal catalysts are used in combination. Examples of these include nickel acetoacetonate, iron acetoacetonate, tin-based catalysts, bismuth-based catalysts, zinc-based catalysts, titanium-based catalysts, aluminum complexes, zirconium complexes, potassium octylate, potassium acetate. , sodium acetate, sodium octylate, metal oxide particles having solid acid points on the surface, quaternary ammonium carboxylic acid, etc. The amount of component c) added is usually 1 to 1 to 100 parts by weight of the total polyol. 5 parts by weight.
[d)水である発泡剤]
本発明に係るポリウレタンスプレーフォームシステムは、低密度で軽量の断熱用又は吸音用の軟質ウレタンフォームを形成するものであり、典型的には、水を主要な発泡剤とする100倍発泡(発泡前のウレタン混合液の密度を仮に1.0g/cm3としたとき、発泡後のフォームの密度が0.01g/cm3となるような高発泡倍率を指す)処方である。そのため、前記システム中の成分a)であるポリエーテルポリオールおよびその他のポリオール成分の和100部に対する水の添加部数は10~40部の範囲内にある必要があり、好ましくは15~35部の範囲内にあり、特に好ましくは15~25部の範囲内にある。
[d) blowing agent that is water]
The polyurethane spray foam system of the present invention produces a low density, lightweight, flexible urethane foam for insulation or sound absorption, typically expanded 100 times with water as the primary blowing agent (before foaming). If the density of the urethane mixed solution is assumed to be 1.0 g/cm3, the density of the foam after foaming is 0.01 g/cm3). Therefore, the number of parts of water added to 100 parts of the sum of polyether polyol and other polyol components as component a) in the system should be in the range of 10 to 40 parts, preferably in the range of 15 to 35 parts. within the range of 15 to 25 parts.
水としては、精製水、純水、蒸留水、イオン交換水、水道水、上水などを好適に使用できる。現場発泡吹付けの場合には、利便性とコスト面から、発泡剤は、実質的に水のみであることが好ましく、特に、水を唯一の発泡剤、すなわち、水のみを発泡剤とすることが特に好ましい。なお、高価な他の発泡剤を併用した場合には、フォームの開放セル構造によりガスが抜けてしまうため、本発明の技術的効果が損なわれ、コスト面で不利になるだけでなく、発明の効果の点でも無駄になってしまう場合がある。このため、d)成分は、その利便性とコスト面から、95質量%以上、より好適には99質量%以上、さらに好適には99~100質量%の範囲で水であることが好ましい。工事現場等で容易かつ安価に調達できる水をそのまま発泡剤として使用できることは、本発明に係る泡増強剤等の商業的および技術的利点の一つである。 Purified water, pure water, distilled water, ion-exchanged water, tap water, tap water, and the like can be suitably used as water. In the case of on-site foaming spraying, the blowing agent is preferably substantially only water from the standpoint of convenience and cost. is particularly preferred. If another expensive foaming agent is used in combination, gas will escape due to the open cell structure of the foam. It may be wasted in terms of effectiveness. Therefore, component d) is preferably water in an amount of 95% by mass or more, more preferably 99% by mass or more, and still more preferably 99 to 100% by mass, from the viewpoints of convenience and cost. It is one of the commercial and technical advantages of the foam enhancer according to the present invention that water, which can be easily and inexpensively procured at construction sites or the like, can be used as it is as a foaming agent.
他方、工場内で断熱パネルなどの型にフォームを自動化作業設備によりスプレー注入~加熱硬化まで行う場合には、難燃性の発泡剤であるHFC-245faおよびHFC-134aのようなハイロドフルオロカーボン類、HFOおよびHCFOのようなハイドロフルオロオレフィン類などを併用しても良い。これらの高価なガスがフォームと共に充填された型から漏れ出ないのであれば、断熱性の向上に役立つ。 On the other hand, when the foam is sprayed into a mold such as a heat insulating panel in a factory and the process from spray injection to heat curing is performed by automated work equipment, flame-retardant foaming agents such as HFC-245fa and HFC-134a Hydrofluorocarbons , hydrofluoroolefins such as HFO and HCFO may be used in combination. If these expensive gases do not leak out of the filled mold with the foam, it helps improve insulation.
[f)ノニオン性の界面活性剤]
f)成分は、本発明に係るポリウレタンスプレーフォームシステムの任意の構成のひとつであり、本発明のポリウレタンスプレーフォームシステム用のプレミクス液の安定化を主たる目的とする。f)成分であるノニオン性の界面活性剤は、ノニオン性の有機系界面活性剤又は乳化剤であり、分子構造中にケイ素原子を含有しないものであり、成分f)の範囲からは、上記のシリコーンポリエーテル共重合体およびそれを含有する泡増強剤は除かれ、特に分子構造中にケイ素原子を有しない非シリコーン系(以下、「有機系」と表現する)の界面活性剤または乳化剤が好適である。
[f) nonionic surfactant]
Component f) is one of the optional constituents of the polyurethane spray foam system of the present invention, whose primary purpose is to stabilize the premix liquid for the polyurethane spray foam system of the present invention. The nonionic surfactant that is component f) is a nonionic organic surfactant or emulsifier that does not contain a silicon atom in its molecular structure. Polyether copolymers and foam enhancers containing them are excluded, and non-silicone surfactants or emulsifiers that do not have a silicon atom in their molecular structure (hereinafter referred to as "organic") are particularly preferred. be.
f)成分は、プレミクス液の温度や経時による保存安定性を確保する上で、系の曇点を向上させることのできるノニオン性有機系界面活性剤の添加が有効である。本発明に係るa)成分:ポリエーテルポリオールとd)成分:水との相溶化剤として働く必要がある点から、高HLB(水溶性)のノニオン乳化剤が好ましく、POEノニルフェニルエーテルやPOEオクチルフェニルエーテルなどのポリオキシエチレンアルキルフェニルエーテルや、POE脂肪アルコールエーテル、POE合成アルコールエーテル、POE分岐アルコールエーテル、POE2級アルコールエーテル等が利用できる。オキシエチレンの付加モル数は通常2~100の高範囲であり得るが、水溶性の観点からは7モル以上が、入手や取扱いの容易さからは30モル以下が好ましい。特に好適なものは、POE(9~20)ノニルフェニルエーテルやPOE(9~20)オクチルフェニルエーテルである。f)成分の好適な使用量は、ポリオールの合計量100重量部に対して5~30重量部である。5部未満では極性の異なるポリオール同士又はポリオールと水とを相溶性化できず均質なプレミクス液が得られ難く、30部を越えるとポリオール成分の相溶性が高くなり過ぎるために連通化(セルの開放)が起こり難くなり、フォーム収縮が生じ易くなる。 For the component f), addition of a nonionic organic surfactant capable of improving the clouding point of the system is effective in ensuring the storage stability of the premixed liquid over time and temperature. Component a) according to the present invention: polyether polyol and component d): high HLB (water-soluble) nonionic emulsifiers are preferable because they need to act as compatibilizers with water, such as POE nonylphenyl ether and POE octylphenyl Polyoxyethylene alkylphenyl ethers such as ethers, POE fatty alcohol ethers, POE synthetic alcohol ethers, POE branched alcohol ethers, POE secondary alcohol ethers and the like can be used. The number of added moles of oxyethylene can usually be in the high range of 2 to 100, but from the viewpoint of water solubility, it is preferably 7 moles or more, and from the viewpoint of availability and ease of handling, it is preferably 30 moles or less. Particularly preferred are POE(9-20) nonylphenyl ether and POE(9-20)octylphenyl ether. The preferred amount of component f) used is 5 to 30 parts by weight per 100 parts by weight of the total amount of polyol. If the amount is less than 5 parts, the polyols having different polarities cannot be made compatible with each other or the polyol and water cannot be made compatible, making it difficult to obtain a homogeneous premix solution. opening) is less likely to occur, and foam shrinkage is more likely to occur.
[g)難燃剤]
g)成分は、に係るポリウレタンスプレーフォームシステムの任意の構成のひとつであり、本発明で使用する難燃剤は、前記a´)に含まれる難燃性ポリオール以外の難燃性成分であり、例えばトリメチルフォスフェート、トリエチルフォスフェート、トリスクロロエチルフォスフェート、トリスクロロプロピルフォスフェート等のリン酸エステル等が挙げられる。その使用量は、難燃性ポリオールを使用しない処方では、ポリオール合計100重量部に対して40~80重量部が好ましい。40重量部未満では難燃効果が不十分となる場合がある。また80重量部を超えるとポリオール成分の相溶性が高くなり過ぎるために連続気泡にすることが困難となる場合がある。特に好ましい使用量は50~70重量部である。一方、難燃性ポリオールをポリオール全体(100重量部)のうち15~35重量部配合する処方では、g)成分の使用量は20~40重量部が好ましい。尚、当該難燃剤g)はポリイソシアネート成分に混合してウレタンフォーム形成に供することもできる。これらの難燃剤は、ウレタン混合液の粘性を低下させ、スプレーによる均質なフォーム形成を容易にする働きも有すると共に、ポリウレタン樹脂の可塑剤としても働き、基材へのフォームの密着性の向上に寄与する。
[g) flame retardant]
The g) component is one of the arbitrary configurations of the polyurethane spray foam system according to the above, and the flame retardant used in the present invention is a flame retardant component other than the flame retardant polyol included in a') above, such as Phosphate esters such as trimethyl phosphate, triethyl phosphate, trischloroethyl phosphate and trischloropropyl phosphate. The amount used is preferably 40 to 80 parts by weight per 100 parts by weight of the total polyol in a formulation that does not use a flame-retardant polyol. If it is less than 40 parts by weight, the flame retardant effect may be insufficient. On the other hand, if the amount exceeds 80 parts by weight, the compatibility of the polyol component becomes too high, which may make it difficult to form open cells. A particularly preferred amount is 50 to 70 parts by weight. On the other hand, in a formulation in which 15 to 35 parts by weight of the flame-retardant polyol is added to the total polyol (100 parts by weight), the amount of component g) used is preferably 20 to 40 parts by weight. The flame retardant g) can also be mixed with the polyisocyanate component to form the urethane foam. These flame retardants reduce the viscosity of the urethane mixture and facilitate uniform foam formation by spraying. They also act as plasticizers for the polyurethane resin, improving the adhesion of the foam to the substrate. contribute.
[h)任意成分]
h)成分は、本発明に係る泡増強剤以外のウレタンフォーム用整泡剤、希釈剤、鎖伸長剤、架橋剤、副次的な量の非水発泡剤、セル開放剤、充填剤、強化剤、顔料、染料、着色剤、抗酸化剤、抗オゾン剤、紫外線安定化剤、静電気防止剤、殺菌剤および抗菌剤などの当分野に公知であり任意のものであり、本発明の技術的効果を損なわない範囲で、それらの通常の含有量の範囲内で含んでよい。Low Emission特性を付与する観点からは、これらの任意成分であっても、フォームからマイグレーションや揮発によるリリースを起こさないような成分のみから構成されている材料であることを確認して、フォーム処方に配合することが、ポリウレタンフォーム形成性組成物の処方設計上重要である。
[h) optional component]
h) component is a foam stabilizer for urethane foam other than the foam enhancer according to the present invention, a diluent, a chain extender, a cross-linking agent, a secondary amount of a non-aqueous foaming agent, a cell opening agent, a filler, a reinforcing agents, pigments, dyes, colorants, antioxidants, antiozonants, UV stabilizers, antistatic agents, bactericides and antibacterial agents, etc., which are known in the art and optional, and which are technically useful in the present invention. They may be included within the range of their normal content as long as the effect is not impaired. From the viewpoint of imparting low emission characteristics, even if these optional ingredients, it is confirmed that the material is composed only of ingredients that do not cause release due to migration or volatilization from the foam, and the foam formulation is adjusted. Compounding is important in formulating polyurethane foam-forming compositions.
例えば、本発明に係る泡増強剤以外のウレタンフォーム用整泡剤として、本発明の効果を損なわない範囲で、一般的な軟質スラブフォーム用整泡剤を併用しても良い。例えば、ユニオンカーバイド社で最初に商品化されたL-520(Si-O-C型シリコーンポリエーテル共重合体)や、ダウ・ケミカル社より販売中のVORASURF DC198 Additive,DC5950 Additive,DC5943 Additive,DC5160 Additive,DC5900 Additive,DC5933 Additive,DC5982 Additive,DC5986 Additive,DC5987 Additive,DC5990 Additive(Si-C型シリコーンポリエーテル共重合体)及びダウ・東レ社より販売中のSRX 280A,SRX 294A,SRX 298,SH 190(Si-C型シリコーンポリエーテル共重合体)などが挙げられる。この他、前記a´)として比較的低分子量且つ高官能性のポリエーテルポリオールを併用する処方では、より高極性のシステムに適合させる観点から、本発明の効果を損なわない範囲で、適量の硬質フォーム用シリコーン整泡剤を併用することも可能である。更に、一般のHRフォーム用シリコーン整泡剤やマイクロセルラーフォーム用シリコーン整泡剤は、本発明に係るシステムにおいてはセル開放剤として働く場合があるので、必要に応じ、これらを適量併用しても良い。 For example, as a foam stabilizer for urethane foam other than the foam enhancer according to the present invention, a general foam stabilizer for flexible slab foam may be used in combination within a range that does not impair the effects of the present invention. For example, L-520 (Si—O—C type silicone polyether copolymer) first commercialized by Union Carbide, and VORASURF DC198 Additive, DC5950 Additive, DC5943 Additive, DC5160 sold by Dow Chemical Company. Additive, DC5900 Additive, DC5933 Additive, DC5982 Additive, DC5986 Additive, DC5987 Additive, DC5990 Additive (Si-C type silicone polyether copolymer) and SRX28H280A, SRX9SRX9SRX9SRX9SRX9SRX4SRX sold by Dow Toray 190 (Si—C type silicone polyether copolymer). In addition, in the formulation using a polyether polyol with a relatively low molecular weight and high functionality as the above a'), from the viewpoint of adapting to a higher polarity system, an appropriate amount of hard It is also possible to use a silicone foam stabilizer for foam together. Furthermore, general silicone foam stabilizers for HR foams and silicone foam stabilizers for microcellular foams may act as cell-opening agents in the system according to the present invention. good.
任意のh)成分である架橋剤もしくは鎖伸長剤として、1分子当たり2から8個のヒドロキシル基と62~500の分子量を持つポリヒドロキシル末端化合物を含有し得る。3から8個のヒドロキシル基を持つ架橋剤はグリセリン、トリメチロールプロパン、ペンタエリスリトール、マンニトール、ソルビトール等を含む。二個のヒドロキシル基を持つ有用な鎖伸長剤の例は、ジプロピレングリコール、トリプロピレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、1,4-ブタンジオール、エチレングリコール、2,3-ブタンジオール、2-メチル-1,3-プロパンジオール、1,2-プロパンジオール、1,3-プロパンジオールおよびネオペンチルグリコール等を含む。ジエタノールアミンおよびモノエタノールアミンなども使用できる。これらの化合物を、希釈剤として扱っても構わない。その他の好適な希釈剤としては、25℃で液状のポリアルキレングリコールまたはその誘導体が挙げられる。 The optional h) component crosslinker or chain extender may contain a polyhydroxyl terminated compound having 2 to 8 hydroxyl groups per molecule and a molecular weight of 62-500. Crosslinkers with 3 to 8 hydroxyl groups include glycerin, trimethylolpropane, pentaerythritol, mannitol, sorbitol, and the like. Examples of useful chain extenders with two hydroxyl groups are dipropylene glycol, tripropylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, ethylene glycol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,2-propanediol, 1,3-propanediol and neopentyl glycol and the like. Diethanolamine, monoethanolamine, and the like can also be used. These compounds may also be treated as diluents. Other suitable diluents include polyalkylene glycols or derivatives thereof that are liquid at 25°C.
任意のh)成分はまた、たとえば無機充填剤または充填剤の組み合わせのような充填剤を含んでよい。充填剤は、密度改質、機械的性能もしくは音吸収のような物理的性能、難燃性または例えば、炭酸カルシウムのような改善された経済性を含むものを含む他の利点の改善のためのもの、あるいは発泡体製造のコストを減ずる他の充填剤、水酸化アルミニウムもしくは他の難燃性充填剤、音吸収に用いられる硫酸バリウムもしくは他の高密度充填剤、発泡体密度をさらに減ずるガラスもしくはポリマーのような物質のミクロスフェアを含む。発泡体の剛性もしくは屈曲性のモジュールのような機械的性能を改質するために用いられる高いアスペクト比の充填剤ないし強化剤は、粉砕ガラス繊維もしくはグラファイト繊維のような人工繊維;珪灰石のような天然鉱物繊維;羊毛のような天然動物もしくは綿のような植物繊維;粉砕ガラスのような人工プレート状繊維;雲母のような天然鉱物プレート状充填剤を含む。添加する可能性のある顔料、染料、着色剤の任意のものを含む。さらに、本発明は、抗オゾン剤、抗酸化剤;熱もしくは熱-酸素分解阻害剤、紫外線安定剤、紫外線吸収剤もしくは、発泡体形成組成物に添加されるとき、生じる発泡体の熱、光および/もしくは化学的な分解を避けるか阻害する任意の他の添加剤の使用を意図する。ここでの使用をまた意図するものは、任意の公知で従来的な静電気防止剤、殺菌剤、抗菌剤およびガス退色阻害剤である。 The optional h) component may also contain fillers, such as inorganic fillers or combinations of fillers. Fillers may be used for density modification, improving physical performance such as mechanical performance or sound absorption, flame retardancy or other benefits including improved economics such as calcium carbonate. or other fillers that reduce the cost of foam production, aluminum hydroxide or other flame retardant fillers, barium sulfate or other high density fillers used for sound absorption, glass or other fillers that further reduce foam density Contains microspheres of polymer-like material. High aspect ratio fillers or reinforcing agents used to modify the mechanical performance of foams, such as rigid or flexible modules, include man-made fibers such as ground glass or graphite fibers; natural animal fibers such as wool or vegetable fibers such as cotton; artificial plate-like fibers such as ground glass; and natural mineral plate-like fillers such as mica. Including any pigments, dyes or colorants that may be added. Furthermore, the present invention includes anti-ozonants, antioxidants; heat or thermo-oxygen decomposition inhibitors, UV stabilizers, UV absorbers, or the resulting foam heat, light when added to the foam-forming composition. and/or use of any other additive that avoids or inhibits chemical degradation is contemplated. Also contemplated for use herein are any of the known and conventional antistatic agents, disinfectants, antibacterial agents and gas fade inhibitors.
[プレミックス液]
本発明に係るポリウレタンスプレーフォームシステム用のプレミックス液は、前記a)ポリエーテルポリオール、c)ウレタン触媒、d)水である発泡剤:前記システム中の成分a)であるポリエーテルポリオールおよびその他のポリオール成分の和100質量部に対して10~40質量部の添加部数、e)前記シリコーンポリエーテル共重合体を含有する疎水性向上効果を有する泡増強剤、を少なくとも含有する。
[Premix liquid]
The premix liquid for the polyurethane spray foam system according to the present invention comprises: a) polyether polyol, c) urethane catalyst, d) water blowing agent: polyether polyol as component a) in said system and other It contains at least 10 to 40 parts by weight per 100 parts by weight of the total polyol components, and e) a foam enhancer having a hydrophobicity-enhancing effect containing the silicone polyether copolymer.
更に、本発明に係るポリウレタンスプレーフォームシステム用のプレミクス液は、前記f)ノニオン性の界面活性剤、特に、有機系のノニオン性の界面活性剤を更に含有することが好ましい。本発明に係るポリウレタンスプレーフォームシステム用のプレミックス液は、基材由来の色を有していてよいが、通常は透明均一液体の性状を有する。 Furthermore, the premix liquid for the polyurethane spray foam system according to the present invention preferably further contains f) a nonionic surfactant, particularly an organic nonionic surfactant. Premix fluids for polyurethane spray foam systems according to the present invention may have a color derived from the substrate, but usually have the properties of clear homogeneous fluids.
[ポリウレタンスプレーフォーム形成用組成物]
本発明に係るポリウレタンスプレーフォーム形成用組成物は、前記a)、b),c)、d)、e)成分を含有し、更に任意選択により、前記a´)及びf)から選択される1つ以上を含有することができる。また、同組成物は、g)難燃剤をさらに含み、任意でh)その他の添加剤を含んでもよい。なお、各成分の種類および使用量はポリウレタンスプレーフォームシステムにおいて説明した通りである。
[Composition for Forming Polyurethane Spray Foam]
The composition for forming a polyurethane spray foam according to the present invention comprises components a), b), c), d) and e), and optionally one selected from a′) and f) above. can contain one or more The composition also further comprises g) a flame retardant and optionally h) other additives. The types and amounts of each component are as described for the polyurethane spray foam system.
本発明に係るポリウレタンスプレーフォーム形成用組成物の処方の一例を以下に示す。ここで、以下の成分a)は、「分子内の平均水酸基数が2~4であり、オキシプロピレン基からなる繰り返し単位を有し、数平均分子量が1000~6000の範囲内にある、1種類以上のポリエーテルポリオール」の要件を満たすものである。また、以下の成分b)のイソシアネート基の濃度は、30.5~32.0 wt.%の範囲にある。
処方1
a)ポリプロピレングリコール系ポリエーテルポリオール(三洋化成No.33)100重量部
c)DABCO 33LV(トリエチレンジアミン、Sigma Aldrich)        2重量部
e)泡増強剤、又は比較用整泡剤                    1重量部
d)水                                 25重量部
g)トリスクロロプロピルフォスフェート(大八化学、難燃剤TMCPP)   60重量部
b)ミリオネートMR-100(東ソー、ポリメリックMDI)         207重量部
An example of the formulation of the polyurethane spray foam-forming composition according to the present invention is shown below. Here, the following component a) is "one type having an average number of hydroxyl groups in the molecule of 2 to 4, having a repeating unit composed of an oxypropylene group, and having a number average molecular weight within the range of 1000 to 6000. It satisfies the above polyether polyol requirements. Also, the concentration of the isocyanate groups in component b) below is 30.5 to 32.0 wt. % range.
Formula 1 :
a) Polypropylene glycol-based polyether polyol (Sanyo Kasei No. 33) 100 parts by weight c) DABCO 33LV (triethylenediamine, Sigma Aldrich) 2 parts by weight e) Foam enhancer or comparative foam stabilizer 1 part by weight d) Water 25 parts by weight g) Trischloropropyl phosphate (Daihachi Chemical, flame retardant TMCPP) 60 parts by weight b) Millionate MR-100 (Tosoh, Polymeric MDI) 207 parts by weight
本発明に係るポリウレタンスプレーフォーム形成用組成物は、特に軟質ポリウレタン発泡体の形成に好適に利用でき、厳しいVOC(Volatile Organic Compound)管理或いはエミッション管理を要求される現在のポリウレタン産業界のニーズに応えることが可能である。より具体的には、泡増強剤における、前記のケイ素原子数が20以下の低分子シロキサンの含有量が5000ppm(重量)以下、2000ppm(重量)以下、1000(重量)ppm以下に容易に抑制でき、かつ、泡増強剤としての使用量自体も少ないため、最終的に得られるポリウレタンフォームにおいて、これらの揮発性シロキサンに由来するVOCおよびそのエミッションをほぼ完全に抑制することができる。なお、泡増強剤におけるこれらの成分の含有量が5000ppmを超えると、前記泡増強剤をポリウレタン発泡体用の整泡剤として用いた場合、ポリウレタンフォームが設置された場所の周辺部材を汚染し、電気・電子装置の接点障害を引き起こす可能性があり、好ましくない。 The composition for forming polyurethane spray foam according to the present invention can be used particularly suitably for forming flexible polyurethane foams, and meets the current needs of the polyurethane industry, which requires strict VOC (volatile organic compound) control or emission control. It is possible. More specifically, the content of the low-molecular-weight siloxane having 20 or less silicon atoms in the foam enhancer can be easily suppressed to 5000 ppm (weight) or less, 2000 ppm (weight) or less, or 1000 ppm (weight) or less. Moreover, since the amount itself used as a foam enhancer is small, VOCs derived from these volatile siloxanes and their emissions can be almost completely suppressed in the finally obtained polyurethane foam. If the content of these components in the foam enhancer exceeds 5000 ppm, when the foam enhancer is used as a foam stabilizer for a polyurethane foam, the surrounding members around the place where the polyurethane foam is installed will be contaminated, It is not preferable because it may cause contact failure of electric/electronic devices.
本発明に係るポリウレタンスプレーフォーム形成用組成物を硬化させてなる軟質ポリウレタン発泡体は、その用途が限定されるものではないが、現場発泡により硬化させてなる建築材料、特に、断熱材又は吸音材として好適に利用可能である。 The flexible polyurethane foam obtained by curing the composition for forming polyurethane spray foam according to the present invention is not limited in its use, but is a building material cured by on-site foaming, in particular, a heat insulating material or a sound absorbing material. It can be suitably used as
本発明に係る軟質ポリウレタン発泡体は、そのプレミックス液が安定しており、取り扱い作業性に優れ、発泡性に優れ、建造物の製造現場において、少量の使用であっても大容積の発泡体(=フォーム体積)を形成できるため、建造物用途等におけるコスト面、作業効率に優れ、得られる発泡体が微細なセル構造を有し、断熱材/吸音材等の用途に適合しており、かつ、従来の泡増強剤を使用した場合に比べて、ポリウレタン発泡体(特に、軟質ポリウレタンフォーム)の疎水性を顕著に改善可能であるという、従来技術にはない主要な利点を兼ね備え、かつ、近年、特に建造物用途における重要度が高い、Low Emission/Low VOCの要求を充足できるものである。 The flexible polyurethane foam according to the present invention has a stable premixed liquid, excellent handling workability, and excellent foaming properties, and can be used at a building manufacturing site even if it is used in a small amount. (= foam volume), it is excellent in terms of cost and work efficiency in building applications, etc. The resulting foam has a fine cell structure and is suitable for applications such as heat insulation / sound absorption Moreover, compared with the use of conventional foam enhancers, the hydrophobicity of polyurethane foams (especially flexible polyurethane foams) can be significantly improved, which is a major advantage not found in the prior art, and In recent years, it can satisfy the requirements of Low Emission/Low VOC, which are of high importance especially in building applications.
以下、実施例と比較例により本発明を更に詳細に説明するが、本発明は、これらにより限定されるものではない。なお、「式量」以外の数平均分子量は、クロロホルム溶離液によるGPC(検出器:屈折率計)により、ポリスチレン換算値として得られた値である。 EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these. The number average molecular weight other than the "formula weight" is a value obtained as a polystyrene equivalent by GPC (detector: refractometer) using a chloroform eluent.
以下、本発明にかかる泡増強剤の性能評価手順を、A:プレミクス相溶性試験、B:ウレタンフォームの形成、C:ウレタンフォームの体積/セル構造の評価、D:ウレタンフォームの吸水率試験の順に説明する。 Hereinafter, the performance evaluation procedure of the foam enhancer according to the present invention is A: Premix compatibility test, B: Formation of urethane foam, C: Evaluation of volume / cell structure of urethane foam, D: Water absorption test of urethane foam I will explain in order.
[A:プレミクス相溶性試験]
本発明の泡増強剤と比較用整泡剤について、プレミクス液中での相溶性試験を以下の手順に従って行った。
A1.50gのa)ポリエーテルポリオール、及び所定の比率のd)水、c)ウレタン触媒、e)泡増強剤又は比較用整泡剤を100mLガラス瓶に仕込む。
A2.鋸刃付きの円盤型ディスパーミキサーを用いて、上記内容物を1分間攪拌して均質化する。
A3.ガラス瓶に栓をして室温で1夜間静置し、泡を消す。
A4.混合液の外観(透明性)を目視確認し、記録する。
[A: Premix compatibility test]
For the foam enhancer of the present invention and the foam stabilizer for comparison, a compatibility test in a premix liquid was conducted according to the following procedure.
A 1. Charge 50 g of a) polyether polyol and proportions of d) water, c) urethane catalyst, e) foam enhancer or comparative foam stabilizer to a 100 mL glass bottle.
A2. Homogenize the contents by stirring for 1 minute using a disk-shaped disper mixer with a saw blade.
A3. Cap the vial and let stand overnight at room temperature to allow bubbles to dissipate.
A4. Visually check the appearance (transparency) of the mixture and record it.
[B:ウレタンフォームの形成]
B1.前記Aで調製したプレミクス液、g)難燃剤、b)ポリイソシアネートを、合計重量が20gとなるような所定の比率で200mLプラスチックカップに仕込み、即座に、鋸刃付きの円盤型ディスパーミキサーで3500rpm,7秒間攪拌する。
B2.ミキサーの攪拌を止め、即座に、得られた均質混合されたポリウレタンスプレーフォーム形成用組成物を1Lプラスチックカップに注ぎ込み、自然に発泡させる。注ぎ込み開始から終了までの時間は8秒間で固定する。
B3.得られたフォームを室温で1夜間静置する。
[B: Formation of urethane foam]
B1. The premix liquid prepared in A above, g) flame retardant, and b) polyisocyanate were charged in a predetermined ratio such that the total weight was 20 g in a 200 mL plastic cup, and immediately, a disk-shaped disper mixer with a saw blade was added to the mixture at 3500 rpm. , stirring for 7 seconds.
B2. The agitation of the mixer is stopped and immediately the resulting homogeneously mixed polyurethane spray foaming composition is poured into a 1 L plastic cup and allowed to foam naturally. The time from the start of pouring to the end is fixed at 8 seconds.
B3. The resulting foam is allowed to stand overnight at room temperature.
[C:ウレタンフォームの体積/セル構造の評価]
C1.前記Bで作成されたプラスチックカップ入りのフォームを、電動カッターを用いて上下半分に切断する。
C2.フォームの高さ(単位mm)とフォーム断面のセル構造の均質さを、記録する。
[C: Evaluation of Urethane Foam Volume/Cell Structure]
C1. Cut the foam containing the plastic cup prepared in B above into upper and lower halves using an electric cutter.
C2. The height of the foam (in mm) and the homogeneity of the cell structure of the cross section of the foam are recorded.
[D:ウレタンフォームの吸水率試験]
D1.前記Cで得られたフォーム片を電動カッターにて更に細断し、縦6.5cm×横6.5cm×高さ4cmの直方体状のテストピースを作成する。ここで、このテストピースは前記Bで作成されたプラスチックカップ入りのフォームの中央部から採取されたものとする。
D2.前記テストピースの重量を測定し、記録する。
D3.水浴を準備する。
D4.前記テストピースの下部半分を水浴に2時間浸した後、取り出して重量を測定し、記録する。
D5.テストピースの吸水率(重量%)を計算し、記録する。
[D: Water absorption test of urethane foam]
D1. The foam pieces obtained in C above are further chopped with an electric cutter to prepare rectangular parallelepiped test pieces of length 6.5 cm x width 6.5 cm x height 4 cm. Here, it is assumed that this test piece was sampled from the center of the foam containing the plastic cup prepared in B above.
D2. Measure and record the weight of the test piece.
D3. Prepare a water bath.
D4. The bottom half of the test piece is immersed in the water bath for 2 hours, then removed and weighed and recorded.
D5. Calculate and record the water absorption (% by weight) of the test piece.
第一ラウンドの試験においては、比較用整泡剤として以下の2つのグループ間の比較を行った。これらは、主として市販の整泡剤からなる。なお、これらの整泡剤の主成分であるシリコーンポリエーテル共重合体を表す組成式において、MeSiO基(又は、MeSi基)を「M 」、MeSiO基を「D 」、MeHSiO基を「M 」、MeHSiO基を「D 」と表記し、MおよびD中のメチル基の一つを何らかの置換基(*または**である変性基)によって変性した単位をMおよびD等と表記する。また、(EO)とはオキシエチレン基を表し、(PO)とはオキシプロピレン基を表し、Me基はメチル基、Ac基はアセチル基を表すものとする。
[比較用整泡剤(第一ラウンド)]
・グループR:硬質ウレタンフォーム用整泡剤9種
・グループF:軟質スラブフォーム用整泡剤3種
In the first round of testing, a comparison was made between the following two groups as comparative foam stabilizers. These consist primarily of commercially available foam stabilizers. In addition, in the composition formula representing the silicone polyether copolymer which is the main component of these foam stabilizers, the Me 3 SiO group (or Me 3 Si group) is “M ”, the Me 2 SiO group is “D ”, A Me 2 HSiO group is denoted as “M H ”, a MeHSiO group is denoted as “D H ”, and a unit obtained by modifying one of the methyl groups in M and D with some substituent (modifying group * or **) is It is written as M * , D * , and so on. (EO) represents an oxyethylene group, (PO) represents an oxypropylene group, Me represents a methyl group, and Ac represents an acetyl group.
[Comparative foam stabilizer (first round)]
・Group R: 9 foam stabilizers for rigid urethane foam ・Group F: 3 foam stabilizers for flexible slab foam
以下に、グループRに属する比較用整泡剤の識別番号と、主成分の平均組成式を示した。なお、簡易的に(EO)と(PO)がブロック結合しているような形式で表現をしているが、実際にはランダム付加構造である。
比較整泡剤R1:M25 =-CO(EO)15(PO)-H
比較整泡剤R2:MD43 6.8M,=-CO(EO)26(PO)-CH
比較整泡剤R3:MD50 M,=-CO(EO)11(PO)3.5-H
比較整泡剤R4:M18 =-CO(EO)15(PO)-CH
比較整泡剤R5:M25 =-CO(EO)24(PO)-CH
比較整泡剤R6:MD34 5.7M,=-CO(EO)12(PO)-H
比較整泡剤R7:MD34 5.7M,=-CO(EO)11(PO)3.5-H
比較整泡剤R8:M42 =-CO(EO)17(PO)-CH
比較整泡剤R9:MD37 3.4** 2.1M,=-CO(EO)11(PO)3.5-CH**=-CO(EO)11(PO)3.5-H
The identification numbers of the comparative foam stabilizers belonging to Group R and the average compositional formula of the main components are shown below. Although (EO) and (PO) are expressed in a block-bonded form for simplicity, it is actually a random addition structure.
Comparative foam stabilizer R1 : M * D25D * 1M * , * =- C3H6O (EO) 15 (PO) 5 - H
Comparative foam stabilizer R2: MD 43 D * 6.8 M, * = -C 3 H 6 O(EO) 26 (PO) 6 -CH 3
Comparative foam stabilizer R3: MD 50 D * 7 M, * = -C 3 H 6 O(EO) 11 (PO) 3.5 -H
Comparative foam stabilizer R4: M * D18D * 3M * , * =-C3H6O(EO) 15 ( PO) 5 - CH3
Comparative foam stabilizer R5: M * D25 D * 1 M * , * =-C3H6O ( EO) 24 (PO) 6 - CH3
Comparative foam stabilizer R6: MD 34 D * 5.7 M, * = -C 3 H 6 O(EO) 12 (PO) 2 -H
Comparative foam stabilizer R7: MD 34 D * 5.7 M, * = -C 3 H 6 O(EO) 11 (PO) 3.5 -H
Comparative foam stabilizer R8: M * D42 D * 5 M * , * =-C3H6O ( EO) 17 (PO) 7 - CH3
Comparative foam stabilizer R9: MD 37 D * 3.4 D ** 2.1 M, * = - C 3 H 6 O(EO) 11 (PO) 3.5 - CH 3 , ** = - C 3 H 6 O(EO) 11 (PO) 3.5 -H
以下に、グループFに属する比較用整泡剤の識別番号と、主成分の平均組成式を示した。なお、簡易的に(EO)と(PO)がブロック結合しているような形式で表現をしているが、実際にはランダム付加構造である。
比較整泡剤F1:MD50 5.9M,=-CO(EO)22(PO)22-CH
比較整泡剤F2:MD33 2.8M,=-CO(EO)22(PO)22-CH
比較整泡剤F3:MD53 M,=-CO(EO)22(PO)22-COCH
The identification numbers of the comparative foam stabilizers belonging to Group F and the average compositional formula of the main components are shown below. Although (EO) and (PO) are expressed in a block-bonded form for simplicity, it is actually a random addition structure.
Comparative foam stabilizer F1: MD 50 D * 5.9 M, * = -C 3 H 6 O(EO) 22 (PO) 22 -CH 3
Comparative foam stabilizer F2: MD 33 D * 2.8 M, * = -C 3 H 6 O(EO) 22 (PO) 22 -CH 3
Comparative foam stabilizer F3: MD 53 D * 3 M, * = -C 3 H 6 O(EO) 22 (PO) 22 -COCH 3
以下に、前記比較用整泡剤12点の構造要素をまとめた。
[表1]:比較用整泡剤(第一ラウンド)の構造
Figure JPOXMLDOC01-appb-T000006


The structural elements of the 12 foam stabilizers for comparison are summarized below.
[Table 1]: Structure of comparative foam stabilizer (first round)
Figure JPOXMLDOC01-appb-T000006


以下に、前記比較用整泡剤12点の性能評価結果をまとめた。なお、データの採取をしていないもの又は記録の無いものは「-」と記してある。
[表2]:比較用整泡剤(第一ラウンド)の性能と構造の関係
Figure JPOXMLDOC01-appb-T000007


The performance evaluation results of the 12 foam stabilizers for comparison are summarized below. Data not collected or not recorded are indicated with "-".
[Table 2]: Relationship between performance and structure of comparative foam stabilizers (first round)
Figure JPOXMLDOC01-appb-T000007


以上の結果より、シリコーン整泡剤のポリエーテル末端基YがHを主体とする構造である場合には、プレミクス液との相溶性が不足し、透明な外観が得られにくい傾向にあることが分かった。加えて、フォーム高さ(体積)に優れるものは、全てプレミクス液の外観が透明であったことから、プレミクス相溶性に優れた構造設計がまず重要であることが分かった。次に、フォームの吸水率に関しては、全般的に硬質フォーム用の整泡剤(グループR)よりも軟質スラブ用整泡剤(グループF)を使用した方が低い値が得られていることが分かった。 From the above results, when the polyether terminal group Y of the silicone foam stabilizer has a structure mainly composed of H, the compatibility with the premix liquid is insufficient, and it tends to be difficult to obtain a transparent appearance. Do you get it. In addition, all foams with excellent foam height (volume) had a transparent appearance of the premix liquid, indicating that structural design with excellent premix compatibility is important. Next, regarding the water absorption rate of the foam, it was found that generally lower values were obtained when using the foam stabilizer for soft slabs (Group F) than when using the foam stabilizer for rigid foams (Group R). Do you get it.
しかしながら、前記軟質スラブ用整泡剤を使用した場合と同レベルのフォーム体積を稼ぎながら、吸水率の低いフォームが求められていることから、従来技術からの改良が必要であった。そこで、構造の異なるシリコーンポリエーテル共重合体を新たに12点合成し、前記R8及びF3と比較する形で、性能の評価を実施した。詳細は以下の通りである。 However, there is a demand for a foam with a low water absorption rate while obtaining the same level of foam volume as when using the foam stabilizer for soft slabs. Therefore, 12 silicone polyether copolymers with different structures were newly synthesized, and their performance was evaluated by comparing them with the above R8 and F3. Details are as follows.
[実施例/比較例用共重合体の合成(第二ラウンド)]
以下に、実施例のシリコーンポリエーテル共重合体(本発明の泡増強剤)1点について、合成手順を参考までに示す。この他の実施例サンプル、比較例サンプル(比較整泡剤)については、主原料であるオルガノハイドロジェンポリシロキサンと片末端アリル基含有ポリエーテルの構造或いは組み合わせが異なるが、本例と概ね同様の手順で合成を行った。なお、これらのシリコーンポリエーテル共重合体を表す組成式において、MeSiO基(又は、MeSi基)を「M 」、MeSiO基を「D 」、MeHSiO基を「M 」、MeHSiO基を「D 」と表記し、MおよびD中のメチル基の一つを何らかの置換基(*または**)によって変性した単位をMおよびD等と表記する。また、(EO)とはオキシエチレン基を表し、(PO)とはオキシプロピレン基を表し、Me基はメチル基、Ac基はアセチル基を表すものとする。
[Synthesis of copolymer for example/comparative example (second round)]
For reference, the synthesis procedure for one silicone polyether copolymer (foam enhancer of the present invention) of the example is shown below. Other example samples and comparative example samples (comparative foam stabilizers) differed in the structure or combination of the organohydrogenpolysiloxane and the one-end allyl group-containing polyether, which are the main raw materials, but were generally the same as in this example. synthesized according to the procedure. In the composition formulas representing these silicone polyether copolymers, the Me 3 SiO group (or Me 3 Si group) is "M", the Me 2 SiO group is "D", and the Me 2 HSiO group is "M H , a MeHSiO group is denoted as “D H ”, and units obtained by modifying one of the methyl groups in M and D with some substituent (* or **) are denoted as M * and D * , and the like. (EO) represents an oxyethylene group, (PO) represents an oxypropylene group, Me represents a methyl group, and Ac represents an acetyl group.
<実施例1>識別番号SI-1の泡増強剤の製造
平均組成式 MD53 M で表され、ケイ素原子に結合した水素基の濃度分析値が0.072質量%であるオルガノハイドロジェンポリシロキサン原料を139.68g、平均組成式CH=CH-CH-O(CO)(CO)22-Hで表され、不飽和基の濃度分析値が0.45ミリモル/g且つ水酸基価の分析値が28.4mg-KOH/gである片末端アリルポリエーテル原料310.32g、IPA(イソプロピルアルコール)135gを1Lフラスコに仕込み、窒素流通下で攪拌しながら油浴の温度設定を85℃として加温を開始した。なお、この反応系におけるアリル/SiHのモル比は1.4であった。フラスコ内容物の温度45~50℃で、白金-ジビニルジシロキサン錯体(カールシュタット触媒)のIPA溶液(Pt濃度0.4wt%)を244ppm(白金として10ppm相当)添加したところ、18分後に反応液が透明化した。フラスコ内容液の温度を80℃に維持して80分間の反応を行なった。次いで反応液を1g採取し、アルカリ分解ガス発生法により確認したところ反応は完結していた。油浴の温度設定を125℃として、窒素流量を増やし常圧にてIPAの留去を開始した。留出速度が遅くなったところで、レシーバーのIPAを一旦廃棄し、泡立ちや突沸に注意しながら、系内を徐々に30mmHgまで減圧した。その後、フラスコ内容液の温度を110~125℃、圧力を10mmHg以下の条件下で75分間維持し、更に揮発分の除去を行った。その後、加熱を停止してフラスコを95℃以下まで放冷し、復圧した。
<Example 1> Production of foam enhancer with identification number SI-1 An organohydrogen represented by the average composition formula MD 53 D H 3 M and having a concentration analysis value of hydrogen groups bonded to silicon atoms of 0.072% by mass. 139.68 g of genpolysiloxane raw material, represented by the average compositional formula CH 2 ═CH—CH 2 —O(C 2 H 4 O) 9 (C 3 H 6 O) 22 —H, concentration analysis value of unsaturated groups is 0.45 mmol/g and the hydroxyl value analysis value is 28.4 mg-KOH/g. Heating was started while setting the temperature of the oil bath to 85°C. The allyl/SiH molar ratio in this reaction system was 1.4. At a temperature of 45 to 50 ° C. to the contents of the flask, 244 ppm of an IPA solution (Pt concentration 0.4 wt%) of a platinum-divinyldisiloxane complex (Karlstadt catalyst) (equivalent to 10 ppm as platinum) was added, and after 18 minutes, the reaction liquid has become transparent. The reaction was carried out for 80 minutes while maintaining the temperature of the liquid in the flask at 80°C. Next, 1 g of the reaction solution was sampled and confirmed by the alkali decomposition gas generation method, and the reaction was completed. The temperature of the oil bath was set to 125° C., the nitrogen flow rate was increased, and distillation of IPA was started under normal pressure. When the distillation rate slowed down, the IPA in the receiver was temporarily discarded, and the pressure in the system was gradually reduced to 30 mmHg while paying attention to bubbling and bumping. After that, the temperature of the liquid in the flask was maintained at 110 to 125° C. and the pressure was kept at 10 mmHg or less for 75 minutes to remove volatile matter. After that, the heating was stopped, the flask was allowed to cool to 95°C or less, and the pressure was restored.
これにより、平均組成式MD53 M{=-CO(CO)(CO)22-H}で表されるシリコーンポリエーテル共重合体を含む、淡黄褐色透明均一液体を得た。なお、簡易的にポリオキシエチレン基とポリオキシプロピレン基がブロック結合しているような形式で表現をしているが、実際にはランダム付加構造である。
泡増強剤SI-1:MD53 M,=-CO(EO)(PO)22-H
As a result, a silicone polyether copolymer represented by the average composition formula MD 53 D * 3 M { * = -C 3 H 6 O(C 2 H 4 O) 9 (C 3 H 6 O) 22 -H} A pale yellowish brown transparent homogeneous liquid containing It should be noted that although the polyoxyethylene group and the polyoxypropylene group are expressed in a form of block bonding for the sake of simplicity, it is actually a random addition structure.
Foam booster SI-1: MD 53 D * 3 M, * = -C 3 H 6 O(EO) 9 (PO) 22 -H
<実施例2~実施例4>識別番号SI-2~SI-4の泡増強剤の構造
以下に、実施例サンプルの識別番号と、主成分の平均組成式を示した。なお、簡易的に(EO)と(PO)がブロック結合しているような形式で表現をしているが、実際にはランダム付加構造である。
泡増強剤SI-2:MD53 M,=-CO(EO)18(PO)16-H
泡増強剤SI-3:MD54 6.5M,=-CO(EO)18(PO)16-H
泡増強剤SI-4:MD83 7.7M,=-CO(EO)18(PO)16-H
<Examples 2 to 4> Structures of foam enhancers with identification numbers SI-2 to SI-4 Below are shown the identification numbers of the example samples and the average compositional formula of the main components. Although (EO) and (PO) are expressed in a block-bonded form for simplicity, it is actually a random addition structure.
Foam booster SI-2: MD 53 D * 3 M, * = -C 3 H 6 O(EO) 18 (PO) 16 -H
Foam booster SI-3: MD 54 D * 6.5 M, * = - C 3 H 6 O(EO) 18 (PO) 16 -H
Foam booster SI-4: MD 83 D * 7.7 M, * = - C 3 H 6 O(EO) 18 (PO) 16 -H
<比較例1~比較例8>識別番号SR-1~SR-8
以下に、比較例サンプルの識別番号と、主成分の平均組成式を示した。なお、簡易的に(EO)と(PO)がブロック結合しているような形式で表現をしているが、実際にはランダム付加構造である。
比較整泡剤SR-1:MD53 M,=-CO(EO)30(PO)10-H
比較整泡剤SR-2:MD54 6.5M,=-CO(EO)15(PO)-H
比較整泡剤SR-3:MD54 6.5M,=-CO(EO)21(PO)-H
比較整泡剤SR-4:MD54 6.5M,=-CO(EO)30(PO)10-H
比較整泡剤SR-5:MD83 7.7M,=-CO(EO)21(PO)-H
比較整泡剤SR-6:MD83 7.7M,=-CO(EO)30(PO)10-H
比較整泡剤SR-7:MD54 6.5M,=-CO(EO)21(PO)-CH
比較整泡剤SR-8:MD83 7.7M,=-CO(EO)21(PO)-CH
<Comparative Examples 1 to 8> Identification numbers SR-1 to SR-8
The identification numbers of the comparative samples and the average compositional formula of the main components are shown below. Although (EO) and (PO) are expressed in a block-bonded form for simplicity, it is actually a random addition structure.
Comparative foam stabilizer SR-1: MD 53 D * 3 M, * = -C 3 H 6 O (EO) 30 (PO) 10 -H
Comparative foam stabilizer SR-2: MD 54 D * 6.5 M, * = -C 3 H 6 O(EO) 15 (PO) 5 -H
Comparative foam stabilizer SR-3: MD 54 D * 6.5 M, * = -C 3 H 6 O(EO) 21 (PO) 9 -H
Comparative foam stabilizer SR-4: MD 54 D * 6.5 M, * = -C 3 H 6 O(EO) 30 (PO) 10 -H
Comparative foam stabilizer SR-5: MD 83 D * 7.7 M, * = -C 3 H 6 O(EO) 21 (PO) 9 -H
Comparative foam stabilizer SR-6: MD 83 D * 7.7 M, * = -C 3 H 6 O(EO) 30 (PO) 10 -H
Comparative foam stabilizer SR-7: MD 54 D * 6.5 M, * = -C 3 H 6 O(EO) 21 (PO) 9 -CH 3
Comparative foam stabilizer SR-8: MD 83 D * 7.7 M, * = -C 3 H 6 O(EO) 21 (PO) 9 -CH 3
以下に、実施例/比較例用共重合体サンプル12点の構造要素をまとめた。なお、比較のため、前記R8及びF3も含めて表示してある。
[表3]:試作サンプル(第二ラウンド)の構造
Figure JPOXMLDOC01-appb-T000008


The structural elements of the 12 example/comparative copolymer samples are summarized below. For comparison, R8 and F3 are also included in the display.
[Table 3]: Structure of prototype sample (second round)
Figure JPOXMLDOC01-appb-T000008


以下に、実施例/比較例用共重合体サンプル12点の性能評価結果をまとめた。なお、データの採取をしていないもの又は記録の無いものは「-」と記してある。また、比較のため、前記R8及びF3も含めて表示してある。
[表4]:試作サンプル(第二ラウンド)の性能と構造の関係
Figure JPOXMLDOC01-appb-T000009


The performance evaluation results of 12 copolymer samples for Examples/Comparative Examples are summarized below. Data not collected or not recorded are indicated with "-". For comparison, R8 and F3 are also included in the display.
[Table 4]: Relationship between performance and structure of prototype samples (second round)
Figure JPOXMLDOC01-appb-T000009


以上の結果より、シリコーン整泡剤のポリエーテル末端基YがHを主体とする構造であったとしても、比Zの値が大きい(ここではPO-リッチな長いポリエーテル鎖を有する)場合には、プレミクスシステムとの相溶性に優れ、体積が大きくセル構造の良好な、しかも吸水率の小さなフォームが得られることが分かった。すなわち、ウレタンフォーム用整泡剤として利用されるシリコーンポリエーテル共重合体に関し、本発明の特定の化学構造を選択することにより、ウレタンフォーム自体の疎水性を向上できることが見出された。一方で、シリコーン整泡剤のポリエーテル末端基YがMe或いはAcなどキャップされた構造の場合には、比Zの値が小さくともプレミクスとの相溶性に優れるという特徴を有するが、得られたフォームの吸水率が大きくマーケットニーズを満たせないことが明らかである。 From the above results, even if the polyether terminal group Y of the silicone foam stabilizer has a structure mainly composed of H, when the value of the ratio Z is large (here, it has a PO-rich long polyether chain) It has been found that the foam has excellent compatibility with the premix system, has a large volume, has a good cell structure, and has a low water absorption rate. That is, it was found that the hydrophobicity of the urethane foam itself can be improved by selecting the specific chemical structure of the silicone polyether copolymer used as a foam stabilizer for urethane foam. On the other hand, when the polyether terminal group Y of the silicone foam stabilizer has a capped structure such as Me or Ac, it is characterized by excellent compatibility with the premix even if the value of the ratio Z is small. It is clear that the foam has a high water absorption rate and cannot meet the market needs.
特に、本発明の泡増強剤SI-1~SI-4は、その原料である片末端アリルポリエーテルの水酸基部分をキャップ処理する必要がないため、現在スプレーフォームシステム向けに転用されている軟質スラブフォーム用整泡剤よりも安価に製造できる利点がある。それにもかかわらず、先の表4に示した通り、総合的な性能のバランスにおいてF3を上回っている。従って、本発明の泡増強剤は、社会及び産業の健全な発展への貢献が大である。 In particular, the foam enhancers SI-1 to SI-4 of the present invention do not require capping of the hydroxyl group portion of the single-ended allyl polyether, which is the raw material, and therefore the soft slabs currently being diverted to spray foam systems It has the advantage of being cheaper to manufacture than foam stabilizers. Nevertheless, as shown in Table 4 above, it outperforms F3 in terms of overall performance balance. Therefore, the foam enhancer of the present invention greatly contributes to the sound development of society and industry.
 [Low Emission性の確認]
本発明の泡増強剤SI-1~SI-3について、以下の手順に従ってヘッドスペースGC法により揮発性の環状シロキサン類(D4~D6)の分析を行った。
E1.サンプル約1gを20mLのバイアル瓶に秤量して、密封した。
E2.バイアルを150℃で30分間加熱後、ヘッドスペースサンプラーにて1mLのヘッドスペースをGCへ注入し測定した。
[Confirmation of Low Emission Properties]
The foam enhancers SI-1 to SI-3 of the present invention were analyzed for volatile cyclic siloxanes (D4 to D6) by the headspace GC method according to the following procedure.
E1. About 1 g of sample was weighed into a 20 mL vial and sealed.
E2. After heating the vial at 150° C. for 30 minutes, 1 mL of headspace was injected into GC using a headspace sampler and measured.
上記のGCにおける分析結果を、以下の表5にまとめた。環状シロキサンの各成分は夫々0.10%(1000ppm)を大きく下回っており、Low Emissionの観点から問題のないことを確認できた。
[表5]:本発明の泡増強剤の揮発性シロキサン含有量(単位:wt.ppm)
Figure JPOXMLDOC01-appb-T000010

The analysis results in the above GC are summarized in Table 5 below. Each component of the cyclic siloxane was well below 0.10% (1000 ppm), and it was confirmed that there was no problem from the viewpoint of Low Emission.
Table 5: Volatile siloxane content of foam boosters of the invention (unit: wt.ppm)
Figure JPOXMLDOC01-appb-T000010

以下は、本発明の泡増強剤の使用に適した、水100倍発泡ポリウレタン断熱用スプレーフォーム形成用組成物の処方例である。
[表6]:軟質ポリウレタン断熱用スプレーフォーム形成用組成物(水100倍発泡)
なお、下表の成分a)は、「分子内の平均水酸基数が2~4であり、オキシプロピレン基からなる繰り返し単位を有し、数平均分子量が1000~6000の範囲内にある、1種類以上のポリエーテルポリオール」の要件を満たすものである。また、下表の処方2及び処方3のイソシアナート指数の計算値は約30である。
Figure JPOXMLDOC01-appb-T000011
The following is a formulation example of a composition for forming a 100 times water expanded polyurethane thermal insulation spray foam suitable for use with the foam enhancer of the present invention.
[Table 6]: Composition for forming flexible polyurethane thermal insulation spray foam (100-fold expansion with water)
In addition, component a) in the table below is "one type having an average number of hydroxyl groups in the molecule of 2 to 4, having a repeating unit consisting of an oxypropylene group, and having a number average molecular weight within the range of 1000 to 6000. It satisfies the above polyether polyol requirements. Also, the calculated isocyanate index for Formulation 2 and Formulation 3 in the table below is about 30.
Figure JPOXMLDOC01-appb-T000011

Claims (13)

  1. 一般式(1):
    Figure JPOXMLDOC01-appb-C000001
    {式中、Rは各々独立にアルキル、アリール、アラルキル基から選択される炭素原子数1~16の1価の炭化水素基を表し、
    Xは、各々独立に式:-C2kO-(CO)p(CO)q(CO)r-Yで示される1種類または2種類以上のポリエーテル基を表し、
    Yは、100モル%がH基であるか、75モル%以上のH基と25モル%以下のC1~C4アルキル又はアセチル基から選ばれるその他の基からなり、
    m、n、k、p、q 、r は以下の条件を満たす数である。
    12≦(m+n)≦230、
    10≦m、
    2≦n、
    n≦m、
    3≦k≦4、
    p、q、rは、Xで表されるポリエーテル基部分の式量が1400~4000の範囲内にあり、
    {(CO)qで表されるオキシプロピレン基部分および(CO)rで表されるオキシブチレン基部分の式量の和}/{(CO)pで表されるオキシエチレン基部分の式量の和)}である比の値Zが、
    (51/49)≦Z≦(95/5)の条件を満たす数である。
    ただし、式中のXにおいて、1≦pかつq=r=0である構造を有するポリエーテル基は除く。}
    で表されるシリコーンポリエーテル共重合体を含有する泡増強剤であって、以下のa)~d)成分を含む水発泡型ポリウレタンスプレーフォームシステムに適用されるもの:
    a)分子内の平均水酸基数が2~4であり、オキシプロピレン基からなる繰り返し単位を有し、数平均分子量が1000~6000の範囲内にある、1種類以上のポリエーテルポリオール、
    b)ポリイソシアネート、
    c)硬化触媒、
    d)水である発泡剤 同システム中の成分a)であるポリエーテルポリオールおよびその他のポリオール成分の和 100質量部に対して10~40質量部の範囲。
    General formula (1):
    Figure JPOXMLDOC01-appb-C000001
    {wherein each R independently represents a monovalent hydrocarbon group having 1 to 16 carbon atoms selected from alkyl, aryl and aralkyl groups,
    Each X is independently one or more of the formula: -C k H 2k O-(C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r -Y represents the polyether group of
    Y is 100 mol % of H groups, or consists of 75 mol % or more of H groups and 25 mol % or less of other groups selected from C1-C4 alkyl or acetyl groups;
    m, n, k, p, q, and r are numbers satisfying the following conditions.
    12≦(m+n)≦230,
    10≦m,
    2≦n,
    n≦m,
    3≤k≤4,
    p, q, and r have a formula weight of the polyether group moiety represented by X in the range of 1400 to 4000,
    {sum of the formula weights of the oxypropylene group moiety represented by ( C3H6O )q and the oxybutylene group moiety represented by ( C4H8O )r}/ { ( C2H4O )p The sum of the formula weights of the oxyethylene group moieties represented by)} is the ratio value Z,
    It is a number that satisfies the condition (51/49)≤Z≤(95/5).
    However, in X in the formula, a polyether group having a structure where 1≤p and q=r=0 is excluded. }
    A foam booster containing a silicone polyether copolymer of the formula for application in water-blown polyurethane spray foam systems comprising the following components a)-d):
    a) one or more polyether polyols having an average number of hydroxyl groups in the molecule of 2 to 4, having repeating units composed of oxypropylene groups, and having a number average molecular weight in the range of 1,000 to 6,000;
    b) polyisocyanates,
    c) a curing catalyst,
    d) Blowing agent, which is water: 10 to 40 parts by mass per 100 parts by mass of the sum of polyether polyol and other polyol components, which is component a) in the same system.
  2. 前記一般式(1)において、
    Xが、各々独立に式:-CO(CO)p(CO)q-H
    で示される1種類または2種類以上のポリエーテル基であり、
    Xで表されるポリエーテル基部分の式量が1500~2500の範囲内にあり、かつ、
    前記の比Zが(54/46)≦Z≦(80/20)の条件を満たす、
    請求項1に記載の泡増強剤。
    In the general formula (1),
    each X independently of the formula: -C 3 H 6 O(C 2 H 4 O) p (C 3 H 6 O) q -H
    One or two or more polyether groups represented by
    The formula weight of the polyether group portion represented by X is in the range of 1500 to 2500, and
    The ratio Z satisfies the condition of (54/46)≤Z≤(80/20),
    2. The foam enhancer of claim 1.
  3. 前記一般式(1)において、Rがメチル基であり、m、nが、40≦m≦90、かつ、2≦n≦8の条件を満たす、
    請求項1または請求項2に記載の泡増強剤。
    In the general formula (1), R is a methyl group, m and n satisfy the conditions of 40 ≤ m ≤ 90 and 2 ≤ n ≤ 8,
    3. The foam enhancer according to claim 1 or claim 2.
  4. 前記の水発泡型ポリウレタンスプレーフォームシステムにおいて、
    b)ポリイソシアネートが、MDI(ジフェニルメタンジイソシアネート)、ポリメリックMDI(ポリメチレンポリフェニルポリイソシアネート),クルードMDI,イソシアナート基含有プレポリマー、およびこれらの誘導体から選ばれる成分であり、かつ、
    同システムの発泡剤がd)水のみであることを特徴とする、
    請求項1~3のいずれか1項に記載の泡増強剤。
    In said water-blown polyurethane spray foam system,
    b) the polyisocyanate is a component selected from MDI (diphenylmethane diisocyanate), polymeric MDI (polymethylene polyphenyl polyisocyanate), crude MDI, isocyanate group-containing prepolymers, and derivatives thereof, and
    characterized in that the blowing agent in the system is d) water only,
    The foam enhancer according to any one of claims 1-3.
  5. 前記のa)~d)成分、およびe)請求項1~4のいずれか1項に記載の泡増強剤を含む、ポリウレタンスプレーフォームシステム用のプレミックス液。 A premix fluid for a polyurethane spray foam system comprising components a)-d) above and e) a foam booster according to any one of claims 1-4.
  6. a´) a)成分であるポリエーテルポリオール以外の、少なくとも1つ以上のポリオール成分 を更に含有する、請求項5に記載のポリウレタンスプレーフォームシステム用のプレミックス液。 6. The premix liquid for a polyurethane spray foam system according to claim 5, further comprising at least one or more polyol components other than the polyether polyol as component a').
  7. f) ノニオン性の界面活性剤を更に含有する、請求項6に記載のポリウレタンスプレーフォームシステム用のプレミックス液。 f) The premix liquid for a polyurethane spray foam system according to claim 6, further containing a nonionic surfactant.
  8. 前記のa)~d)成分、およびe)請求項1~4のいずれか1項に記載の泡増強剤を含み、任意で、前記の成分a´)および成分f)から選ばれる1種類以上をさらに含んでもよい、ポリウレタン発泡体形成用組成物。 components a) to d) above, and e) a foam booster according to any one of claims 1 to 4, optionally one or more selected from components a') and component f) above. A composition for forming a polyurethane foam, further comprising:
  9. g)難燃剤をさらに含み、任意でh)その他の添加剤を含んでもよい、請求項8に記載のポリウレタン発泡体形成用組成物。 9. The polyurethane foam-forming composition of Claim 8, further comprising g) a flame retardant and optionally h) other additives.
  10. 請求項8または請求項9に記載のポリウレタン発泡体形成用組成物を硬化させてなる、軟質ポリウレタン発泡体。 A flexible polyurethane foam obtained by curing the composition for forming a polyurethane foam according to claim 8 or 9.
  11. Low Emission/Low VOC特性を有する、請求項10に記載の軟質ポリウレタン発泡体。 11. The flexible polyurethane foam according to claim 10, having Low Emission/Low VOC properties.
  12. 請求項10または請求項11に記載の軟質ポリウレタン発泡体を有する断熱材又は吸音材。 A heat insulating or sound absorbing material comprising the flexible polyurethane foam according to claim 10 or claim 11.
  13. 一般式(1):
    Figure JPOXMLDOC01-appb-C000002
    {式中、Rは各々独立にアルキル、アリール、アラルキル基から選択される炭素原子数1~16の1価の炭化水素基を表し、
    Xは、各々独立に式:-C2kO-(CO)p(CO)q(CO)r-Yで示される1種類または2種類以上のポリエーテル基を表し、
    Yは、100モル%がH基であるか、75モル%以上のH基と25モル%以下のC1~C4アルキル又はアセチル基から選ばれるその他の基からなり、
    m、n、k、p、q 、r は以下の条件を満たす数である。
    12≦(m+n)≦230、
    10≦m、
    2≦n、
    n≦m、
    3≦k≦4、
    p、q、rは、Xで表されるポリエーテル基部分の式量が1400~4000の範囲内にあり、
    {(CO)qで表されるオキシプロピレン基部分および(CO)rで表されるオキシブチレン基部分の式量の和}/{(CO)pで表されるオキシエチレン基部分の式量の和)}である比の値Zが、
    (51/49)≦Z≦(95/5)の条件を満たす数である。
    ただし、式中のXにおいて、1≦pかつq=r=0である構造を有するポリエーテル基は除く。}
    で表されるシリコーンポリエーテル共重合体を含有する泡増強剤を使用することを特徴とする、ポリウレタン発泡体の疎水性の改善方法。
    General formula (1):
    Figure JPOXMLDOC01-appb-C000002
    {wherein each R independently represents a monovalent hydrocarbon group having 1 to 16 carbon atoms selected from alkyl, aryl and aralkyl groups,
    Each X is independently one or more of the formula: -C k H 2k O-(C 2 H 4 O) p (C 3 H 6 O) q (C 4 H 8 O) r -Y represents the polyether group of
    Y is 100 mol % of H groups, or consists of 75 mol % or more of H groups and 25 mol % or less of other groups selected from C1-C4 alkyl or acetyl groups;
    m, n, k, p, q, and r are numbers satisfying the following conditions.
    12≦(m+n)≦230,
    10≦m,
    2≦n,
    n≦m,
    3≤k≤4,
    p, q, and r have a formula weight of the polyether group moiety represented by X in the range of 1400 to 4000,
    {sum of the formula weights of the oxypropylene group moiety represented by ( C3H6O )q and the oxybutylene group moiety represented by ( C4H8O )r}/ { ( C2H4O )p The sum of the formula weights of the oxyethylene group moieties represented by)} is the ratio value Z,
    It is a number that satisfies the condition (51/49)≤Z≤(95/5).
    However, in X in the formula, a polyether group having a structure where 1≤p and q=r=0 is excluded. }
    A method for improving the hydrophobicity of a polyurethane foam, characterized by using a foam booster containing a silicone polyether copolymer represented by:
PCT/JP2021/023397 2021-06-21 2021-06-21 Foam booster, premix solution including same, composition for polyurethane foam molding including these, and polyurethane foam with improved hydrophobicity WO2022269684A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008174689A (en) * 2007-01-22 2008-07-31 Toyo Tire & Rubber Co Ltd Polyol composition for open-cell rigid polyurethane foam and production method of open-cell rigid polyurethane foam
JP2010270877A (en) * 2009-05-25 2010-12-02 Bridgestone Corp Spray heat insulating material
US20120157558A1 (en) * 2010-12-16 2012-06-21 Evonik Goldschmidt Gmbh Silicone stabilizers for rigid polyurethane or polyisocyanurate foams
JP2014071147A (en) * 2012-09-27 2014-04-21 Tokai Rubber Ind Ltd Tonner supply roll for electrophotographic equipment
JP2016044269A (en) * 2014-08-25 2016-04-04 日本発條株式会社 Polyurethane foam
WO2018074257A1 (en) * 2016-10-18 2018-04-26 東レ・ダウコーニング株式会社 Polyether-modified silicone composition, surfactant, foam stabilizer, polyurethane foam forming composition, and cosmetic preparation including said composition, and method for producing said composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008174689A (en) * 2007-01-22 2008-07-31 Toyo Tire & Rubber Co Ltd Polyol composition for open-cell rigid polyurethane foam and production method of open-cell rigid polyurethane foam
JP2010270877A (en) * 2009-05-25 2010-12-02 Bridgestone Corp Spray heat insulating material
US20120157558A1 (en) * 2010-12-16 2012-06-21 Evonik Goldschmidt Gmbh Silicone stabilizers for rigid polyurethane or polyisocyanurate foams
JP2014071147A (en) * 2012-09-27 2014-04-21 Tokai Rubber Ind Ltd Tonner supply roll for electrophotographic equipment
JP2016044269A (en) * 2014-08-25 2016-04-04 日本発條株式会社 Polyurethane foam
WO2018074257A1 (en) * 2016-10-18 2018-04-26 東レ・ダウコーニング株式会社 Polyether-modified silicone composition, surfactant, foam stabilizer, polyurethane foam forming composition, and cosmetic preparation including said composition, and method for producing said composition

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