JP2020002382A - Foam stabilizer, and polyurethane foam body formation composition containing the same - Google Patents

Abstract

To provide a foam stabilizer effectively inhibiting generation of odor causative material such as aldehyde and capable of forming a polyurethane foam extremely less in odorization and odor, when used as a foam stabilizer for polyurethane foam, and a polyurethane foam body formation composition and a polyurethane foam body.SOLUTION: There is provided a foam stabilizer containing a polyoxyalkylene modified polysiloxane compound obtained by a manufacturing method including a process [A] for synthesizing the polyoxyalkylene modified polysiloxane compound, and a process [B] for removing an odor causative material by treating the polyoxyalkylene modified polysiloxane compound in a presence of (c) one or more kind of acidic inorganic salt, which is solid at 25°C, is water soluble, and has pH of a solution when 50 g is dissolved in ion exchange water of 1 L at 25°C of 4 or less, and a polyurethane foam body formation composition containing the same.SELECTED DRAWING: None

Description

The present invention relates to a foam stabilizer containing a polyoxyalkylene-modified polysiloxane composition which has been deodorized by using a specific acidic inorganic salt (including a function as a foam control agent and a foam stabilizer, the same applies hereinafter); The present invention relates to a polyurethane foam-forming composition containing a foaming agent, and a polyurethane foam obtained therefrom.

The average molecular weight of the polyoxyalkylene-modified polysiloxane can be designed, and the EO% and size of the polyoxyalkylene portion, the introduction of a hydroxyl group or a hydrophobic group into the silicone terminal, the modification with two or more different polyether groups, and the like can be used. Can control surface activity, compatibility with foaming agents, affinity for urethane foam systems, etc., so that rigid foam, semi-rigid foam, HR (high elasticity) foam, flexible foam, microcellular foam, etc. It is useful as a foam control or foam stabilizing surfactant in all polyurethane foam (sometimes abbreviated herein as "urethane foam" or "foam") material formulations.

On the other hand, in recent years, there has been a concern that volatile organic substances generated from building materials, automobile interior materials, and the like may adversely affect the human body due to increasing interest in environmental influences. Polyurethane foams used for these building materials, automobile interior materials and the like often contain the volatile organic substance, and there is an increasing demand to reduce the content as much as possible. Further, from the viewpoint of the usability of the polyurethane foam and practical reasons, there is a strong demand in the market for a polyurethane foam which does not contain a volatile odor-causing substance and whose generation is suppressed with time. Furthermore, as market needs in recent years, demand for low emission properties, that is, “Low Emission characteristics” has been increasing. This is a required characteristic characterized by a small amount of components such as chemical substances generated or volatilized from the polyurethane foam, and specifically, a small amount of volatile components generated from the foam (= Low VOC (Volatile) Organic Compound)), a small amount of chemical substances released from the foam over time to prevent sick house allergy and the like (= Low Emission of Chemical Compound), a component volatilized from the foam used inside the automobile. It is sometimes expressed as a requirement such as a phenomenon that fogging of window glass or the like due to the adhesion of glass (= Low fogging) does not occur. However, excluding the difference in the types and properties of chemical substances, the emission components derived from foams In the sense that there is little They are the same.

Here, a polyoxyalkylene-modified polysiloxane useful as a foam stabilizer is usually an addition reaction of an organohydrogensiloxane and a polyether compound having a double bond at a molecular chain terminal under a noble metal catalyst such as chloroplatinic acid. Manufactured by letting By subjecting the polyoxyalkylene-modified polysiloxane obtained by the production method to an acid treatment and a hydrogenation treatment, generation of volatile propionaldehyde, which is an odor-causing substance, is suppressed. There has been proposed a foam stabilizer for polyurethane foams in which the amount of harmful aldehydes generated in the process is extremely small (Patent Document 1). However, polyurethane foams used for automobile interior materials and the like may still generate odor and odor over time, and there is a need for a foam stabilizer that can further reduce odor.

In addition, the applicants disclose in Patent Document 2 a method for producing a polyoxyalkylene-modified polysiloxane composition which produces very little odor over time, and a makeup containing the deodorized composition obtained by this production method. We propose raw materials. However, the document does not describe or suggest any polyurethane foam and foam stabilizer.

JP 2007-186557 A JP 2011-116902 A

The present invention has been made to solve the above problems, and when used as a foam stabilizer for polyurethane foam, effectively suppresses the generation of odor-causing substances such as aldehydes, and has a very low odor and odor. Is provided. Also provided are a polyurethane foam-forming composition and a polyurethane foam containing the same.

In order to solve the above problems, the present inventors have conducted intensive studies and found that a) a polyoxyalkylene compound having a carbon-carbon double bond at the terminal of a molecular chain and (b) an organohydrogenpolysiloxane are hydrosilylated. Step (A) of synthesizing the polyoxyalkylene-modified polysiloxane composition by reacting the polyoxyalkylene-modified polysiloxane composition with (c) a solid at 25 ° C., water-soluble, and 50 g of ionic A step of removing an odor-causing substance by treating in the presence of one or more acidic inorganic salts, wherein the pH of the aqueous solution at 25 ° C. when dissolved in 1 L of exchanged water is 4 or less [B And a foam stabilizer including the polyoxyalkylene-modified polysiloxane composition obtained by the production method. Further, the object of the present invention is achieved by a polyurethane foam-forming composition and a polyurethane foam containing the above-mentioned foam stabilizer.

In particular, the object of the present invention can be suitably achieved by using, as the component (c), one or more acidic inorganic salts selected from the group consisting of sodium hydrogen sulfate, potassium hydrogen sulfate and ammonium hydrogen sulfate. . Further, an object of the present invention is to carry out the step [A], the step [B] and the step [C] of deodorizing the polyoxyalkylene-modified polysiloxane composition by a hydrogenation reaction in the presence of a hydrogenation catalyst. It can be more suitably achieved by a foam stabilizer containing the polyoxyalkylene-modified polysiloxane composition obtained by the production method including the above. The foam stabilizer may further include a polyol, a polyglycol or a derivative thereof, a silicone oil, and a nonionic surfactant (excluding the polyoxyalkylene-modified polysiloxane composition) for the purpose of a dispersion medium or other functions. And one or more selected from antioxidants.

The object of the present invention is to
(A) a polyol,
(B) polyisocyanate,
(C) a catalyst,
(D) a foam stabilizer described above, and (e) optionally, a foam stabilizer other than the component (d), a foaming agent, a diluent, a chain extender, a crosslinking agent, water, a non-aqueous foaming agent, a filler, Contains at least one additive component selected from the group consisting of reinforcing agents, pigments, dyes, colorants, flame retardants, antioxidants, anti-ozonants, ultraviolet stabilizers, antistatic agents, bactericides and antibacterial agents Low, which is a polyurethane foam-forming composition, a polyurethane foam obtained by the polyurethane foam-forming composition, particularly a rigid foam, a semi-rigid foam, an HR (high elasticity) foam, a flexible foam, or a microcellular foam. It is preferably achieved by a polyurethane foam having Emission properties.

The foam stabilizer of the present invention is useful in the production of polyurethane foam as a foam stabilizer for polyurethane foam, since when blended into a polyurethane foam, the odor-causing substance generated over time is extremely small. Further, the polyurethane foam obtained by using the foam stabilizer of the present invention hardly generates unpleasant odor or odor, and thus is particularly useful for building materials, automobile industry (for example, automobile interior materials), beds, sofas and the like. It can be suitably used for a polyurethane foam applied to furniture, bedding, clothing, and the like.

Hereinafter, the method for producing a foam stabilizer of the present invention, a polyurethane foam-forming composition containing the foam stabilizer, and a polyurethane foam obtained by blending the composition will be described in detail.

The foam stabilizer according to the present invention includes a polyoxyalkylene-modified polysiloxane composition obtained by treating with a specific acidic inorganic salt and removing an odor-causing substance, and preferably, the foam stabilizer is It is preferable that the composition be composed only of the polyoxyalkylene-modified polysiloxane composition.

The method for producing the polyoxyalkylene-modified polysiloxane composition,
(A) a polyoxyalkylene compound having a carbon-carbon double bond at a terminal of a molecular chain;
(B) a step [A] of synthesizing a polyoxyalkylene-modified polysiloxane composition by subjecting an organohydrogenpolysiloxane to a hydrosilylation reaction; and
(C) one or more acidic compounds, which are solid at 25 ° C., are water-soluble, and have a pH of 4 or less at 25 ° C. of an aqueous solution when 50 g is dissolved in 1 L of ion-exchanged water. Step of removing odor-causing substances by treating in the presence of an inorganic salt [B]
It is characterized by having.

<Step [A]>
Step [A] is a step of synthesizing a crude product of a polyoxyalkylene-modified polysiloxane composition, which comprises (a) a polyoxyalkylene compound having a carbon-carbon double bond at a molecular chain terminal, and (b) an organohydrogen compound. The reaction is carried out by subjecting genpolysiloxane to a hydrosilylation reaction.

Component (a) is a polyoxyalkylene compound having a carbon-carbon double bond at the terminal of the molecular chain. In addition to the polyoxyalkylene-modified polysiloxane according to the present invention, the component (a) It is a component imparting hydrophilicity derived from an oxyalkylene bond, and is introduced into component (b) by a hydrosilylation reaction.

Examples of the polyoxyalkylene compound having a terminal double bond include a compound represented by the following general formula: R ³ O (R ⁴ O) _a R ³ . In the above formula, R ³ is a hydrogen atom or a monovalent hydrocarbon group, at least one of which is an alkenyl group having a terminal double bond such as a vinyl group or a hexenyl group, and one of R ³ has 2 to 2 carbon atoms. It is preferably an alkenyl group having 12 terminal double bonds. Other monovalent hydrocarbon groups include saturated aliphatic hydrocarbon groups such as alkyl groups having 1 to 12 carbon atoms; saturated alicyclic hydrocarbon groups such as cyclopentyl group and cyclohexyl group; phenyl group, tolyl group, Examples include aromatic hydrocarbon groups such as a naphthyl group and / or a group in which a hydrogen atom bonded to a carbon atom of these groups is partially substituted with a halogen atom or an organic group containing an epoxy group, a carboxyl group, or a methacryl group. You. Preferably, one R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ⁴ is a substituted or unsubstituted divalent hydrocarbon group, and examples include an ethylene group, a propylene group, a butylene group, a pentylene group, a phenylene group, and an alkyl-substituted phenylene group. a is 0 or a positive integer, preferably 1 to 300, more preferably 1 to 100.

From the viewpoint of use as a foam stabilizer, the component (a) contains at least one or more polyoxyalkylene units selected from oxyethylene (EO) groups, oxypropylene (PO) groups and oxybutylene (BO) groups. Is preferred.
Particularly preferably, the following structural formula (1):
_{CH 2 = CH-C p H} 2p O- (C 2 H 4 O) t1 (C 3 H 6 O) t2 (C 4 H 8 O) t3 -Y (1)
And a linear polyoxyalkylene compound represented by the formula:

In the structural formula (1), p is the number of carbon atoms of an alkylene group bonded to a silicon atom excluding a vinyl group portion which is a terminal double bond, and 0 ≦ p ≦ 6, and the same functional group is derived from an alkenyl group. In this case, the number is preferably in the range of 0 to 4. Y is a terminal group of a polyoxyalkylene structure, and is selected from a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a COCH ₃ group. Y is preferably a hydrogen atom or a methyl group from the viewpoint of usefulness as a foam stabilizer and stability and safety of the modified silicone.

t1, t2 and t3 are the numbers of oxyethylene units, oxypropylene units and oxybutylene units constituting the polyoxyalkylene structure, and are numbers satisfying 2 ≦ t1 + t2 + t3 ≦ 110, preferably 2 ≦ t1 + t2 + t3 ≦ 50. And more preferably 2 ≦ t1 + t2 + t3 ≦ 40. t1, t2, and t3 are 0 ≦ t1 ≦ 60, 0 ≦ t2 ≦ 50, and 0 ≦ t3 ≦ 50, respectively.

The terminal structure of the component (a), which is an alkenyl group bonded to a silicon atom by a hydrosilylation reaction and having 3 or more carbon atoms, and an alkylene portion constituting an oxypropylene unit or an oxybutylene unit, are directly It may be a chain hydrocarbon group or a branched hydrocarbon group (for example, an isopropylene group or an isobutylene group).

The preferred polyoxyalkylene-modified polysiloxane obtained by using the above component (a) has a particularly improved emulsifying power and can contain a certain amount of oxypropylene units or oxybutylene units. Therefore, the compatibility between the foaming agent and the polyol or isocyanate, which is the main component of the polyurethane foam-forming composition, is improved, and this is advantageous in that the stability of the premix solution is improved, the convenience is increased, and a desired foaming effect is obtained. It becomes. Furthermore, the function as a foam stabilizer and the handleability during or after synthesis are also improved.

Component (b) is an organohydrogenpolysiloxane, and the organohydrogenpolysiloxane used in the present invention may be any as long as it contains at least one silicon-bonded hydrogen atom in one molecule. The constituent siloxane unit is represented by the general formula: R ¹ _a SiO _{(4-a) / 2} . In the formula, R ¹ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. Specific examples of the monovalent hydrocarbon group include alkyl groups having 1 to 30 carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, A saturated alicyclic hydrocarbon group represented by a cycloalkyl group having 3 to 20 carbon atoms such as a cyclopentyl group and a cyclohexyl group; a phenyl group, a tolyl group, An aromatic hydrocarbon group such as a naphthyl group, a phenylethyl group, an alkylbenzyl group and / or a hydrogen atom bonded to a carbon atom of these groups is partially a halogen atom or an epoxy group, a carboxyl group, an amino group, a methacryl group, A group substituted by an organic group including a mercapto group is exemplified, and may be the same or different.

R ¹ is preferably an alkyl group, more preferably a methyl group. However, at least one of R ^{1 in} the siloxane unit constituting the organohydrogenpolysiloxane as the component (b) is a hydrogen atom. a is 0 <a ≦ 3 on average. The molecular structure of such an organohydrogenpolysiloxane is not limited, and examples thereof include linear, partially branched linear, branched, cyclic, and dendritic, and preferably linear. The molecular weight is not particularly limited, and a low molecular weight to a high molecular weight can be used. Specifically, the number average molecular weight is preferably in the range of 100 to 1,000,000, and more preferably in the range of 300 to 500,000.

式中、Ｒ^２は置換もしくは非置換の一価炭化水素基であり、具体的には、前記Ｒ^１で例示したのと同様の基が挙げられる。ｘは０または正の整数であり、ｙは正の整数であり、ｚは０または正の整数である。 As such an organohydrogenpolysiloxane, an organohydrogenpolysiloxane represented by the following structural formula is exemplified. These organohydrogenpolysiloxanes include (i) a linear organosiloxane having a silicon-bonded hydrogen atom at only a side chain, (ii) one end of a side chain or a molecular chain, and (iii) both ends of a side chain or a molecular chain. 1 shows the structure of hydrogen polysiloxane.

In the formula, R ² is a substituted or unsubstituted monovalent hydrocarbon group, and specific examples thereof include the same groups as those exemplified for R ¹ . x is 0 or a positive integer, y is a positive integer, and z is 0 or a positive integer.

式中、Ｒ^２は置換もしくは非置換の一価炭化水素基であり、前記Ｒ^１で例示したのと同様の基が挙げられるが、特に、Ｒ^２は炭素原子数１〜３０のアルキル基であることが好ましく、全てのＲ^２の少なくとも５０モル％がメチル基であることが特に好ましい。また、ウレタンシステム（ポリウレタン発泡体形成性組成物の硬化に関与する原料成分および硬化機構）との相溶性の改善等を目的として、メチル基以外のＲ^２として、炭素原子数８〜３０の中鎖または長鎖アルキル基を選択してもよく、かつ好ましい。 In the present invention, as a linear organohydrogenpolysiloxane that can be particularly preferably used, a linear polysiloxane represented by the following structural formula (2) is exemplified. One of these organohydrogenpolysiloxanes may be used alone, or two or more thereof may be used in combination.
Structural formula (2):

In the formula, R ² is a substituted or unsubstituted monovalent hydrocarbon group, and examples thereof include the same groups as those exemplified for R ¹ above. In particular, R ² is an alkyl group having 1 to 30 carbon atoms. It is particularly preferred that at least 50 mol% of all R ² is a methyl group. Further, for the purpose of improvement of compatibility with the urethane system (starting components and cure mechanism are involved in the curing of the polyurethane foam forming composition), as R ² other than a methyl group, in the carbon atoms 8 to 30 A chain or long chain alkyl group may be selected and preferred.

In the formula, R is a group selected from a hydrogen atom or R ² , and is particularly preferably a hydrogen atom or a methyl group. m is a number in the range of 0 to 1000, preferably a number in the range of 1 to 500, and more preferably a number in the range of 1 to 300. n is a number in the range of 0 to 200, and preferably in the range of 1 to 150. However, when n = 0, at least one of R is a hydrogen atom. In particular, it is preferable that n and m are numbers in the range of 2 ≦ m + n ≦ 230. Further, it is more preferable that m> n, 25 ≦ m + n ≦ 230, and n is a number in the range of 1 to 50. Furthermore, when at least one of R is a monovalent hydrocarbon group represented by R ^2, n is particularly preferably a number ranging from 1 to 40.

The hydrosilylation reaction for synthesizing the polyoxyalkylene-modified polysiloxane composition can be performed in the presence or absence of a solvent according to a known method. Here, as the reaction solvent, alcohol solvents such as ethanol and isopropyl alcohol; aromatic hydrocarbon solvents such as toluene and xylene; ether solvents such as dioxane and THF; n-hexane, cyclohexane, n-heptane, and cyclohexane Examples thereof include aliphatic hydrocarbon solvents such as heptane and methylcyclohexane; and chlorinated hydrocarbon solvents such as carbon tetrachloride. In addition, one or more specific monol organics described below, which are liquid at 5 ° C., have one alcoholic hydroxyl group in the molecule, and do not contain a hetero atom other than oxygen. The compound may be used as a solvent.

The hydrosilylation reaction may be performed in the absence of a catalyst, but is preferably performed in the presence of a catalyst because the reaction proceeds at a low temperature in a short time. Examples of such a catalyst include compounds such as platinum, ruthenium, rhodium, palladium, osmium, and iridium. A platinum compound is particularly effective because of its high catalytic activity. Examples of the platinum compound include chloroplatinic acid; metal platinum; metal platinum supported on a carrier such as alumina, silica, and carbon black; platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-phosphite complex And a platinum complex such as a platinum alcoholate catalyst. When a platinum catalyst is used, the amount of the catalyst is about 0.0001 to 0.1% by mass as platinum metal, and the range of 0.0005 to 0.05% by mass is suitable, but not limited thereto. .

The reaction temperature of the hydrosilylation reaction is usually 50 to 150 ° C., and the reaction time is generally 10 minutes to 24 hours, preferably 1 to 10 hours.

When performing the above-mentioned hydrosilylation reaction, the ratio of [substance amount of carbon-carbon double bond in component (a) / substance amount of silicon-bonded hydrogen atom in component (b)] is 1.0 to 2.0. A range where the value is 0 can be exemplified. That is, when synthesizing the polyoxyalkylene-modified polysiloxane composition according to the present invention, it is preferable to use an excessive amount of the component (a). More specifically, the ratio of the above components (a) and (b) is preferably in a range of 1.05 to 1.75, and more preferably in a range of 1.10 to 1.55. Such a polyoxyalkylene-modified polysiloxane composition is a mixture of the polyoxyalkylene-modified polysiloxane and the unreacted component (a), and these components are excellent in compatibility and can be obtained as a uniform composition. . After the step [B] and optional step [C] described below, the composition can be used as a foam stabilizer as a uniform composition, and can be blended into a urethane foam formulation.

On the other hand, when the above ratio is less than 1.0, unreacted component (b) remains in the polyoxyalkylene-modified polysiloxane composition according to the present invention. When such a polyoxyalkylene-modified polysiloxane composition is used as a foam stabilizer, the remaining component (b) reacts with another urethane raw material, causing hydrogen gas to be generated. This causes undesired effects such as alteration, fire, and expansion of the container. Therefore, in order for the organohydrogenpolysiloxane to react completely, the above ratio exceeds 1.0, that is, the component (a) to be introduced as a polyoxyalkylene group is reacted in excess of 1 equivalent and in excess. Is preferred.

As an example, in the step [A], (a) a linear polyoxyalkylene compound represented by the above structural formula (1), (b) a linear organohydrogen poly- ylene represented by the above structural formula (2) When siloxane is used and the above hydrosilylation reaction is carried out in such an amount that the amount of the component (a) becomes excessive with respect to the silicon-bonded hydrogen atoms in the component (b), the polyoxy group represented by the following structural formula is obtained. An alkylene-modified polysiloxane is synthesized, and a crude product of the polyoxyalkylene-modified polysiloxane composition according to the present invention containing the polyoxyalkylene-modified polysiloxane and the unreacted component (a) is obtained.

Wherein, ^{R 2} is the same groups, R '' is _{-C 2 H 4 -C p H 2p} O- (C 2 H 4 O) t1 (C 3 H 6 O) t2 (C 4 H 8 O) a polyoxyalkylene group represented by _t3- Y, wherein the range of values of p, t1, and t2 is the same as described above, and Y is the same group as described above. R ′ is a monovalent hydrocarbon group represented by R ² or a group represented by R ″. m and n are the same as defined in the structural formula (2). However, when n = 0, at least one of R ′ is a group represented by R ″.

<Step (B)>
Step (B) is a characteristic step of the method for producing the polyoxyalkylene-modified polysiloxane composition according to the present invention, and the composition is hydrolyzed using a specific acidic inorganic salt to obtain a polysiloxane. Almost no cleavage of the silicon-oxygen bond or the carbon-oxygen bond of the side chain portion constituting the main chain of the compound occurs, which is essential for reducing the odor of the composition and almost completely suppressing generation of odor over time. It is a process.

Specifically, the step (B) is a step of removing an odor-causing substance from a crude product of the polyoxyalkylene-modified polysiloxane composition by hydrolysis, and (c) is a solid at 25 ° C. And performing the treatment in the presence of one or more acidic inorganic salts, wherein the pH of the aqueous solution at 25 ° C. when 50 g is dissolved in 1 L of ion-exchanged water is 4 or less. Features. The pH value in the present invention is a pH value obtained by measuring a sample aqueous solution at room temperature (25 ° C.) using a pH meter using a glass electrode. "HM-10P" manufactured by Denpa Kogyo Co., Ltd. was used.

The acidic inorganic salt as the component (c) must be solid at 25 ° C., water-soluble, and have a pH of 4 or less when 50 g is dissolved in 1 L of ion-exchanged water. Yes, more preferably, the pH is preferably 3.5 or less, particularly preferably 2.0 or less. By hydrolyzing the composition using such a water-soluble acidic inorganic salt, the composition is deodorized with almost no cleavage of carbon-oxygen bond or silicon-oxygen bond, and the odor is reduced with time. Can be almost completely suppressed.

As the acidic inorganic salt as the component (c), for example, an acidic inorganic salt in which at least a monovalent hydrogen atom of a divalent or higher valent inorganic acid is neutralized with a base can be used. Examples of the divalent or higher inorganic acid include sulfuric acid and sulfurous acid. Examples of the base include an alkali metal and ammonia.

More specifically, the component (c) is at least one kind of acidic inorganic salt composed of a hydrogen sulfate ion (HSO ₄ ⁻ ) or a bisulfite ion (HSO ₃ ⁻ ) and a monovalent cation (M ⁺ ). Is preferable, and examples of the monovalent cation (M ⁺ ) include an alkali metal ion and an ammonium ion. Particularly preferably, one or more monovalent cations selected from the group consisting of sodium ion, potassium ion and ammonium ion are preferable. In addition, one kind of these acidic inorganic salts may be used alone, or two or more kinds may be used in combination. Furthermore, since these acidic inorganic salts are solid at room temperature (25 ° C.), they can be easily removed by filtration after the treatment. Further, since it is water-soluble, it can be easily washed off with water even in a washing step after production.

On the other hand, the hydrolysis treatment with an acetate, phosphate, or the like that does not satisfy the condition of the above-mentioned component (c) cannot sufficiently deodorize the hydrolyzed composition. On the other hand, the hydrolysis treatment with a strong acid such as hydrochloric acid or the hydrolysis treatment with a known solid acid such as zirconia sulfate can achieve a certain degree of low odor, but the carbon-oxygen bond or silicon- Breakage of oxygen bonds may occur.

Specific examples of the acidic inorganic salt as the component (c) include lithium hydrogen sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, rubidium hydrogen sulfate, cesium hydrogen sulfate, ammonium hydrogen sulfate, sodium hydrogen sulfite, and hydrates thereof. Illustrated. The pH of the aqueous solution when 50 g of such an acidic inorganic salt is dissolved in 1 L of ion-exchanged water is as shown in the table below. As a water-soluble acidic inorganic salt having a pH of 2.0 or less, one or more acidic inorganic salts selected from the group consisting of sodium hydrogensulfate, potassium hydrogensulfate, and ammonium hydrogensulfate are obtained from the technical effect of reducing odor. Use is most preferred.

The treatment in the presence of an acidic inorganic salt, which is a feature of the present invention, includes, for example, (1) a reaction system (for example, a reaction vessel such as a flask) of a polyoxyalkylene-modified polysiloxane composition synthesized by a hydrosilylation reaction. It means a decomposition treatment in which the above-mentioned acidic inorganic salt is added and stirred, and (2) a hydrolysis treatment in which an acidic inorganic salt and water or an acidic inorganic salt, water and an organic solvent are added and stirred.

In particular, after the above-mentioned step [A], an acidic inorganic salt and water are added to a reaction system containing a crude product of the polyoxyalkylene-modified polysiloxane composition according to the present invention, and the mixture is stirred using mechanical force. Is preferred. The hydrolysis treatment can be performed by selecting an arbitrary temperature and a treatment time, and at a temperature condition of 0 to 200 ° C, more preferably 50 to 100 ° C, 0.1 to 24 hours, more preferably 0.5 to 100 ° C. The reaction is preferably performed for a reaction time of about 10 hours. The amount of the acidic inorganic salt can be appropriately selected according to the treatment apparatus and the treatment time, but is preferably in the range of 1 to 500 ppm, more preferably in the range of 5 to 200 ppm, based on the polyoxyalkylene-modified polysiloxane composition. preferable.

The production method of the present invention preferably includes a stripping step of removing low-boiling components (propionaldehyde and the like) which are substances causing odor. Further, after the stripping, by performing the treatment again in the presence of the acidic inorganic salt, a larger amount of the propenyl ether group-containing polyoxyalkylene can be hydrolyzed, and the odor-causing substance, such as propionaldehyde, can be removed. . At this time, since the acidic inorganic salt remains, there is no need to newly add an acidic inorganic salt, and there is an advantage that only water needs to be added. That is, the step [B] and the stripping step can be repeatedly performed two or more times for the purpose of increasing the degree of odor reduction.

The "low-boiling substances" distilled off in the stripping step include, in addition to propionaldehyde, a substance causing odor, a hydrosilylation reaction (step [A]) or a hydrogenation reaction (step [C]) described later. And the reaction solvent used for the reaction.

The stripping step (distillation of low-boiling substances) may be carried out on the crude product of the polyoxyalkylene-modified polysiloxane composition as a step before the step [B], or after the step [B]. May be carried out on a polyoxyalkylene-modified polysiloxane composition or on a composition after a hydrogenation reaction thereof. Moreover, it can also be implemented as a step before and after the step [B], respectively. Preferably, the step [B] is preferably performed after the step [B] for the purpose of removing propionaldehyde, which is an odor-causing substance generated by the hydrolysis reaction.

As a removing method, stripping under normal pressure or reduced pressure is preferable, and it is preferable to perform the stripping at 120 ° C. or lower. For efficient stripping, the stripping is preferably performed under reduced pressure or under an injection of an inert gas such as nitrogen gas. If an example of the operation of distilling low-boiling substances is specifically shown, a crude product of a polyoxyalkylene-modified polysiloxane composition containing low-boiling substances or a hydrogenated product thereof is passed through a reflux condenser, a nitrogen inlet, or the like. , And the inside is decompressed while supplying nitrogen gas to increase the temperature, and the pressure and the temperature are kept constant to distill off light substances. Here, the reduced pressure condition is generally 0.1 to 10.0 KPa, the heating temperature is 50 to 170 ° C., and the processing time is generally 10 minutes to 24 hours.

After the desired low odor is achieved by the treatment in the presence of the acidic inorganic salt, neutralization treatment can be performed by adding a weak alkaline substance such as sodium bicarbonate, sodium carbonate, potassium carbonate, and sodium acetate. The weakly alkaline substance may be added after being dissolved in water or alcohol. The addition amount is preferably approximately equimolar to the acidic inorganic salt used, and the temperature during the neutralization treatment is in the range of room temperature to the boiling point of the solvent component present in the reaction system or lower, or 100 ° C or lower. It is preferable to carry out. The processing time is generally about 10 minutes to 3 hours. After the neutralization treatment, it is preferable to remove water and other light components by stripping under normal pressure or reduced pressure (refer to paragraph 0048 for conditions).

The polyoxyalkylene-modified polysiloxane composition of the present invention can be subjected to a hydrogenation treatment <Step [C]> as a step before or after the step [B] in the presence of the acidic inorganic salt. The deodorizing treatment by the hydrogenation reaction may be carried out by a hydrogenation reaction after the treatment in the presence of the acidic inorganic salt according to the step (B), or after the treatment by the hydrogenation reaction, The treatment may be carried out in the presence of the acidic inorganic salt according to the above step [B].

<Step [C]>
Step [C] is a step in which the polyoxyalkylene-modified polysiloxane composition after step [A] or step [B] is subjected to a hydrogenation reaction to reduce the odor. The hydrogenation reaction includes a method using hydrogen and a method using a metal hydride, and further includes a homogeneous reaction and a heterogeneous reaction. These can be performed alone or in combination. However, considering the advantage that the used catalyst does not remain in the product, a heterogeneous catalytic hydrogenation reaction using a solid catalyst is most preferable.

Here, as the solid catalyst (hydrogenation catalyst), a common noble metal catalyst such as a platinum catalyst and a palladium catalyst, and a nickel catalyst can be used. More specifically, a simple substance such as nickel, palladium, platinum, rhodium, and cobalt, and a combination of a plurality of metals such as platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-nickel, and nickel-molybdenum Can be exemplified. Activated carbon, silica, silica-alumina, alumina, zeolite and the like can be mentioned as an optional catalyst carrier. The amount of supported metal is 0.1 to 5% by mass, preferably 0 to 5% by mass in a noble metal catalyst system. 0.2 to 3% by mass, and 20 to 70% by mass, preferably 40 to 60% by mass for a nickel-based catalyst. Further, the platinum catalyst used in the synthesis step (hydrosilylation reaction) can be used as it is. These hydrogenation catalysts can be used alone or in combination of two or more.

In step [C] of the present invention, a suitable hydrogenation catalyst is a nickel-based catalyst, and is preferably a nickel / diatomaceous earth or Raney nickel catalyst. In particular, use of a Raney nickel catalyst is most preferable from the viewpoint of promoting deodorization by hydrogenation. The use of such a Raney nickel catalyst is economically superior to a noble metal catalyst, but since the Raney nickel catalyst is usually used after being developed with an alkali, the pH of the reaction solution must be particularly carefully measured. Further, since the inside of the reaction system becomes weakly alkaline, there is a practical advantage that it can be suitably used in the production method of the present invention in that the hydrolysis reaction with an acidic aqueous solution is particularly effective for deodorization.

The hydrogenation reaction can be carried out under normal pressure or under pressure, and is generally desirably carried out at 1 to 100 MPa and 50 to 200 ° C. In practice, the reaction is performed under hydrogen pressure (hydrogen pressure = 0.1 to 20 MPa (about 1 to 200 kg / cm ² ). The reaction temperature is preferably 50 to 170 ° C. from the viewpoint of shortening the reaction time. In addition, the hydrogenation reaction can be performed in the presence of a solvent, and the above-mentioned alcohol-based solvent, ether-based solvent, aliphatic hydrocarbon-based solvent, chlorinated hydrocarbon-based organic solvent and the like are appropriately selected and used. can do.

The hydrogenation reaction may be performed in any of a batch system and a continuous system. The reaction time in the case of performing the batch method varies depending on the amount of the catalyst and the reaction temperature, but is generally in the range of 3 to 12 hours.
In the case of performing the batch method, the end point of the hydrogenation reaction can be the time point when the decrease in the hydrogen pressure is hardly observed by carefully observing the pressure gauge and the time point when the reaction is further performed for 1 to 2 hours. When the hydrogen pressure decreases during the reaction, it is preferable to introduce hydrogen gas again and keep the hydrogen pressure high from the viewpoint of shortening the reaction time.

After completion of the hydrogenation reaction, the hydrogenation reaction catalyst (hydrosilylation reaction catalyst if present in the reaction system) is separated and removed under nitrogen pressure using filter paper, diatomaceous earth or activated carbon, and the solvent is distilled off. By doing so, a hydrogenated product of the polyoxyalkylene-modified polysiloxane composition can be obtained.

[Addition of diluent]
The foam stabilizer of the present invention contains the above-mentioned polyoxyalkylene-modified polysiloxane composition, but may be in the form of a composition to which a diluent or the like is added in practical use.

Specifically, the foam stabilizer of the present invention may contain, in addition to the above polyoxyalkylene-modified polysiloxane composition, a polyol, a polyglycol or a derivative thereof, a silicone oil, a nonionic surfactant (however, (Excluding the alkylene-modified polysiloxane composition) and an antioxidant.

The polyol is a polyether polyol, a polyester polyol, or the like, and may be the same component as the component (a) of the polyurethane foam-forming composition described below. By using the component as a dispersant or diluent for a foam stabilizer, it is possible to adjust the workability, uniform dispersibility, etc. of the foam stabilizer without adversely affecting the polyurethane foam-forming composition. There is.

Polyglycol or a derivative thereof can be used as a dispersant or diluent of a foam stabilizer similarly to a polyol, and examples thereof include polyethylene glycol, polypropylene glycol and their block copolymers, and monoalkyl ethers of these polyglycols. Is done.

Silicone oil is a component that functions as a dispersion medium of a foam stabilizer or a foaming component of a polyurethane foam (sometimes referred to as a gas permeability imparting component or a cell opener). ) Or cyclic polymethylsiloxanes. For example, examples of the linear polymethylsiloxane include dimethylpolysiloxane having a trimethylsiloxy group at both ends of a molecular chain (a low viscosity such as 2 mPa · s or 6 mPa · s to a high viscosity such as 1,000,000 mPa · s); Examples of methylsiloxane include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5); examples of branched polymethylsiloxane include methyltristrimethylsiloxysilane and ethyltristrimethyl Siloxysilane, propyltristrimethylsiloxysilane, tetrakistrimethylsiloxysilane and the like are exemplified. The type and viscosity of the silicone oil and the contribution (function) to the polyurethane foam may be appropriately selected according to the hardness and the type of the polyurethane foam.

Nonionic surfactants are optional surfactant components, except for the above-mentioned low-brominated polyoxyalkylene-modified polysiloxane composition, and organic and silicone nonionic surfactants can be widely used. is there. For example, polyglyceryl diisostearate, diglyceryl polyhydroxystearate, isostearyl glyceryl ether, polyoxyalkylene ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty acid diesters, polyoxyalkylene resin acid Esters, polyoxyalkylene (hardened) castor oil, polyoxyalkylene alkyl phenols, polyoxyalkylene alkyl phenyl ethers, polyoxy alkylene phenyl phenyl ethers, polyoxy alkylene alkyl esters, polyoxy alkylene alkyl esters, sorbitan Fatty acid esters, polyoxyalkylene sorbitan alkyl esters, polyoxyalkylene sorbitas Fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene glycerin fatty acid esters, polyglycerin alkyl ethers, polyglycerin fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, alkyl glucosides, polyoxyalkylene fatty acids Bisphenyl ethers, polypropylene glycol, diethylene glycol, polyoxyethylene / polyoxypropylene block polymer, alkyl polyoxyethylene / polyoxypropylene block polymer ether, polyoxyethylene / polyoxypropylene block polymer, alkyl polyoxyethylene / polyoxypropylene Examples include block polymer ethers and fluorine-based surfactants. Further, silicone surfactants such as polyglyceryl-modified silicone, diglycere-modified silicone, glyceryl-modified silicone, sugar-modified silicone, fluorine polyether-modified silicone, and carboxylic acid-modified silicone are exemplified.

[Addition of antioxidant]
The polyoxyalkylene-modified polysiloxane composition is gradually oxidized and deteriorated by oxygen in the air. To prevent this, an antioxidant such as phenols, hydroquinones, benzoquinones, aromatic amines, or vitamins is added to increase the oxidation stability, which is preferable. As such an antioxidant, for example, BHT (2,6-di-t-butyl-p-cresol), vitamin C, vitamin E and the like can be used. However, from the viewpoint of reducing Emission from polyurethane foam, it is important to select vitamin E and other high molecular weight type antioxidants. At this time, the amount of the antioxidant to be used is in the range of 10 to 1000 ppm, preferably 50 to 500 ppm, based on the weight of the polyoxyalkylene-modified polysiloxane.

[Reduction of low molecular siloxane]
In the polyoxyalkylene-modified polysiloxane composition according to the present invention, the content of the low-molecular siloxane having 20 or less silicon atoms is preferably 5000 ppm (weight) or less, and particularly preferably 2000 ppm (weight) or less. If this value exceeds 5000 ppm, particularly when the polyether-modified silicone composition of the present invention is used as a foam stabilizer such as a polyurethane foam, it may contaminate members around the place where the polyurethane foam is installed, or may cause electric or electric shock. It may cause a contact failure of the electronic device. Such low-molecular-weight siloxanes include cyclic ones and linear ones. For example, cyclic ones represented by the formula [(CH3) 2SiO] n (where n is an integer of 3 to 10). And dimethylsiloxane, and linear dimethylsiloxane oligomers represented by the formula, CH3 [(CH3) 2SiO] mSi (CH3) 3 (where m is an integer of 1 to 10). Some methyl groups are partially substituted with other organic groups. More specific examples of such low-molecular siloxanes include octamethyltetrasiloxane, decamethylpentacyclosiloxane, and dimethylsiloxane oligomers with capped trimethylsiloxy groups at both ends. The content of the low-molecular siloxane can be measured by, for example, analyzing using a gas chromatography analyzer. The method for reducing the low-molecular siloxane is not limited.However, industrially, this is usually carried out by a stripping operation, so that the organohydrogenpolysiloxane, which is a raw material of the polyether-modified silicone composition of the present invention, is purified in advance, It is desirable to remove the siloxane. Alternatively, the low molecular siloxane may be removed during or after the hydrosilylation reaction.

[Solvent consisting of specific monol organic compound]
The polyoxyalkylene-modified polysiloxane composition according to the present invention is liquid at 5 ° C., has one alcoholic hydroxyl group in the molecule, and does not contain a hetero atom other than oxygen. Two or more specific monol organic compounds may be used as the solvent. Such a solvent is a solvent for the polyoxyalkylene-modified polysiloxane, and may be introduced into the composition as a solvent in the synthesis reaction, and the synthesis reaction of the polyether-modified silicone was performed in the presence or absence of another solvent. It may be introduced into the composition later by solvent replacement or solvent addition into the system.

In particular, the solvent is preferably a monool organic compound having a boiling point capable of distillation or purification by distillation, and more preferably a monool organic compound purified by distillation.

In the solvent, the terminal hydrogen is substituted by a hydrocarbon group having 2 to 8 carbon atoms, and the other terminal has a secondary alcoholic hydroxyl group. It may be a glycol ether compound having a number in the range of from 3 to 3, having a relatively low degree of polymerization, having one end blocked with a hydrocarbon group, and having a secondary alcoholic hydroxyl group at the other end. Is preferred. Examples of such compounds include dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, dipropylene glycol mono (iso) propyl ether, tripropylene glycol mono (iso) propyl ether, dipropylene glycol monoethyl ether, tripropylene Glycol monoethyl ether and the like.

Further, the solvent may be tripropylene glycol monomethyl ether.

The solvent composed of the specific monol organic compound may be the compound exemplified above alone or a mixture of both. The mixing ratio is arbitrary, and a mixture of two or more solvents may be used. However, when a monol organic compound which does not correspond to the above-mentioned components is used, particularly, the performance of the intended foam stabilizer becomes insufficient, and the object of the present invention may not be achieved in some cases.

In the polyoxyalkylene-modified polysiloxane composition according to the present invention, the mass ratio of the polyoxyalkylene-modified polysiloxane to the solvent is in the range of 20/80 to 96/4, and the performance, quality, and use of the composition It is preferable from the viewpoint of convenience at the time, handling workability (handling), and the like.

It is important that the viscosity at 25 ° C. of the polyoxyalkylene-modified polysiloxane composition of the present invention containing a solvent is in the range of 10 to 30,000 mm 2 / s from the viewpoint of convenience in use, handling, and the like. .

[Optional additive which is a specific polyalkylene glycol or a derivative thereof]
The polyoxyalkylene-modified polysiloxane composition according to the present invention is further optionally a liquid at 25 ° C., wherein one of the terminal hydroxyl groups has 1 to 8 carbon atoms selected from alkyl, aralkyl and aryl groups. May contain one or more selected from polyalkylene glycols and derivatives thereof in which the number of repetitions of the oxyalkylene unit having 2 to 4 carbon atoms is in the range of 4 to 50. By using such a component, the viscosity and the like of the composition of the present invention are adjusted without adversely affecting the function as a foam stabilizer or a surfactant, and the convenience at the time of use and the handling efficiency (handling) are improved. May be possible. In addition, the component may be used in addition to the polyether-modified silicone composition for the purpose of adjusting the hydroxyl value in the polyurethane foam-forming composition, that is, for controlling various physical properties such as the crosslinking density and strength of the polyurethane foam. is there.

The polyoxyalkylene-modified polysiloxane composition according to the present invention may contain a water-soluble alcohol other than the above-mentioned solvents or additives as long as the technical effect is not impaired. Examples of the water-soluble alcohol include alcohols or glycols having 1 to 4 carbon atoms such as ethanol, ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol, tripropylene glycol, diethylene glycol, triethylene glycol and isopropanol. .

<Low-odor polyoxyalkylene-modified polysiloxane composition>
By the production method of the present invention having the above-mentioned step [A] and step [B], and step [C] and stripping step carried out as necessary, the polyoxyalkylene-modified polysiloxane composition according to the present invention is obtained. can get. The above-mentioned solvent and optional additives may be added to the polyoxyalkylene-modified polysiloxane composition.

The foam stabilizer containing or consisting of the polyoxyalkylene-modified polysiloxane composition may be subjected to hydrolysis in the presence of a specific acidic inorganic salt in step [B], and optionally hydrogenation in step [C]. Since the composition has been subjected to the deodorization treatment by the addition reaction, this composition does not have a peculiar odor (unpleasant odor) and is significantly deodorized. Almost completely suppressed. Further, in the step [B], the silicon-oxygen bond constituting the main chain of the polysiloxane and the carbon-oxygen bond in the side chain are hardly cleaved, and the composition is entirely uniform. Thereby, when the foam stabilizer is used as a foam stabilizer for polyurethane foam, it effectively suppresses the generation of odor-causing substances such as aldehydes, and can form a polyurethane foam with extremely low odor and odor. Provide the agent. Also provided are a polyurethane foam-forming composition and a polyurethane foam containing the same.

[Foam stabilizer]
The low-odor foam stabilizer of the present invention can be suitably used as a surfactant for controlling or stabilizing bubbles, particularly as a foam stabilizer during the production of a foaming resin, particularly a polyurethane foam. In particular, the composition according to the present invention is excellent in homogeneity and stability of the premix solution, and is also excellent in compatibility with various components in the foam-forming emulsion composition. Further, by using in combination with the (AB) n-type polyether-polysiloxane block copolymer composition described in JP-A-08-156143 and the like, it is possible to improve the cell retention in microcellular applications and slow recovery foam applications. There is an advantage that it is possible to achieve both fine cell formation, that is, both bubble retention and low foam density. Further, in the use of a flexible foam, it is possible to manage to a desired air permeability by controlling the ratio with the solvent component. In the case of a rigid foam, it is possible to manage the closed cell rate and the cell size by controlling the ratio with the solvent component.

Further, the foam stabilizer of the present invention can select an organohydrogenpolysiloxane raw material at the time of the synthesis reaction from a small siloxane polymerization degree to a large siloxane polymerization degree by using an optional solvent component, if necessary. The total molecular weight of the oxyalkylene-modified polysiloxane and the amount of the polyoxyalkylene-modified group introduced can be easily designed or adjusted. Also, the surface activity and the affinity to the urethane foam system can be controlled by the EO / PO% and size of the polyether portion and the introduction of a hydroxyl group or a hydrophobic group to the terminal of the polyoxyalkylene-modified group.

In addition, since the foam stabilizer comprising the polyoxyalkylene-modified polysiloxane composition of the present invention can realize low odor by an industrially simple method, it is excellent in productivity and directly linked to industrial production cost. The present invention solves production problems and application problems comprehensively, makes it possible to sufficiently disseminate the novel foam stabilizer in the market, and to use it as a high-performance raw material.

[Polyurethane foam forming composition]
The foam stabilizer is used for producing a polyurethane foam. Accordingly, the polyurethane foam-forming composition of the present invention is not particularly limited in its type, characteristics, and type of applied formulation, as long as it contains the above-mentioned foam stabilizer according to the present invention.

[Form type]
In general, polyurethane foams are classified into hard and soft ones, and are specifically classified into soft urethane foams, highly elastic urethane foams, hard urethane foams, and special foams. Since the polyurethane foam-forming composition of the present invention is excellent in molecular weight design, handling workability (handling), etc., it exhibits an excellent effect as a foam stabilizer capable of realizing low odor / low emission foam in all polyurethane foam formulations. You can do it.

Soft urethane foam is widely used as a cushion material for sofas and beds, and as a seat for automobiles and the like. Since the viscosity of the raw material system of the flexible slab foam is relatively low and the expansion ratio is high, stabilization of the cell film during cell growth is a key. Foam stabilizers of relatively high molecular weight (polyether-modified silicones) are well suited for this system. In addition, in order to ensure compatibility with No. 3000 polyol, a type in which polyether having a relatively high propylene oxide ratio is graft-modified is widely used. Since the modified polyethers with unterminated ends (hydroxyl groups) have the effect of strengthening the cell's closed cell properties, the types with polyether ends capped (mostly methoxy-capped) are widely applied to improve the cell membrane communication. Helping make it easier. The foam stabilizer comprising the polyoxyalkylene-modified polysiloxane composition of the present invention may be a Low Emission (or Low Fogging) type foam stabilizer containing the above monol organic compound, and is also suitable for this system. It can be used for On the other hand, the soft hot mold formulation is composed of a urethane stock solution that is fairly close to the soft slab formulation, has high reactivity, and is packed under a condition in a mold. Is important. The foam stabilizer comprising the polyoxyalkylene-modified polysiloxane composition of the present invention can achieve high air permeability and can be used in the formulation. In addition, since the composition of the present invention is a Low Emission (or Low VOC) type low odor foam control agent, the effect of reducing or alleviating the problem of a sick house is expected.

The flame retardant foam-compatible foam stabilizer is defined as a type capable of reducing the number of flame retardant additions in a formulation and a type capable of reducing adverse effects on foam properties caused by the addition of a flame retardant. However, silicone foam stabilizers are generally positioned as combustion aids. This is because when the foam is melted to a liquid state by heat, the silicone foam stabilizer is collected on the surface of the liquid due to the surface activation effect, thereby preventing carbonization. Therefore, in the flame-retardant foam, a foam stabilizer having a relatively low silicone content and a low foam regulating activity is suitable. A foam stabilizer comprising the polyoxyalkylene-modified polysiloxane composition of the present invention may be used as a flame retardant foam-compatible foam stabilizer.

Since high elastic foam (HR Foam) is mainly formed by foaming a molded article such as an automobile seat, it is required to improve formability and air permeability. The HR foam is relatively easy to stabilize the cell membrane due to the high viscosity and high reactivity of the system, but since the communication does not proceed, cracks due to gas accumulated inside the foam, shrinkage after demolding, etc. It is necessary to prevent defects. For this reason, a foam stabilizer having very low foam regulating ability and having cell open properties is generally widely applied. This type is designed so that the molecular weight of the foam stabilizer is very small, and achieves the initial emulsification of the raw material components, but has the feature that the holding power of the cell membrane is very weak.

Further, in this system, dimethylpolysiloxane having a relatively low molecular weight which is not modified with polyether is also applied. In combination with polyether-modified silicone, they function as foam control aids that provide stable foam control activity (moldability), while adjusting cell openness and foam control power by optimizing molecular weight distribution. be able to.

TDI-based formulations requiring high activity have more foam-regulating power and fine cell type, while MDI-based formulations with relatively strong foaming have less foam-regulating power and good crushing properties. A type that gives high air permeability is suitable. Adjusting the cell size and air permeability by using a combination of a strong type and a weak type in foam control is widely applied to production, and it is a technique unique to this system.

However, very low-molecular-weight polyether-modified silicones and low-molecular-weight dimethylpolysiloxanes, which are widely used in high-elastic foam applications, have the problem of a narrow process range (the degree of freedom in foam formulation and the narrow tolerance range), There is a problem that emission from foams, fogging and odor are strong due to a large amount of volatile components in the foam stabilizer, and in order to reduce these problems, a low-molecular-weight composition comprising the polyoxyalkylene-modified polysiloxane composition of the present invention is used. It is preferred to use a odor control agent. In addition, since the composition of the present invention is a Low Emission (or Low VOC) type foam stabilizer, the effect of reducing or alleviating the problem of sick house is expected.

Rigid urethane foam is widely used as a heat insulating material for building materials and refrigerators because of its light weight, excellent heat insulating properties, and high productivity. In order to improve the heat insulating property of the rigid urethane foam, it is important to make the cell size as small as possible. The number of cells of the finally obtained foam and the number of entrapped gas dispersed at the time of stirring the initial urethane foaming liquid are almost the same. Therefore, a foam stabilizer that enhances the emulsifying power in the initial stirring is optimal. On the other hand, the finer the cells, the easier the foam shrinks. In this case, by prescribing a type having a relatively low foam regulating activity and increasing the cell size, the effect of preventing shrinkage increases. In addition, polyisocyanurate foam having excellent flame retardancy is also classified as one of the rigid urethane foams.

In the case of rigid urethane foam, HCFC141b, which has been used as a foaming agent in the past, is being regulated from the viewpoint of the global environment, and there is a trend that the replacement of HFC compounds will be regulated in the near future. The effect of the foaming agent on the urethane foam formulation is great, and it is necessary to select an optimal foam stabilizer depending on the type.

The initial emulsifying power of the water formulation and the HFC formulation with a large number of water parts is lower than that of the HCFC-141b formulation, which has good compatibility with the urethane stock solution. Therefore, by formulating a foam stabilizer having a high foam regulating activity, it is expected that a good cell can be obtained. Further, in the case of cyclopentane formulation, premix compatibility may be required from the viewpoint of storage stability. In this case, the compatibility with the base polyol is important, and the type in which the modified polyether has a high EO (ethylene oxide) ratio and the terminal is a hydroxyl group (—OH) shows relatively good compatibility. The composition of the present invention has excellent compatibility with not only HFC but also a polyurethane foam-forming composition using cyclopentane, so that the composition is blended with a rigid polyurethane foam formulation or a premix solution using these foaming agents. It is possible and functions as an effective foam stabilizer. In addition, since the composition of the present invention is a Low Emission (or Low VOC) type foam stabilizer, it is expected to have an effect of reducing or alleviating the sick house problem. The composition of the present invention may also be used in combination with a urethane foam formulation containing an HFO (hydrofluoroolefin) or HHO (hydrohaloolefin) blowing agent developed for global warming and ozone depletion. Can be. By using the low-emission and low-odor odor control agent of the present invention, it is possible to produce and use a foam material having less adverse effect on the global environment.

The foam stabilizer comprising the polyoxyalkylene-modified polysiloxane composition of the present invention may be a foam stabilizer comprising a moderate to relatively high molecular weight surfactant and a specific monol organic compound, and if desired, Since the emulsifiability, the molecular weight and the terminal functional group can be adjusted, it can be blended in water-blown rigid urethane foam without any particular limitation.

Special foams include, for example, semi-rigid foams, which are intermediate materials between flexible foams and rigid foams, low-resilience foams derived from flexible foams but with unique viscoelastic behavior that have built up specific uses and positions. Examples include a high-density foam called an integral skin used for the bottom and the like, a microcellular foam manufactured by a mechanical foaming (mechanical floss) method, and the like.

In addition, foams produced using polyester-type polyols rather than general polyether-type polyols as raw material polyols for urethane foams are called ester foams, and this is also classified according to the foam characteristics as described above. is there.

Rigid foams often require a closed-cell foam with a high closed cell rate because insulation is important in many applications.However, in some applications, dimensional stability is more important and partial The selection of the surfactant and the formulation of the foam composition have been devised so as to make the cell open. Conversely, in a typical flexible foam, the formation of a polyurethane structure due to the reaction between the polyol and the isocyanate, and the rise of the foam due to the heat of reaction and the foaming agent are stopped at the moment when the structure increases in strength due to the progress of cross-linking. The prescription is designed so that all the cell (bubble) membranes in the structure are torn (open) and open (continuous ventilation).

The formulation of the low resilience foam is similar to the formulation of a general flexible foam, but a device has been devised to incorporate a viscoelastic structural element into the raw polyol. For this reason, the degree of difficulty of cell communication is increasing, and the importance of a surfactant having a high open cell effect is increasing. Further, in the field of high-density microcellular foam by HR or mechanical foaming method, various uses are created by controlling the open cell rate.

Preferably, the polyurethane foam-forming composition of the present invention comprises:
(A) a polyol,
(B) polyisocyanate,
(C) a catalyst,
(D) a foam stabilizer described above, and (e) optionally, a foam stabilizer other than the component (d), a foaming agent, a diluent, a chain extender, a crosslinking agent, water, a non-aqueous foaming agent, a filler, Contains at least one additive component selected from the group consisting of reinforcing agents, pigments, dyes, colorants, flame retardants, antioxidants, anti-ozonants, ultraviolet stabilizers, antistatic agents, bactericides and antibacterial agents To do.
In particular, when achieving a high degree of odor reduction, it is necessary to previously remove or reduce odor-causing substances such as aldehydes and amines from each raw material, and to add an antioxidant or an antioxidant to each raw material. Particularly preferred.
Hereinafter, each component is outlined.

[(A) polyol]
Examples of the polyol include a polyether polyol and a polyester polyol. The polyether polyol is obtained by adding an alkylene oxide to a polyhydric alcohol, a saccharide, a phenol, a phenol derivative, an aromatic amine, and the like.For example, glycerin, propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol , Trimethylolpropane, pentaerythritol, sucrose, sorbitol, novolak, nonylphenol, bisphenol A, bisphenol F, tolylenediamine, diphenylmethanediamine, and the like. . Polyester polyols include condensation polymerization of polyfunctional carboxylic acids such as adipic acid, phthalic acid, and succinic acid with polyfunctional hydroxyl compounds such as glycerin, propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, trimethylolpropane, and pentaerythritol. And a polyol having a hydroxyl group at the terminal. The polyol may be used alone or in combination of two or more. From the viewpoint of imparting Low Emission characteristics to the polyurethane foam, it is important to select an additive (for example, an antioxidant or a stabilizer) contained in the polyol of a high molecular weight type having no volatility.

Suitable polyols for preparing the polyurethane foams of the present invention are those having 2 to 8 hydroxyl groups per molecule and having a number average molecular weight of 200 to 10,000, preferably 500 to 7,500. . Examples of useful polyether polyols include the products of Voranol 220-028, Voranol 220-094, Voranol 225, Voranol 270, Voranol 490 and Voranol 800 (Dow Chemical Company) and Arcol 11-34 (Bayer Material Science).

Polyols, such as polyether polyols and polyester polyols, usually have a hydroxyl number (hydroxyl number) in the range of about 15 to about 700. The hydroxyl number is preferably about 20-60 for flexible foam, about 100-300 for semi-flexible (or semi-rigid) foam, and about 250-700 for rigid foam. For flexible foams, the preferred functionality, i.e. the average number of hydroxyl groups per polyol molecule of the polyol, is from about 2 to 4, most preferably from about 2.3 to about 3.5. For rigid foams, the preferred functionality is from about 2 to about 8, most preferably from about 3 to about 5.

The foam stabilizer of the present invention can be used as a suitable foam stabilizer for most polyurethane foams. The compounding amount is in the range where the polyoxyalkylene-modified polysiloxane (A) in the foam stabilizer comprising the polyoxyalkylene-modified polysiloxane composition is 0.3 to 8.0 parts by mass with respect to 100 parts by mass of the polyol. And a range of 0.5 to 4.0 parts by mass is preferable, and 1.0 to 2.0 parts by mass is more preferable.

[(B) Polyisocyanate]
As the polyisocyanate, any known organic polyisocyanate can be used, but the most common ones are tolylene diisocyanate (hereinafter abbreviated as “TDI”) and diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”). It is. TDI is a mixture of isomers, that is, 2,4-isomer 100%, 2,4-isomer / 2,6-isomer = 80/20, 65/35 (respectively by mass) and many others. Crude TDI containing functional tars can also be used. As the MDI, in addition to a pure product containing 4,4′-diphenylmethane diisocyanate as a main component, a polymeric MDI containing a polynuclear substance having three or more nuclei can be used.

Of these isocyanate compounds, MDI is usually used for producing a rigid polyurethane foam, and TDI is usually used for producing a flexible polyurethane foam.

The isocyanate prepolymer of MDI is made from the reaction of MDI with a polyol, modified such as uretonimine modified, and any combination of the above mentioned MDI derivatives in any proportion. Also suitable are toluene diisocyanates (TDI), the 2,4 and 2,6 isomers and isocyanate prepolymers of TDI made from the reaction of TDI and polyol, and other aromatic or aliphatic polyisocyanates and uretonimines Includes modified versions thereof, including modified polyisocyanates and their prepolymers. Mixtures of polyisocyanates naturally fall within the scope of the present invention.

The blended amount of polyisocyanate with respect to the amount of other materials in the formulation is represented by "isocyanate index". "Isocyanate index" is the actual amount of polyisocyanate used divided by the stoichiometric amount of polyisocyanate required for reaction with all active hydrogens in the reaction mixture and multiplied by 100. . The isocyanate index of the polyurethane foam-forming composition used in the method of the present invention is generally from 60 to 140. Typically, the isocyanate index is typically 85-120 for flexible TDI foams, typically 90-105 for molded TDI foams that are high modulus (HR) foams, usually 70-90 for molded MDI foams, and is generally 70-90 for rigid MDI foams. 90-130. Some examples of polyisocyanurate rigid foams are produced with high indices of 250-400.

[(C) Catalyst]
Nickel acetoacetonate, iron acetoacetonate, tin catalyst, bismuth catalyst, zinc catalyst, titanium catalyst, aluminum complex, zirconium complex, potassium octylate, potassium acetate, sodium acetate, sodium octylate, solid acid on the surface Metal oxide particles having dots, tertiary amine urethane catalysts such as triethylenediamine, bis (dimethylaminoethyl) ether, imidazole derivatives, carboxylic acid quaternary ammonium salts, slow-acting tertiary amine catalysts, general tertiary amines Catalysts, low-emission tertiary amine catalysts, non-emission tertiary amine catalysts, and DABCO® catalysts, for example, from Air Products.

Among these catalysts, an amine-based catalyst is preferable for producing a rigid polyurethane foam, and a combination of an amine-based catalyst and a tin-based catalyst is preferable for producing a flexible polyurethane foam.

[(D) Foam stabilizer containing the polyoxyalkylene-modified polysiloxane composition of the present invention]
Although the polyoxyalkylene-modified polysiloxane composition according to the present invention is as described above, generally, there is a correlation between the compatibility of silicones containing a polyether portion as a foam stabilizer and the type of foamed resin. There are, in order from foam suitable for low molecular weight foam stabilizer to foam suitable for high molecular weight foam stabilizer,
High elasticity foam <hard foam <soft foam <microcellular foam.

In addition, since the structure of the polyether portion in the foam stabilizer molecule also greatly affects the size of the foam, etc., if it is desired to reduce the cell size and reduce the air permeability, select a polyether structure having a high EO content. If you want to stabilize or retain bubbles, select a polyether with a high molecular weight, expand the process range, or use multiple polyethers with different molecular weights or structures to ensure compatibility with a wide range of applications and formulations. There is a method of expanding the molecular weight distribution of the polyether portion, for example, by using as a raw material, and is also applicable to a foam stabilizer comprising the polyoxyalkylene-modified polysiloxane composition of the present invention. In addition, the polyol, which is one of the main raw materials of polyurethane, has a PPG structure, and the polyether portion in the polyether-modified silicone also contains a PO (propyleneoxy) chain from the viewpoint of compatibility in the foam formulation. It is often desirable to keep it.

These requirements differ depending on the type of polyurethane foam in which the foam stabilizer comprising the polyoxyalkylene-modified polysiloxane composition of the present invention is blended. Types of hydrogen polysiloxane, (a) the polyoxyalkylene compound having a carbon-carbon double bond at the terminal of the molecular chain, or the linear polyoxyalkylene compound represented by the general formula (1), Surface activity and affinity to urethane foam system can be controlled by appropriately adjusting the reaction ratio, EO / PO% and size of polyether moiety, and introduction of hydroxyl group or hydrophobic group into copolymer terminal. Therefore, there is an advantage that a suitable foam stabilizer can be freely designed as desired.

[(E) Optional component]
Of particular importance among the optional components (e) in the polyurethane foam-forming composition are water and non-aqueous blowing agents. Water acts as a chemical blowing agent by reacting with the polyisocyanate to produce carbon dioxide gas. In addition, one or more non-aqueous blowing agents in physical and / or chemical form can be included in the reaction mixture. Water may not be used depending on the prescription. These blowing agents include hydrofluorocarbons such as HFC-245fa and HFC-134a, hydrofluoroolefins such as HFO and HCFO, and low boiling hydrocarbons such as iso-, cyclo- and n-pentane; It may contain supercritical carbon dioxide, formic acid and the like.

Water is frequently used as a reactive foaming agent in both flexible and rigid foams. In the production of flexible slab foam, water can generally be used, for example, at a concentration of 2 to 6.5 parts per 100 parts of polyol, typically 3.5 to 5.5 parts. The moisture content of the TDI molded foam among the high elasticity (HR) foams is usually, for example, 3 to 4.5 parts. In an MDI molded foam, the water content is typically, for example, 2.5 to 5 parts. On the other hand, the water content of the rigid foam is, for example, 0.5 to 5 parts, usually 0.5 to 1 part. Physical blowing agents, such as those based on volatile or halogenated hydrocarbons or other non-reactive gases, can also be used to make the polyurethane foams according to the present invention. The rigid insulating foam produced is foamed in a significant proportion with volatile or halogenated hydrocarbons, the preferred blowing agents being hydrochlorofluorocarbon (HCFC) and the volatile hydrocarbons pentane and cyclopentane. Hydrofluoroolefins (HFO, HCFO) can also be used. In the production of flexible slab foam, water is the main blowing agent, but other blowing agents can be used as auxiliary blowing agents. For flexible slab foams, preferred auxiliary blowing agents are carbon dioxide and dichloromethane. High resilience (HR) foams generally do not use inert supplemental blowing agents, and in any case contain less supplemental blowing agents than slab foams. However, for some molding technologies, the use of carbon dioxide is of paramount importance. The amount of blowing agent depends on the desired foam density and foam hardness. The amount of the hydrocarbon-type blowing agent used is, for example, from a trace amount to 50 parts per 100 parts of polyol, and CO2 is, for example, about 1 to about 10%.

However, in particular, for microcellular applications, polyurethane foam by chemical foaming using water, hydrofluorocarbons, low boiling point hydrocarbons, etc. as a foaming agent has a hardness that is too low, and it is difficult to obtain the dimensional accuracy required for the final product, Due to insufficient mechanical strength such as tensile strength and abrasion resistance, high-density foams are usually produced by mechanical foaming. That is, here, air or nitrogen gas entrained by mechanical stirring mainly constitutes the core of the bubble.

Here, a polyol a), a polyisocyanate b), a catalyst c), a foam stabilizer d) comprising the polyoxyalkylene-modified polysiloxane composition of the present invention, and an optional component e) which may be contained in the polyurethane foam-forming composition. Certain water, non-aqueous blowing agents, and other components can vary over a wide range, for example, as set forth below. The reason for allowing a wide range is that the formulation of the polyurethane foam-forming composition must be adjusted according to the required foam characteristics, application, foam type, equipment and the like.

Examples of composition ranges for polyurethane foam-forming compositions:
6 to 85 parts by weight of polyol a), 10 to 80 parts by weight of polyisocyanate b), 0.01 to 5.0 parts by weight of catalyst c), 0.1 to 20 parts by weight of polyoxyalkylene modified according to the invention A foam stabilizer d) comprising a polysiloxane composition; and 0 to 9 parts by mass of water and 0 to 45 parts by mass of a non-aqueous foaming agent as optional components.

Further, the mass of water that can be contained in the polyurethane foam-forming composition is preferably in the range of 0 to 10% based on the mass of the polyol.

Other optional components e) are other polymers and / or copolymers, diluents, chain extenders, crosslinkers, fillers, reinforcing agents, pigments, dyes, colorants, flame retardants, antioxidants, antiozonants Any known and known in the art such as UV stabilizers, antistatic agents, bactericides and antimicrobial agents may be included within their normal contents. Further, the silicone oil may be added as a foaming component. From the viewpoint of imparting Low Emission characteristics, it was confirmed that even these optional components were composed of only components that would not cause migration or release due to volatilization from the foam. Mixing is important in the formulation design of the polyurethane foam-forming composition.

For example, optional component e) may contain a polyhydroxyl-terminated compound having from 2 to 8 hydroxyl groups per molecule and a molecular weight of from 62 to 500 acting as a crosslinker or chain extender. Crosslinkers with 3 to 8 hydroxyl groups include glycerin, trimethylolpropane, pentaerythritol, mannitol, sorbitol and the like. Examples of useful chain extenders having two hydroxyl groups are dipropylene glycol, tripropylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, ethylene glycol, 2,3-butanediol, It includes 2-methyl-1,3-propanediol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol and the like. Diethanolamine and monoethanolamine can also be used.

Optional component e) may also comprise a filler, such as, for example, an inorganic filler or a combination of fillers. Fillers may be used to improve density, physical performance such as mechanical performance or sound absorption, flame retardancy or other benefits including, for example, 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 materials that further reduce foam density Includes microspheres of materials such as polymers. High aspect ratio fillers or reinforcing agents used to modify the mechanical performance of the foam, such as rigid or flexible modules, include artificial fibers such as ground glass fibers or graphite fibers; Natural mineral fibers; natural animals such as wool or plant fibers such as cotton; artificial plate-like fibers such as ground glass; natural mineral plate-like fillers such as mica. Includes any of the pigments, dyes, and colorants that may be added. In addition, the present invention relates to organic flame retardants, anti-ozonants, anti-oxidants; heat or thermo-oxygen decomposition inhibitors, UV stabilizers, UV absorbers or foams formed when added to foam-forming compositions. The use of any other additive that avoids or inhibits the thermal, light and / or chemical decomposition of the compound is contemplated. Also contemplated for use herein are any known and conventional antistatic agents, bactericides, antimicrobial agents, and gas fading inhibitors.

The polyurethane foam obtained from the polyurethane foam-forming composition of the present invention is preferably a rigid foam, a semi-rigid foam, a high elasticity foam (HR Foam), a flexible foam, or a microcellular foam.

Regarding the process for producing a polyurethane foam from the polyurethane foam-forming composition of the present invention, various existing production steps can be used. For example, for a flexible foam, a polyurethane foam can be produced using a one-shot foaming method, a quasi-prepolymer method, or a prepolymer method. Common flexible foams are usually industrially produced as slab foams. Some slab foams are made by injecting the reactant mixture into a large box (a discontinuous process called box foam), while regular slab stock foam is continuously produced by discharging the reaction mixture onto a conveyor with a paper liner. To be manufactured. The foam expands and hardens as the conveyor advances, and the foam is cut into large blocks when leaving the foaming machine.

In the case of a rigid foam, a more subdivided manufacturing method is adopted depending on the purpose and application. For example, what is called “spray foam” is a system in which a polyurethane foam-forming composition is spray-foamed at a site such as a building site and solidified. What is called a "lamination board" is mainly used as a heat insulating material for prefabricated buildings, but it is also sometimes called a "heat insulation board" or "continuous lamination board stock". In the production of lamination boards, a foamed foam-forming composition continuously supplied through rollers between the facing materials facing up and down is hardened while flowing, and finally a plate-like foam having a thickness of about 10 cm is formed. The body is obtained. The so-called "appliance" is a foam exclusively for insulation for refrigerators, and is produced in a factory by a fully automatic process by injection molding. However, in this case, the foam-forming composition is injected into the mold, foamed and cured, and the process is completed, and the foam is not removed from the mold. A feature of the formulation of the refrigerator foam is that water is not used as a foaming agent because the heat insulating property is emphasized (since carbon dioxide has a property of easily transmitting heat). What is called "in-situ injection" has a literal meaning, but is a method of injecting a foam-forming composition into a mold at the site, foaming and curing, and terminating the injection, and refers to a use other than a refrigerator application.

In "microcellular" which is one of the special foams, a uniform, fine, high-density foam is manufactured by a mechanical foaming system called a mechanical floss system. Here, a so-called foaming agent is not used, and air or nitrogen gas or the like that is entrained by mechanical stirring mainly forms the core of the bubbles.

The low-resilience foam, which is one of the flexible foams, is manufactured in a slab or a mold format similar to a general flexible foam or an HR foam. For the slab product, the mixed stock solution is poured on a continuous conveyor, and the cross section of width 1-2m and height 0.2-0.6m is continuously foamed in a square or squirrel shape, and then a predetermined length (mostly 1-2m) Cut into bread shape. It is shipped to the processing establishment in this form, and products of various shapes can be cut out and processed from slab products. A molded product is obtained by injecting an undiluted solution into a plastic or metal mold (mold), foaming the molded product, and then removing the molded product from the mold. Thus, even a product having a complicated shape can be molded in large quantities with high dimensional accuracy.

In addition, a method for producing an individual polyurethane foam can be appropriately selected, and in particular, the foam stabilizer of the present invention is described in the detailed description of the following patent publications or patent publications, particularly in Examples and the like. In the method for producing a polyurethane foam, a silicone-based foam stabilizer, a silicone surfactant, or a silicone copolymer surfactant can be replaced and suitably applied. Note that the disclosure of these detailed descriptions or examples includes disclosure relating to a manufacturing apparatus, and a part of a component is further replaced by a normal design change of a person skilled in the art, and a change in viscosity or the like is performed. The manufacturing conditions may be appropriately changed.
・ Method for producing high rebound resilience foam described in JP-B-54-3715 public information ・ Method for producing polyurethane flexible molded foam described in JP-A-2001-181362 (Patent No. 4081235) ・ JP-A-2008-013763 Production method of flame-retardant rigid polyurethane or polyisocyanurate foam described in the public information, JP-T-2013-500362, Production method of polyurethane foam described in the public information, JP-T-2005-534770, JP-T-2005-534770 And a method for producing a polyurethane foam described in JP-T-2010-535931;
-Process for producing open-cell polyurethane described in JP-T-2010-529280-Seal material containing urethane foam described in JP-A-2012-24697, JP-A-2009-265425, etc.-JP-A-2012-2012 Production of urethane foam described in JP-A-0827273, JP-A-2010-247532, JP-A-2010-195870, JP-A-2002-137234, and the like

Polyurethane foams obtained by applying the foam stabilizer of the present invention to the production methods described in the above-mentioned patent publications are included in the scope of the present invention. Further, needless to say, the scope of the invention of the polyurethane foam using the foam stabilizer of the present invention is not limited to these.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. The methyl hydrogen polysiloxane used in each synthesis example was produced by a conventional equilibration reaction. Further, each of the polyoxyalkylene-modified polysiloxane compositions was blended, and the foam stabilizer product was dissolved in a diluent (hereinafter, referred to as a “sample”). The odor (odor test) and the amount of aldehyde generation of the foam stabilizer composition were determined as follows. The evaluation was carried out by the method and described in Table 2.

[Quantitative test method for generated aldehydes]
Immediately after the prepared foam stabilizer and after storage at 50 ° C. for 6 months, 1 g of a foam stabilizer sample, 0.3 g of 1N sulfuric acid and 1 g of liquid paraffin were added to a 20 ml vial, Seal with a rubber septum with aluminum cap. Thereafter, the mixture was heated with a headspace sampler at 80 ° C. for 60 minutes, 1 mL of the headspace was injected into the GC and detected by FID, and aldehyde was quantitatively analyzed. In Example 1 and Comparative Example 1, the amounts of acetaldehyde and propionaldehyde were measured and are shown in Table 2.

[Odor test]
100 g of the foam stabilizer sample was placed in a 200 ml glass bottle, heated at 40 ° C. for 1 hour, and the presence or absence of smell was confirmed according to the following criteria. In addition, in the case of the odor of △ or more, when used as an industrial product, there is a concern that odor is generated from the polyurethane foam.
◎: No odor 〇: Almost no odor-only a slight odor △: Feel the odor ×: Feel the strong odor

The following Synthesis Examples 1 to 4, Comparative Synthesis Example 1, and Reference Synthesis Example 1 show production examples of a polyoxyalkylene-modified polysiloxane composition. The above-mentioned evaluation is performed about the foam stabilizer containing these compositions.

<Synthesis example 1>
In a 1000 ml (1 L) four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet, the amount of hydrogen gas generated was 60 ml / g, and the structural formula was

(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] ₂ [(CH ₃ ) HSiO] ₁ Si (CH ₃ ) ₃

130 g of methyl hydrogen polysiloxane,
315 g of allyl polyether having a structural formula of CH ₂ ＣＨCHCH ₂ O (C ₂ H ₄ O) ₃ CH ₃
And 0.35 g of vitamin E, and the platinum concentration was 3. A 0% by mass solution of platinum divinyltetramethyldisiloxane-isopropyl alcohol was added, and the reaction was performed at 80 ° C. Further, 130 g of this methyl hydrogen polysiloxane was added, and the reaction was continued. Further, 140 g of this methyl hydrogen polysiloxane was added, and the reaction was continued. The total amount of methyl hydrogen polysiloxane used in the reaction was 400 g. After 3 hours, sampling was performed, and it was confirmed by a hydrogen gas generation method using an alkaline solution that the hydrosilylation reaction was completed.
Next, after low-boiling components were distilled off under reduced pressure, 0.1 g of sodium hydrogen sulfate monohydrate and 10.5 g of purified water were added, and a hydrolysis treatment was performed at 75 ° C. for 2 hours. After that, low-boiling components were distilled off under reduced pressure.
Further, after adding 10.5 g of purified water and performing a hydrolysis treatment at 75 ° C. for 1 hour, low boiling components are distilled off under reduced pressure in the same manner as described above, and the obtained reaction product is cooled to room temperature. Then, the pressure was returned to normal pressure, 10 g of diatomaceous earth was mixed, and pressure filtration was performed to perform a solid-liquid separation (removal of catalyst) operation. “Polyoxyalkylene-modified polysiloxane composition 1” was obtained as a filtrate after the operation.

<Synthesis Example 2>
In a 1000 ml (1 L) four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet, the amount of hydrogen gas generated was 75 ml / g, and the structural formula was

(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] ₁ [(CH ₃ ) HSiO] ₁ Si (CH ₃ ) ₃

100 g of methyl hydrogen polysiloxane,
329 g of allyl polyether having a structural formula of CH ₂ ＣＨCHCH ₂ O (C ₃ H ₆ O) ₂ CH ₃
And 0.35 g of vitamin E, and the platinum concentration was 3. A 0% by mass solution of platinum divinyltetramethyldisiloxane-isopropyl alcohol is added, and the reaction is performed at 80 ° C. Subsequently, the reaction is continuously carried out in the same manner as in Synthesis Example 1 with the charge of 100 g being divided. The total amount of methyl hydrogen polysiloxane used in the reaction was 400 g.
Next, low-boiling components were distilled off under reduced pressure, and then 0.1 g of sodium hydrogensulfate monohydrate and 10.5 g of purified water were added, followed by hydrolysis at 75 ° C. for 2 hours. Thereafter, low-boiling components are distilled off under reduced pressure.
Further, 10.5 g of purified water was added thereto, and a hydrolysis treatment was performed at 75 ° C. for 1 hour. Thereafter, low-boiling components were distilled off under reduced pressure in the same manner as described above, and the obtained reaction product was cooled to room temperature. Then, the pressure is returned to normal pressure, 10 g of diatomaceous earth is mixed, and the mixture is subjected to pressure filtration to perform a solid-liquid separation (removal of a catalyst). "Polyoxyalkylene-modified polysiloxane composition 2" is obtained as the filtrate after the operation.

<Synthesis example 3>
In a 1000 ml (1 L) four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet, the amount of hydrogen gas generated was 44 ml / g, and the structural formula was

(CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] ₃₄ [(CH ₃ ) HSiO] ₆ Si (CH ₃ ) ₃

100 g of methyl hydrogen polysiloxane,
663 g of allyl polyether having a structural formula of CH ₂ ＣＨCHCH ₂ O (C ₂ H ₄ O) ₁₈ (C ₃ H ₆ O) ₂₆ CH ₃
Further, 0.35 g of vitamin E and 140 g of toluene were charged. A 0% by mass platinum-divinyltetramethyldisiloxane-toluene solution is added, and the reaction is performed at 80 ° C. for 3 hours.
Next, after distilling off low boiling components under reduced pressure, 0.11 g of sodium hydrogen sulfate monohydrate and 11 g of purified water were added, and the mixture was hydrolyzed at 80 ° C. for 2 hours. The low boiling components are distilled off under reduced pressure.
Further, after adding 11 g of purified water and performing a hydrolysis treatment at 80 ° C. for 1 hour, low-boiling components were distilled off under reduced pressure in the same manner as above, and the obtained reaction product was cooled to room temperature. After returning to normal pressure, 10 g of diatomaceous earth is mixed and filtered under pressure to perform a solid-liquid separation (removal of catalyst) operation. “Polyoxyalkylene-modified polysiloxane composition 3” is obtained as the filtrate after the operation. In addition, the composition 3 is useful as a foam stabilizer for soft slabs.

<Synthesis example 4>
In a 1000 ml (1 L) four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet, the amount of hydrogen gas generated was 27 ml / g, and the structural formula was (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] ₁₉ [(CH ₃ ) HSiO] ₂ Si (CH ₃ ) ₃
200 g of methyl hydrogen polysiloxane,
400 g of allyl polyether having a structural formula of CH ₂ ＣＨCHCH ₂ O (C ₂ H ₄ O) ₂₁ (C ₃ H ₆ O) ₅ CH ₃
Furthermore, 0.3 g of vitamin E and 60 g of isopropyl alcohol were charged. A 0% by mass platinum-divinyltetramethyldisiloxane-toluene solution is added, and the reaction is performed at 80 ° C. for 3 hours.
Next, after low-boiling components were distilled off under reduced pressure, 0.1 g of sodium hydrogen sulfate monohydrate and 10 g of purified water were added, and the mixture was hydrolyzed at 80 ° C. for 2 hours. The low boiling components are distilled off under reduced pressure.
Further, after adding 10 g of purified water and performing a hydrolysis treatment at 80 ° C. for 1 hour, low-boiling components were distilled off under reduced pressure in the same manner as described above, and the obtained reaction product was cooled to room temperature, After returning to normal pressure, 10 g of diatomaceous earth is mixed and filtered under pressure to perform a solid-liquid separation (removal of catalyst) operation. “Polyoxyalkylene-modified polysiloxane composition 4” is obtained as the filtrate after the operation. Composition 4 is useful as a foam stabilizer for soft slabs.

<Comparative Synthesis Example 1>
"Comparative composition 1" was obtained in the same manner as in Synthesis Example 1 except that the low-bromination treatment after the treatment with sodium hydrogen sulfate monohydrate was not performed.

<Reference synthesis example>
In Synthesis Example 2, instead of performing a low-bromination treatment after the treatment with sodium hydrogen sulfate monohydrate, Raney nickel was added using an autoclave, hydrogen gas was introduced, and the hydrogenation reaction was performed at 100 ° C. and 1 MPa. Then, "polyoxyalkylene-modified polysiloxane composition 5" is obtained.

<Example 1>
Foam stabilizer 1 was obtained by mixing 15% of polyoxyalkylene-modified polysiloxane composition 1 obtained in Synthesis Example 1 and 85% of polyoxyethylene polyoxypropylene glycerol ether (SPECFLEX NC 138, manufactured by Dow Chemical). The foam stabilizer is useful as a foam stabilizer for a highly elastic mold foam. Table 2 shows the aldehyde content and odor test of the foam stabilizer 1.

<Comparative Example 1>
15% of Comparative Composition 1 obtained in Comparative Synthesis Example 1 and 85% of polyoxyethylene polyoxypropylene glycerol ether (SPECFLEX NC 138, manufactured by Dow Chemical) were mixed to obtain Comparative Foaming Agent 1. Table 2 shows the aldehyde content and odor test of Comparative Foam Control Agent 1. The foam stabilizer is useful as a foam stabilizer for a highly elastic mold foam, except for the problem of generation of odor and aldehydes.

Both the above-mentioned foam stabilizer 1 and comparative foam stabilizer 1 are compositions that are useful as foam stabilizers for high-elasticity molded foams. Even after that, generation of aldehydes is suppressed, and it is expected to be useful as a low-odor foam control agent. On the other hand, in the comparative examples, the foam stabilizer had an odor, and generation of aldehydes such as propionaldehyde was particularly remarkable immediately after production / after the acceleration test.

(Foam stabilizer 2)
In Example 1, even when the polyoxyalkylene-modified polysiloxane composition 1 is replaced with the polyoxyalkylene-modified polysiloxane composition 2 obtained in Synthesis Example 2, the foam stabilizer according to the present invention can be obtained. Each of the foam stabilizers has no odor, suppresses the generation of aldehydes even immediately after production / after the accelerated test, and is expected to be useful as a low-odor foam stabilizer.

(Foam stabilizers 3, 4)
Similarly, the polyoxyalkylene-modified polysiloxane composition 3 or 4 obtained according to Synthesis Example 3 or Synthesis Example 4 is useful as a foam stabilizer, and both have no odor and immediately after production / after the accelerated test. Also, generation of aldehydes is suppressed, and it is expected to be useful as a low-odor foam control agent.

Hereinafter, the foaming evaluation of the polyurethane foam using the foam stabilizer / comparative foam stabilizer 1 according to Example 1 / Comparative Example 1 and the foam stabilizers 3 and 4 will be described. Here, each foam evaluation example gives the following type of urethane foam. The number of parts in the table is parts by mass, and the ratio is set so that the OH equivalent in the polyol mix and the NCO equivalent ratio of the isocyanate are 100: 100 (= Index100) or 100: 110 (= Index110).
Foaming evaluation example 1: High elasticity molded urethane foam (foam stabilizer 1 or comparative foam stabilizer 1)
Foaming evaluation example 2: Soft slab urethane foam (foam stabilizer 3)
Foaming evaluation example 3: rigid slab urethane foam (foam stabilizer 4)

＊TM-20はTDI/MDI=80/20混合物
＊＊Index 100は、ポリオールミックス中のOH当量とイソシアネートのNCO当量比が100：100を意味する。 <Exposure evaluation example 1>
Using the foam stabilizer 1 of Example 1 or the comparative foam stabilizer 1 of Comparative Example 1, a highly elastic molded urethane foam can be prepared. Specifically, a polyol (foam stabilizer, foaming agent, and catalyst) having the composition (formulation) shown in Table 3 below is put into a polyethylene cup, mixed, stirred for 10 seconds, then charged with isocyanate, stirred for 5 seconds, and then immediately molded. Transfer to After heating at 60 ° C., a urethane foam can be obtained.

* TM-20 is a mixture of TDI / MDI = 80/20 ** Index 100 means that the ratio of OH equivalent to isocyanate NCO equivalent in the polyol mix is 100: 100.

In the above foaming formulation, a polyol and a polymer polyol having a reduced odor and a reduced volatile content are used, and the amine catalyst is replaced with a reactive catalyst. Obtainable. The foam is useful for automotive interior materials and the like.

**TDI-80は2,4-isomer / 2,6-isomer = 80/20混合物
＊＊＊＊Index 110は、ポリオールミックス中のOH当量とイソシアネートのNCO当量比が100：110を意味する。 <Example 2 of foam evaluation>
A flexible slab urethane foam can be prepared using the above foam stabilizer 3. Specifically, a polyol (foam stabilizer), a foaming agent, and a catalyst were charged into a polyethylene cup with the composition (formulation) shown in Table 4 below, mixed, stirred for 10 seconds, then charged with isocyanate, stirred for 8 seconds, and then immediately added to the wood. Transfer to a box. Then, after heating in a 150 ° C. oven for 10 minutes, a urethane foam can be obtained.

** TDI-80 is a 2,4-isomer / 2,6-isomer = 80/20 mixture. **** Index 110 means that the ratio of OH equivalent to isocyanate NCO equivalent in the polyol mix is 100: 110.

***PAPI-135はポリメリックMDI、NCO=31.5％
＊＊＊＊Index 110は、ポリオールミックス中のOH当量とイソシアネートのNCO当量比が100：110を意味する。 <Foaming evaluation example 3>
A rigid urethane foam can be prepared using the foam stabilizer 4 described above. Specifically, a polyol (foam stabilizer), a foaming agent, and a catalyst were charged into a polyethylene cup with the composition (formulation) shown in Table 5 below, mixed, stirred for 10 seconds, and then charged with isocyanate. Transfer to a box. Then, after heating in a 150 ° C. oven for 10 minutes, a urethane foam can be obtained.

*** PAPI-135 is polymeric MDI, NCO = 31.5%
*** Index 110 means that the ratio of OH equivalent to NCO equivalent of isocyanate in the polyol mix is 100: 110.

[Reference example]
The polyoxyalkylene-modified polysiloxane composition 5 obtained by the reference synthesis example (hydrogenation) can be used as a foam stabilizer similarly to the polyoxyalkylene-modified polysiloxane composition 2 of Synthesis Example 2. For example, in Example 1, even if the polyoxyalkylene-modified polysiloxane composition 1 is replaced with the polyoxyalkylene-modified polysiloxane composition 5, a foam stabilizer having a relatively low odor can be obtained, and In Evaluation Example 1, the foam stabilizer 1 can be used in place of the foam stabilizer. However, as compared with the foam stabilizer 1 or the foam stabilizer 2, the foam stabilizer of Reference Example 1 requires a hydrogenation reaction, so that it is difficult to mass-produce it industrially, and the degree of odor reduction is also low. It is equivalent to or slightly inferior to the foam stabilizer of the invention. Therefore, the foam stabilizer 1 or the foam stabilizer 2 according to the present invention (Example) has an advantage over the foam stabilizer in terms of industrial productivity and cost.

Claims (6)

(A) a polyoxyalkylene compound having a carbon-carbon double bond at a terminal of a molecular chain;
(B) a step [A] of synthesizing a polyoxyalkylene-modified polysiloxane composition by subjecting an organohydrogenpolysiloxane to a hydrosilylation reaction; and
(C) one or more acidic compounds, which are solid at 25 ° C., are water-soluble, and have a pH of 4 or less at 25 ° C. of an aqueous solution when 50 g is dissolved in 1 L of ion-exchanged water. Step of removing odor-causing substances by treating in the presence of an inorganic salt [B]
A foam stabilizer comprising a polyoxyalkylene-modified polysiloxane composition obtained by a production method comprising: 2. The composition according to claim 1, further comprising at least one selected from a polyol, a polyglycol or a derivative thereof, a silicone oil, a nonionic surfactant (excluding the polyoxyalkylene-modified polysiloxane composition) and an antioxidant. Foam stabilizer. A polyurethane foam-forming composition comprising the foam stabilizer according to claim 1 or 2. (A) a polyol,
(B) polyisocyanate,
(C) a catalyst,
(D) a foam stabilizer according to claim 1 or 2, and (e) optionally a foam stabilizer other than the component (d), a foaming agent, a diluent, a chain extender, a crosslinking agent, water, Selected from the group consisting of non-aqueous blowing agents, fillers, reinforcing agents, pigments, dyes, colorants, flame retardants, antioxidants, anti-ozonants, UV stabilizers, antistatic agents, bactericides and antibacterial agents , A polyurethane foam-forming composition comprising at least one additional component. A polyurethane foam obtained by using the polyurethane foam-forming composition according to claim 3. The polyurethane foam according to claim 5, wherein the polyurethane foam has a low emission property, which is a rigid foam, a semi-rigid foam, an HR (high elasticity) foam, a flexible foam, or a microcellular foam.