JP2006143982A - Soundproofing material and molded product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a soundproofing material using glass fibers or a fabric thereof and to provide various kinds of molded products using the material. <P>SOLUTION: The soundproofing material is characterized as impregnating the glass fibers or the fabric thereof with a silane-modified polyurethane resin. The molded products characterized as comprising a layer (A) using the soundproofing material are used. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a soundproofing material and a molded product thereof. More specifically, the present invention relates to a soundproof material excellent in various properties such as light weight, step stability, mechanical strength, soundproofing property, and flame retardancy, and various molded products using the material.

  Sound insulation materials can be generally classified into sound insulation materials and sound absorption materials based on their effects. Sound-absorbing materials are materials that convert sound energy into heat, such as various fiber materials (glass wool, rock wool, chemical fibers, etc.), rigid materials (foamed concrete, ceramic particle bonded bodies, glass particle bonded bodies, etc.) Metal materials (aluminum fibers, aluminum sintered bodies, SUS sintered bodies, etc.) are known. On the other hand, sound-absorbing materials generally depend on the mass law (the sound insulation effect is proportional to the surface density of the material) in single-layer products, so the thickness of the material can be adjusted according to the use of the material, It is used as a multilayer structure, for example, board system (slate, flexible board, plaster board, etc.), concrete system (ALC, concrete block, etc.), metal system (iron plate, lead plate, etc.) are known. Yes.

  The use of the above-mentioned soundproofing materials covers a wide range such as home appliances / OA equipment, automobiles, construction / housing, bridges / highways, railway vehicles, etc. In particular, soundproofing materials using glass fiber and the fabric are used for construction / housing. It is suitable for automobile applications, and is used for floor materials, wall materials, soundproof curtains, automobile linings, and the like.

Prior art relating to soundproof materials using glass fiber and the fabric will be described more specifically below. Patent Document 1 discloses a multilayer product having a layer of a semi-rigid polymer (for example, heat-sensitive polyurethane resin) in which a glass fiber base material is impregnated with a polyurethane resin. The multilayer product is lightweight and mechanically resistant. It is described as having excellent aesthetic effects and soundproofing effects. Patent Document 2 describes a reinforcing member for flooring, which is made of a glass fiber fabric subjected to a polyurethane resin treatment.

In addition, the applicant has proposed inventions relating to various silane-modified polyurethanes, the production method, and the application, and the silane-modified polyurethane has excellent adhesiveness to various inorganic base materials, and is used for various coating agents and adhesives. It discloses about what can be done (see Patent Documents 3 to 8). However, no sound insulation effect based on these silane-modified polyurethanes has been recognized.

JP 2002-192877 A Japanese Patent Laid-Open No. 2003-213572 JP-A-11-315264 JP 2000-1647 A JP 2000-63661 A JP 2000-327739 A JP 2001-64346 A Japanese Patent Laid-Open No. 2002-220431

  It is an object of the present invention to provide a soundproofing material using glass fiber or the fabric and various molded products using the material.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that when a silane-modified polyurethane, which is a specific organic-inorganic hybrid, is used as a binder for a glass fiber fabric, a soundproofing material capable of solving the above-mentioned problems and its The present inventors have unexpectedly found that a molded product can be obtained, and have completed the present invention.

  That is, the present invention relates to a soundproof material obtained by impregnating a glass fiber fabric with a silane-modified polyurethane resin; and a molded product containing a layer (A) using the soundproof material.

  According to the present invention, it is possible to provide a soundproofing material excellent in various characteristics such as light weight, dimensional stability, mechanical strength, and soundproofing, and various molded products using the material.

The glass fiber used in the present invention for the glass fiber and the cloth includes a glass filament (single fiber), a strand formed by converging the single fiber, a glass yarn obtained by twisting the strand, and the strand is not twisted. And rovings that are arranged in a row. Examples of the fabric composed of the glass fiber include glass cloth such as plain weave, leno weave, satin weave or twill weave woven from the yarn, roving cloth woven from roving, glass net or knitted fabric. Examples include woven and knitted fabrics. These can be produced by known methods, and commercially available products can be used for convenience. The glass as these raw materials may be any of alkali-free glass (for example, E glass), alkali-containing glass (for example, C glass), ECR glass with a reduced content of alkali, boron, fluorine, or the like. Good.

The glass fiber used in the present invention or the fabric (hereinafter simply referred to as “glass substrate”) may have a surface treated with a silane coupling agent. The silane coupling agent is usually an organic chain part for bringing affinity or bondability with an organic material, and -SiOH or -SiOR for forming a chemical / electric bond with the surface of the glass fiber or the fabric. And an inorganic chain part having a functional group such as Therefore, when a silane coupling process is performed, the adhesiveness of a glass base material and the silane modified polyurethane resin mentioned later can be improved further. Examples of the silane coupling agent include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, imidazoline silane, N-aminoethylaminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane or 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride A well-known compound can be mentioned. When these silane coupling agents are used, the adhesion amount is about 0.05 to 1% by weight with respect to the glass substrate.

Silane-modified polyurethane resin As the silane-modified polyurethane resin used in the present invention, a polyoxyalkylene diol having 3 or more carbon atoms in an alkylene group, a polyisocyanate, and a chain extender as necessary are reacted. A polyurethane (PU1) having a contact angle with water of 70 degrees or more and a hydrolyzable alkoxysilane (S1); having alkoxysilyl groups at both ends Composition (C2) comprising polyurethane (PU2) and hydrolyzable alkoxysilane (S1); polyurethane (PU3) having a polymer polyol and a polyisocyanate as main components and having hydroxyl groups at both ends, and hydrolysis Compound (C1) obtained by dealcoholization reaction with functional alkoxysilane (S1) ); Obtained by reacting at least one selected from the group consisting of a hydroxyl group-containing polyamine, a primary and a secondary amino group-containing polyamine as a chain extender after reacting the polymer polyol and the polyisocyanate. A composition (C4) comprising a polyurethane (PU4) having a hydroxyl group and / or an amino group in the molecule and having a total hydroxyl value and amine value of 1 or more and a hydrolyzable alkoxysilane (S1). ); Dealcoholization reaction of polyurethane (PU5) having a polymer polyol and polyisocyanate as main constituents and having reactivity with an epoxy group, an epoxy compound having one hydroxyl group in one molecule, and a hydrolyzable alkoxysilane Obtained by reacting with the epoxy group-containing alkoxysilane partial condensate (S2) obtained by The compound (C5). These silane modified polyurethane resin may be used in combination of one kind alone or two or more as appropriate.

More specifically, the composition (C1) is disclosed in JP-A No. 11-315264, the composition (C2) is disclosed in JP-A 2000-63661, and the compound (C3) is disclosed in JP-A 2000-327739. The composition (C4) is described in detail in JP-A No. 2001-64346, and the compound (C5) is described in detail in JP-A No. 2002-220431.

Regarding composition C1, PU1, and S1, PU1, which is a constituent component of composition C1, is obtained by reacting a polyoxyalkylene diol having 3 or more carbon atoms of an alkylene group, a polyisocyanate, and, if necessary, a chain extender. Polyurethane having a contact angle with water of 70 degrees or more. Here, the contact angle to water refers to a contact angle observed between the dry film of PU1 and a water drop dripped thereon. PU1 is composed of a hard segment and a hydrophobic soft segment. The hard segment is a part that contains many urethane bonds, urea bonds, etc., and aggregates to form a domain. The hydrophobic soft segment is a hard segment that gives flexibility to PU1, which can be a long chain. Are sites that form a matrix phase (continuous phase) that may exist as a dispersed phase. The hydrophobic soft segment is such that the obtained PU1 has a contact angle with water of usually 70 degrees or more, preferably 75 degrees or more, and more preferably 80 degrees or more. Say things. In addition, when the polyurethane which has a hydrophilic soft segment is used, there exists a disadvantage that the contact bonding layer of the composition C1 obtained and a glass base material becomes weak.

  The polyoxyalkylene diol having 3 or more carbon atoms in the alkylene group, which is a hydrophobic polymer polyol, forms a soft segment of PU1, and preferably has 4 to 6 carbon atoms in the alkylene group. it can. The alkylene group may be linear or branched. The polyoxyalkylene diol is usually obtained by ring-opening polymerization or copolymerization of an alkylene oxide having 3 or more carbon atoms, such as propylene oxide, oxetane, tetrahydrofurofuran, 3-methyltetrahydrofuran, and the like. Specific examples thereof include polyoxypropylene diol and polyoxybutylene diol, and polyoxybutylene diol is particularly preferable. In addition, when the number of carbon atoms of the alkylene group such as polyoxyethylene diol is 2 or less, the effect of the present invention cannot be exhibited because the hydrophilicity is strong.

  The number average molecular weight of the polyoxyalkylene diol is not particularly limited, but it is usually preferably about 1500 to 6000.

  The polyisocyanate forms a hard segment of PU1, and includes various types such as a chain aliphatic polyisocyanate, a cyclic aliphatic polyisocyanate, an aromatic polyisocyanate, an araliphatic polyisocyanate, and a polyisocyanate obtained from an amino acid derivative. Can be illustrated.

  Specific examples of the chain aliphatic polyisocyanate include methylene diisocyanate, isopropylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexa Examples include methylene diisocyanate and dimerized isocyanate in which the carboxyl group of dimer acid is replaced with an isocyanate group. Specific examples of the cycloaliphatic polyisocyanate include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-di (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate and the like. . Specific examples of the aromatic polyisocyanate include dialkyldiphenylmethane diisocyanate such as 4,4′-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate such as 4,4′-diphenyltetramethylmethane diisocyanate, 1,5-naphthylene diisocyanate, Examples include 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and the like. . Specific examples of the araliphatic polyisocyanate include xylylene diisocyanate and m-tetramethylxylylene diisocyanate. Specific examples of the diisocyanate obtained from the amino acid derivative include lysine diisocyanate.

  The chain extender used for PU1 forms a hard segment of PU1, and usually a low molecular polyol and / or a low molecular polyamine having about 2 to 6 carbon atoms can be preferably used.

  Examples of the low molecular polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, Low molecular weight glycols such as 3-methyl-1,5-pentanediol and 1,6-hexanediol, trihydric alcohols such as glycerin, butanetriol, pentanetriol, hexanetriol, trimethylolethane and trimethylolpropane; pentaerythritol And tetravalent or higher alcohols such as sorbitol.

  Examples of the low-molecular polyamine include amine compounds such as ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4′-diamine; 2-hydroxyethylethylenediamine, 2-hydroxy Examples thereof include diamine compounds having a hydroxyl group such as ethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine.

  The amount of these chain extenders used is up to about 20% by weight, preferably 15% by weight or less, of the total amount of the polyoxyalkylene diol and the polyisocyanate.

  PU1 is obtained by reacting the polyoxyalkylene diol, polyisocyanate, and, if necessary, a chain extender. As the reaction, a general polyurethane production method can be adopted. In addition to a batch preparation method of these components, a urethane prepolymer method in which the polyoxyalkylene diol and polyisocyanate are reacted in advance when a chain extender is used. Can be adopted. Moreover, you may introduce | transduce any functional group of a hydroxyl group, an isocyanate group, and an amino group into the terminal of the polyurethane of this invention by adjusting the usage-amount of each component suitably. Furthermore, in production of PU1, a chain length terminator such as dialkylamines such as di-n-butylamine; monohydric alcohols such as ethanol and isopropanol may be used as necessary. The number average molecular weight of PU1 thus obtained is preferably about 1800 to 100,000.

As the hydrolyzable alkoxysilane (S1), those generally used in the sol-gel method can be used. For example, general formula: R ¹ _m Si (OR ² ) _4-m (wherein m represents an integer of 0 to 2 and R ¹ is a lower alkyl group which may have a functional group directly connected to a carbon atom, An aryl group or an unsaturated aliphatic residue which may be the same or different from each other, and R ² represents a hydrogen atom or a lower alkyl group.) Or a partial condensate thereof, etc. it can. In addition, a lower alkyl group shows a C6 or less linear or branched alkyl group.

  Specific examples of S1 include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and methyl. Tributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriet Trialkoxysilanes such as silane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyl Dialkoxysilanes such as dimethoxysilane and diethyldiethoxysilane; or partial condensates thereof.

  Among these, tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane or partial condensates thereof are preferable. In particular, the general formula (a):

  Poly (tetramethoxysilane) which is a partial condensate of tetramethoxysilane represented by the formula (wherein Me represents a methyl group and n is an integer of 0 to 8) is preferable. The number average molecular weight of the poly (tetramethoxysilane) is preferably about 260 to 1116. Unlike tetramethoxysilane, such poly (tetramethoxysilane) is preferable in terms of reaction operation because it does not distill out of the system together with the produced methanol in the demethanol reaction, and there is no concern about toxicity. On the other hand, in the general formula (a), if the value of n exceeds 8, the compatibility with PU1, PU2, PU4, etc. tends to deteriorate.

The amount of S1 used is determined in consideration of the adhesiveness and soundproofing effect between the silane-modified polyurethane and the glass substrate in the composition C1 among the performance of the soundproofing material of the present invention to be obtained. Specifically, PU1 ( The amount is preferably about 1 to 50 parts by weight, more preferably 3 to 30 parts by weight in terms of the silica to be produced. That is, when the silica produced by the condensation of S1 exceeds the total amount of domains formed by the hard segment of PU1, the silica is phase-separated in the adhesive layer, and the adhesion to the glass substrate tends to be reduced. This is because of this.

  In composition C1, since a part of functional group in S1 turns into a silanol group, it is thought that it contributes to the adhesive improvement with a glass base material. In addition, most of the silica produced by the reaction of S1 is introduced into the hard segment domain of PU1 to become a composite domain, and the composite domain and the hydrophobic soft segment have a two-layer separated (sea island) structure. Become. The resulting cured product of composition C1 retains the flexibility of the soft segment of PU1 based on such a two-layer separation structure, and can exhibit good heat resistance and soundproofing properties due to the toughness of the composite domain. .

About composition C2, PU2, S1 PU2 which is a constituent component of composition C2 is not particularly limited as long as it has a structure having an alkoxysilyl group at both ends of polyurethane. For example, an isocyanate group, This corresponds to a reaction product obtained from a polyurethane (a) having both functional groups selected from a hydroxyl group and an amino group at both ends and an alkoxysilane (b) having a functional group capable of reacting with the terminal functional group of the polyurethane. To do. The polyurethane (a) can be produced by reacting a polyol component and a polyisocyanate, and further a chain extender, and adjusting the amount of each of the polyol component, polyisocyanate and chain extender appropriately. , A desired functional group can be introduced at the terminal. Note that PU2 is preferably a reaction product of a polyurethane having isocyanate groups at both ends and an alkoxysilane having an amino group, from the viewpoint of ease of synthesis.

The polyol component in the polyurethane (a) forms a soft segment of PU2, and various compounds having two or more hydroxyl groups can be used. However, the use of a polymer polyol is a point of flexibility and toughness. To preferred. Examples of the polymer polyol include polyether polyols such as polymers or copolymers such as ethylene oxide, propylene oxide, and tetrahydrofuran; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3- Propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, octanediol, 1,4-butyne Various known or unsaturated low molecular weight glycols such as diol and dipropylene glycol, or alkyl glycidyl ethers such as n-butyl glycidyl ether and 2-ethylhexyl glycidyl ether, versatic acid glycidyl ester, etc. Monocarboxylic acid glycidyl esters and adipic acid, maleic acid, fumaric acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, suberic acid Polyester polyols obtained by dehydration condensation of dibasic acids such as acid anhydrides or dimer acids corresponding thereto; polyester polyols obtained by ring-opening polymerization of cyclic ester compounds; other polycarbonate polyols, polybutadienes Polyolefin diols such as diol, polyisoprene diol, polychloroprene diol, polybutadiene glycol hydride, polyisoprene glycol hydride, and the like obtained by adding ethylene oxide or propylene oxide to bisphenol A Obtained by polymerizing various radical polymerizable unsaturated monomers such as alkyl (meth) acrylate in the presence of a chain transfer agent having one chain transfer group such as two or more hydroxyl groups and mercapto groups. And a macromonomer such as acrylic polymer, polyalkoxysilanes such as polydimethylsiloxane, castor oil polyol, chlorinated polypropylene polyol and the like. Among these polymer polyols, polyester polyols are preferably used because of their excellent adhesion to glass substrates. In addition, the number average molecular weight of these polymer polyols is usually about 1500 to 6000.

The polyisocyanate component forms a hard segment of PU2, and includes various types such as a chain aliphatic polyisocyanate, a cyclic aliphatic polyisocyanate, an aromatic polyisocyanate, an araliphatic polyisocyanate, and a polyisocyanate obtained from an amino acid derivative. Can be illustrated. More specifically, it is the same as the polyisocyanate component similar to that described in PU1.

As the chain extender which is a constituent component of the polyurethane (a), it is usually preferable to use a low molecular polyol and / or a low molecular polyamine having about 2 to 6 carbon atoms. More specifically, it is the same as the chain extender in PU1, and the amount of the chain extender used is the same as in PU1.

The polyurethane (a) can be produced in the same manner as the production method of PU1, and the number average molecular weight is preferably about 1800 to 100,000.

  The alkoxysilane (b) to be reacted with the polyurethane (a) is appropriately selected from those having a functional group corresponding to the functional group of the polyurethane (a). That is, when the terminal functional group of the polyurethane (a) is an isocyanate group, an alkoxysilane (b) having a hydroxyl group and / or an amino group is used, and the terminal functional group of the polyurethane (a) is a hydroxyl group or an amino group. In this case, alkoxysilane (b) having an isocyanate group is used.

  Examples of the alkoxysilane having an amino group include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltriethoxysilane, 3-aminopropyltris (trimethylsiloxy) silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (6 -Aminohexyl) -aminopropyltrimethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane, aminophenyltrimethoxysilane and the like. Examples of the alkoxysilane having an isocyanate group include 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmonomethyldiethoxysilane, and 3-isocyanatopropyldimethylethoxysilane.

Although the manufacturing method of PU2 is not particularly limited, for example, the following method can be adopted. For the polyurethane (a) having an isocyanate group at the end, an amino group or hydroxyl group-containing alkoxysilane (b) having an amount equal to or less than the terminal functional group is added, and similarly the polyurethane having a terminal functional group being a hydroxyl group or an amino group ( Also for a), it can be produced by adding an isocyanate group-containing alkoxysilane (b) equal to or less than the functional group and reacting in the range of 30 to 100 ° C. for about 1 to 12 hours.

S1 which is a constituent component of the composition C2 is the same as that used in the PU1. The amount of S1 used is also determined in consideration of the adhesiveness between the silane-modified polyurethane and the glass substrate in the composition C2 in the obtained soundproofing material performance of the present invention, and is the same as the usage rate in the PU1.

About compounds C3, PU3 and S1 PU3 which is a constituent component of the compound (C3) is a polyurethane having a high molecular polyol and a polyisocyanate as main constituent components and having hydroxyl groups at both ends. The polymer polyol forms a soft segment of PU3, and various polymer polyols having two or more hydroxyl groups can be exemplified. Specific examples thereof are the same as those described in the polyurethane (a) which is a constituent component of the PU2. Among the high-molecular polyols, polyoxyalkylene glycol is preferable because it is excellent in performance (flexibility and toughness) of the cured product of the composition (C3), and in particular, polypropylene glycol, poly (propylene glycol-ethylene glycol). Examples include block copolymers. The number average molecular weight of these polymer polyols is preferably about 1500 to 6000, as described above.

In addition, as a structural component of PU3, it is preferable to use a low molecular polyol having about 2 to 6 carbon atoms, if necessary, using a low molecular polyol. In particular, it is more preferable to use a diol compound having a tertiary amino group because a uniform cured product can be obtained. The amount of the low molecular polyol used is usually 1 or less, preferably 0.8 or less, based on 1 equivalent of the hydroxyl group of the polymer polyol.

The said polyisocyanate forms the hard segment of PU3, The polyisocyanate similar to what was used as a component of said PU1 and PU2 can be used.

  PU3 is composed of the above-described polymer polyol and polyisocyanate, and if necessary, a low-molecular-weight polyol as a main constituent and having hydroxyl groups at both ends, and the polymer polyol so that both ends of the PU3 molecule are hydroxyl groups. And polyisocyanate, and if necessary, the amount of low molecular polyol can be adjusted appropriately to cause the reaction. The manufacturing method is the same as in the case of PU1 or PU2. The number average molecular weight of PU3 is preferably about 3000 to 50000.

  Compound C3 is obtained by subjecting PU3 and S1 to a dealcoholization reaction, and the use ratio (PU3 / S1) of these is usually preferably in the range of 100 / (3 to 40) by weight. In the usage ratio, when the ratio of S1 decreases, tack tends to remain in the cured product of compound C3. Therefore, the ratio of S1 is more preferably 5 or more. On the other hand, since the shrinkage | contraction at the time of hardening of compound C3 will become large and the crack may be caused when the ratio of S1 increases, the ratio of S1 is more preferably 35 or less.

Compound C3 is obtained, for example, by subjecting each of the above components to an ester exchange reaction while distilling off the alcohol produced by heating. The reaction temperature is about 70 to 150 ° C., preferably 80 to 130 ° C., and the total reaction time is about 2 to 15 hours. In the above dealcoholization reaction, a conventionally known ester-hydroxyl ester exchange catalyst can be used for promoting the reaction. For example, organic acids such as acetic acid, para-toluenesulfonic acid, benzoic acid, propionic acid, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, Examples thereof include metals such as lead, antimony, arsenic, cerium, boron, cadmium and manganese, and oxides, organic acid salts, halides and alkoxides thereof. Among these, organic acid type, organic tin, and organic acid tin are particularly preferable, and specifically, acetic acid and dibutyltin dilaurate are effective.

  The dealcoholization reaction can be carried out in the absence of a solvent or in the presence of a solvent. In the case of using a solvent from the viewpoint of workability, there is no particular limitation. However, it is preferable to use an aprotic polar solvent such as dimethylformamide, dimethylacetamide, or methyl ethyl ketone.

  The compound C3 thus obtained contains, as a main component, polyurethane in which both terminal hydroxyl groups of the molecule are silane-modified, but the product may contain a small amount of unreacted PU3 or S1.

Compositions C4, PU4, and S1 PU4, which is a constituent of composition C4, reacts with a polymer polyol and a polyisocyanate, and then uses a hydroxyl group-containing polyamine, primary and secondary as a chain extender. It is obtained by reacting at least one selected from the group consisting of amino group-containing polyamines, has a hydroxyl group and / or an amino group in the molecule, and the sum of the hydroxyl value and the amine value is 1 or more. Polyurethane. Since the hydroxyl group and / or amino group in PU4 has a function of hydrogen-bonding or chemically bonding with a silanol group generated by hydrolysis of S1 to lead silica to a hard segment, the sum of the hydroxyl value and amine value of PU4 is It is preferably 1 or more, and more preferably 2 or more. Further, when the total of the hydroxyl value and the amine value is increased, the solubility of PU4 in an organic solvent may be reduced or gelation may occur during synthesis. Therefore, the total of the hydroxyl value and the amine value is 100 or less, Further, it is preferably 50 or less.

  The hydroxyl group and / or amino group in PU4 is present in the main chain of the molecule, but may be further present at the terminal. The hydroxyl group and / or amino group is appropriately adjusted by various means so that the polyol component and the polyisocyanate, as well as the chain extender and chain length terminator, can be adjusted so that the sum of the hydroxyl value and the amine value falls within the predetermined range. Thus, it can be introduced into PU4.

  For example, when a hydroxyl group is introduced into the molecular terminal of PU4, the polyol component and the polyisocyanate are reacted so that the equivalent of the hydroxyl group of the polyol component is excessive with respect to the equivalent of the isocyanate group of the polyisocyanate.

  The polyol component in PU4 forms a soft segment of PU4, and various compounds having two or more hydroxyl groups can be used, but it is preferable to use a polymer polyol. Specific examples thereof include the same compounds as described in PU1 to PU3. Moreover, the polyisocyanate of PU4 can mention the compound similar to having described by said PU1-PU3.

When the polyol component and the polyisocyanate are further reacted with a chain extender, a hydroxyl group and / or an amino group can be introduced into the main chain of PU4 and further to the terminal. For the reaction of the polyol component, polyisocyanate and chain extender, a general polyurethane production method can be used. Usually, the urethane prepolymer method in which the polyol component and polyisocyanate are reacted in advance and then the chain extender is reacted is employed. To do.

In the production of PU4, in order to introduce a hydroxyl group and / or amino group into the main chain of the molecule, a compound having a hydroxyl group and / or amino group that does not participate in the chain extension reaction is used as the chain extender. A hydroxyl group-containing polyamine compound can be used as the chain extender, but only the amino group of the compound is involved in the chain extension reaction, and the hydroxyl group remains unreacted in the main chain of PU4. Examples of the hydroxyl group-containing polyamine compound include 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropyl. Examples include ethylenediamine.

In order to introduce an amino group into the molecular main chain of PU4, a polyamine compound having a primary amino group and a secondary amino group is used as a chain extender. In the polyamine compound, only the primary amino group having good reactivity is involved in the chain extension reaction, and the secondary amino group remains in the main chain of PU4. Examples of the polyamine compound include triethylenetetramine and diethylenetriamine.

When introducing a hydroxyl group into the molecular end chain of PU4, a low molecular polyol is used as the chain extender, and when introducing an amino group at the terminal, a low molecular polyamine compound is used as the chain extender. In these cases, each component is adjusted so that the equivalent of the amino group and / or the hydroxyl group of the chain extender exceeds the equivalent of the isocyanate group of the urethane polymer.

As the low molecular polyol, the same compounds as described in the PU1 and the like can be used. Examples of the low molecular weight polyamine include ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine and the like.

  These chain extenders can be used alone or in combination of two or more. However, when a low molecular polyol and the polyamine compound are used in combination, the chain is first extended with the low molecular polyol and then further extended with the polyamine compound. It is preferable to employ a two-stage chain extension method.

  In addition, for the preparation of PU4, if the total of the hydroxyl value and the amine value falls within the predetermined range, dialkylamines such as di-n-butylamine; Chain length terminators such as monohydric alcohols can also be used.

  The amount of the chain extender and the chain extension terminator used is not particularly limited as long as the sum of the hydroxyl value and the amine value falls within the predetermined range, but the total amount of the polyol component and the polyisocyanate. Of about 20% by weight, more preferably 15% by weight or less.

  The number average molecular weight of PU4 thus obtained is preferably about 5000 to 100,000.

SI which is a constituent component of the composition C4 is the same compound as described in the PU1 and the like. The amount of S1 used is also determined in consideration of the adhesiveness between the silane-modified polyurethane and the glass substrate in the composition C4 in the obtained soundproofing material performance of the present invention, and is the same as the usage ratio in the PU1.

About compounds C5, PU5, and S2 PU5, which is a constituent of composition C5, is a polyurethane having a high-molecular polyol and a polyisocyanate as main constituents and having reactivity with epoxy groups. The polyol component in the polymer polyol is the same compound as described in the polyurethane (a) which is a constituent component of the PU2. Moreover, the point which can substitute a part of high molecular polyol by low molecular diol is the same as the description in a polyurethane (a).

Also for the polyisocyanate, the same compounds as described in the PU1 and polyurethane (a) can be used. Further, as the chain extender, the same compounds as described in PU1 can be used, and glycols having a carboxyl group in the molecule such as dimethylolpropionic acid and dimethylolbutanoic acid can be used. Moreover, in order to adjust the molecular weight of PU5, the same chain length terminator as described in PU1 and polyurethane (a) can be used.

The method for manufacturing PU5 can adopt the same method as in PU1.

The functional group having reactivity with the epoxy group in PU5 may be present at either the terminal or main chain of the molecule. Examples of the functional group include an acidic group such as a carboxyl group, a sulfone group, and a phosphoric acid group, an amino group, a hydroxyl group, and a mercapto group. Usually, the reactivity with an epoxy group and the ease of imparting a functional group are included. Therefore, an acidic group and an amino group are preferable. Although there is no limitation on the method for imparting an acidic group to PU5, for example, among the chain extenders and chain length terminators described above, a carboxyl group can be easily imparted if one having a carboxyl group is used. The method for imparting amino groups to PU5 is not limited. For example, polyamines may be reacted with the terminal isocyanate groups of the prepolymer so that the amino groups are excessive. The amount of the epoxy group-reactive functional group in PU5 is not particularly limited, but it is usually preferably 0.1 to 20 mgKOH / g. When it is less than 0.1 mgKOH / g, the flexibility and heat resistance of the resulting silane-modified polyurethane resin cured product are lowered, and when it exceeds 20 mgKOH / g, the water resistance of the silane-modified polyurethane resin cured product tends to be lowered.

  S2, which is another component of the compound C5, is obtained by a dealcoholization reaction between the epoxy compound (α) and the alkoxysilane partial condensate (B).

The number of epoxy groups is not particularly limited as long as the epoxy compound (α) is an epoxy compound having one hydroxyl group in one molecule. In addition, as the epoxy compound (α), the smaller the molecular weight, the better the compatibility with the alkoxysilane partial condensate (B), and the higher the heat resistance and adhesion imparting effect. Is preferred. Specific examples include monoglycidyl ethers having one hydroxyl group at the molecular end obtained by reacting epichlorohydrin with water, dihydric alcohol or phenol; epichlorohydrin and glycerin, pentaerythritol, etc. Polyglycidyl ethers having one hydroxyl group at the molecular end obtained by reacting with a trihydric or higher polyhydric alcohol of the above; one hydroxyl group at the molecular end obtained by reacting epichlorohydrin and amino monoalcohol Examples thereof include alicyclic hydrocarbon monoepoxides having one hydroxyl group in the molecule (for example, epoxidized tetrahydrobenzyl alcohol). Among these epoxy compounds, glycidol is most excellent in terms of heat resistance and toughness, and is also optimal because of its high reactivity with the alkoxysilane partial condensate (B).

The alkoxysilane partial condensate (B) is the same compound as S1, but the alkoxysilane partial condensate (B) has a number average molecular weight of about 230 to 2,000, and has good reactivity. It can be preferably used because it is difficult to be distilled off.

  S2 is obtained by subjecting the epoxy compound (α) and the alkoxysilane partial condensate (B) to dealcoholization (transesterification). The use ratio of the epoxy compound (α) and the alkoxysilane partial condensate (B) is not particularly limited as long as the alkoxy group substantially remains, but usually the equivalent of the hydroxyl group of the epoxy compound (α). The alkoxysilane partial condensate (B) and the epoxy compound (α) are subjected to a dealcoholization reaction at a charging ratio of equivalent of alkoxyl group of the / alkoxysilane condensate (B) = 0.01 / 1 to 0.7 / 1. It is preferable. Since the ratio of the alkoxysilane partial condensate (B) that is not epoxy-modified increases when the charging ratio decreases, the charging ratio is preferably 0.03 or more / 1. Moreover, since the epoxy group of the epoxy group-containing alkoxysilane partial condensate becomes multifunctional and easily gels when synthesizing the silane-modified urethane resin when the charging ratio increases, the charging ratio is set to 0.5 or less / 1. Is preferred.

  The reaction between the alkoxysilane partial condensate (B) and the epoxy compound (α) is carried out, for example, while the above components are charged and the alcohol produced by heating is distilled off. The reaction temperature is about 50 to 150 ° C., preferably 70 to 110 ° C., and the total reaction time is about 1 to 15 hours. If the dealcoholization reaction is carried out at a temperature exceeding 110 ° C., the molecular weight of the reaction product increases too much with the condensation of alkoxysilane in the reaction system, and there is a tendency to increase the viscosity or gel. In such a case, viscosity increase and gelation can be prevented by a method such as stopping the dealcoholization reaction during the reaction. In the dealcoholization reaction, a catalyst which does not open an epoxy ring among conventionally known catalysts can be used for promoting the reaction. For example, metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, , These oxides, organic acid salts, halides, alkoxides and the like. Among these, organic tin and organic acid tin are particularly preferable, and specifically, dibutyltin dilaurate and tin octylate are effective. The reaction can also be performed in a solvent. The solvent is not particularly limited as long as it dissolves the alkoxysilane condensate (B) and the epoxy compound (α) and is inert to the epoxy group of the epoxy compound (α). As such an organic solvent, it is preferable to use the solvent used in the production of PU5.

  Compound C5 is obtained by reacting PU5 and S2. The use ratio of PU5 and S2 is not particularly limited, but it is preferable that the total equivalent (equivalent ratio) of the epoxy group reactive functional group of PU5 / equivalent of the epoxy group of S2 is in the range of 0.30 to 5. If it is less than 0.30, the resulting compound C5 cannot sufficiently exhibit the effects of the present invention, and if it exceeds 5, the proportion of unreacted S2 in the compound C5 increases, such being undesirable.

  In the production of compound C5, for example, each of the above components is charged and reacted in a substantially anhydrous state by heating. The main purpose of this reaction is to react the acidic group and / or amino group of PU5 with the oxirane group of S2, and it is necessary to suppress the formation of silica due to the sol-gel reaction of the alkoxysilyl moiety of S2 during this reaction. Therefore, the reaction temperature is room temperature to about 150 ° C., preferably 40 to 120 ° C., and the total reaction time is preferably about 1 to 10 hours.

  In the above reaction, a catalyst is not particularly required, but a conventionally known catalyst can be used for promoting the reaction. For example, tertiary amines such as 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) urethane; 2 -Imidazoles such as methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; Organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine; Tetraphenylphosphonium / tetraphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, etc. Such as Ron salt can be mentioned. You may use a reaction catalyst in the ratio of 0.01-5 weight part with respect to 100 weight part of solid content of PU5.

  In addition, the above reaction can be selected appropriately in a solvent or in the absence of a solvent according to the purpose of use. The solvent is not particularly limited as long as it is a solvent capable of dissolving PU5 and S2, and as the solvent, the same solvent as used in the production of PU5 or S2 can be used.

The compound C5 thus obtained has an alkoxy group derived from the alkoxysilane partial condensate (B) in the molecule. The content of the alkoxy group is not particularly limited, but the alkoxy group is bonded to each other by evaporation of a solvent, heat treatment, or sol-gel reaction or dealcoholization condensation by reaction with moisture (humidity). Since it is necessary to form a cured product, the alkoxy group-containing silane-modified polyurethane resin is usually 50 to 95 mol%, preferably 60 to 90 mol% of the alkoxy group of the alkoxysilane partial condensate (B). It is better to keep it.

The cured product obtained from the compound C5 has a fine gelled silica portion (a high-order network structure of siloxane bonds). Compound C5 is mainly composed of a polyurethane resin in which a part of the epoxy group-reactive functional group in PU5 is silane-modified. In compound C5, unreacted alkoxysilane partial condensate (B), S2, The solvent and catalyst used for the reaction may be contained. The unreacted alkoxysilane partial condensate (B) and S2 are cured with silica by hydrolysis and polycondensation during the curing, and are integrated with the compound C5.

  The various silane-modified polyurethanes (composition C1, composition C2, compound C3, composition C4, and compound C5) prepared in this way are excellent in adhesiveness to the glass substrate. The soundproofing material of the present invention can be prepared by blending. In preparing the soundproofing material of the present invention, fillers (silica, alumina, titanium oxide, calcium carbonate, aluminum hydroxide, magnesium hydroxide, etc.), solvents, plasticizers, antibacterial agents, antifungal agents, leveling agents, antifoaming Various additives such as a colorant, a colorant, and a stabilizer can be appropriately added. Moreover, it cannot be overemphasized that the component normally used can be mix | blended and used in various uses.

In the present invention, when the glass substrate is a fiber, the fiber is immersed in the silane-modified polyurethane or an organic solvent solution thereof. When the glass substrate is a fabric, the fabric may be dipped in a silane-modified polyurethane resin or an organic solvent solution thereof and then pulled up, or may be applied to one side or both sides of the fabric. As a coating method, for example, known means such as an applicator, knife coater, reverse roll coater, gravure coater, flow coater, rod coater or brush coating can be employed.

The coating amount or impregnation amount of the silane-modified polyurethane resin is about 1 to 50% by weight, preferably 5 to 25% by weight, based on the glass substrate coated or impregnated with the polyurethane resin. By applying this treatment to the glass substrate, the binding of the glass substrate is strengthened, and the soundproofing properties and strength of the resulting soundproof material molding are improved.

The soundproofing property and strength of the soundproofing material of the present invention are related to the type and thickness of the glass substrate used and the coating amount or impregnation amount of the silane-modified polyurethane resin. Although the thickness of a glass base material can be suitably determined according to the use of the soundproof material obtained, Usually, it is about 1 mm or less, and it is preferable that it is about 30-500 micrometers. In general, if the thickness of a single layer of the molded product exceeds 500 μm, the fabric eyes may appear on the molded product of the soundproofing material when the molding press is applied, causing warping, swelling, etc. There is a tendency that it becomes too difficult and the flexibility is impaired and the construction becomes difficult. In this case, by using a molded product having a multi-layer structure, problems such as embossing, warping, and swelling of the fabric can be reduced.

The reason why the soundproofing material of the present invention having the silane-modified polyurethane resin as an essential component exhibits the above-mentioned properties is not necessarily clear, but the sites derived from S1 and S2 in the silane-modified polyurethane resin are the glass substrate and filler. By interacting or reacting strongly, strength, heat resistance, adhesion to the base material will be improved, and the soft segment in the silane-modified polyurethane resin will retain the flexibility, and will exhibit appropriate flexibility Presumed to be possible.

The soundproofing material of the present invention can be provided with a picture layer or an overcoat layer as necessary in consideration of design and the like. The pattern layer and the topcoat layer are not particularly limited, and various known layers may be appropriately selected and used.

  Hereinafter, the present invention will be described more specifically with reference to production examples, examples and comparative examples. In each example, parts and% are in principle based on weight.

Production Example 1 (Production of polyurethane resin (PU1))
In a reaction apparatus equipped with a stirrer, a thermometer, a condenser tube and a nitrogen introduction tube, 1000 parts of polytetramethylene glycol (number average molecular weight 2000) and 278 parts of isophorone diisocyanate were charged, and reacted at 80 ° C. for 4 hours under a nitrogen stream. Next, 2820 parts of methyl ethyl ketone was added to the system, and after cooling to 50 ° C. with good stirring, a solution prepared by dissolving 114 parts of isophoronediamine and 18.2 parts of dibutylamine in 1410 parts of isopropyl alcohol was added dropwise over 10 minutes. The mixture was reacted at the same temperature for 1 hour. Thus, a polyurethane solution (PU1) having a number average molecular weight of about 20,000 and a solid content of 25% was obtained. The contact angle of the obtained polyurethane to water was 82 degrees.

Production Example 2 (Production of silane-modified polyurethane resin composition C1)
100 parts of polyurethane solution (PU1) obtained in Production Example 1, tetramethoxysilane partial condensate (S1) (manufactured by Tama Chemical Co., Ltd., trade name “methyl silicate 51”, Si average number is 4) 3.43 Part and 0.06 part of tin octylate were mixed to prepare a silane-modified polyurethane resin composition C1. The Si content in the solid content in the silane-modified polyurethane resin was 6.5% in terms of silica weight.

Production Example 3 (Production of epoxy group-containing alkoxysilane partial condensate (S2))
In a reactor equipped with a stirrer, a thermometer, a water separator, a cooling pipe and a nitrogen introduction pipe, 1400 parts of glycidol (manufactured by NOF Corporation, trade name “Epiol OH”) and a tetramethoxysilane partial condensate (the above-mentioned product) 8957.9 parts of the name “methyl silicate 51”) were charged, and the temperature was raised to 90 ° C. with stirring under a nitrogen stream, and then 2.0 parts of dibutyltin dilaurate was added as a catalyst to react. During the reaction, methanol was distilled off using a water separator, and the reaction was cooled when the amount reached about 630 parts. It took 5 hours to cool after raising the temperature. Subsequently, about 80 parts of methanol remaining in the system was removed under reduced pressure at 13 kPa for about 10 minutes. In this way, an epoxy group-containing alkoxysilane partial condensate (S2) was obtained. In addition, the equivalent of the hydroxyl group of the epoxy compound (A) at the time of preparation / the equivalent of the alkoxyl group of the alkoxysilane condensate (B) (equivalent ratio) = 0.10, and the epoxy equivalent is 512 g / eq.

Production Example 4 (Production of polyurethane resin (PU5))
In a reactor similar to Production Example 1, 1000 parts of polycarbonate diol (manufactured by Daicel Chemical Industries, Ltd., trade name “Placcel CD220”, molecular weight 2000) and 278 parts of isophorone diisocyanate were charged, and the mixture was heated at 100 ° C. for 6 hours under a nitrogen stream. The mixture was reacted, and 548 parts of methyl ethyl ketone was added thereto to obtain a uniform solution of urethane prepolymer. Subsequently, in the presence of a mixture comprising 46.4 parts of isophoronediamine, 14.2 parts of 2-hydroxyethylethylenediamine, 6.1 parts of di-n-butylamine, 1249 parts of methyl ethyl ketone and 776 parts of isopropyl alcohol, the above urethane prepolymer solution. 1000 parts were added and reacted at 50 ° C. for 3 hours. Thus, a polyurethane solution (PU5) having a number average molecular weight of about 15,000, an amine value of resin solid content of 4.0 mgKOH / g, and a solid content of 25% was obtained.

Production Example 5 (Production of silane-modified polyurethane resin C5)
After heating 100 parts of the polyurethane resin (PU5) obtained in Production Example 4 to 50 ° C., 3.7 parts of the epoxy group-containing alkoxysilane partial condensate (S2) obtained in Production Example 3 was added, And reacted at 60 ° C. for 4 hours to obtain a silane-modified polyurethane resin (C5). In addition, Si content in the solid residue in the alkoxy group-containing silane-modified polyurethane resin was 6.5% in terms of silica weight.

Example 1 (Preparation of soundproof molding)
An 80 cm × 80 cm glass cloth (single fiber diameter: 6 μm, cloth weight: 335 g / m ² , cloth density (number of single fibers per 2.5 cm) of 30 × 28) was obtained in Production Example 2. After impregnating the silane-modified polyurethane resin composition C1 so as not to contain bubbles, the resin composition C1 is applied on one side and the total thickness is about 0.8 mm with seven layers in total, and the silane-modified polyurethane resin A soundproof sheet having 6 layers was prepared. The thickness of each layer is about 0.1 mm.

Comparative Example 1
In Example 1, in place of the silane-modified polyurethane resin composition C1 obtained in Production Example 2, the polyurethane resin PU1 obtained in Production Example 1 was used, except that the polyurethane resin PU1 was used. A soundproof sheet having an overall thickness of about 0.8 mm was obtained. The thickness of each layer is about 0.1 mm.

Example 2
The same glass cloth as used in Example 1 was impregnated with the polyurethane resin PU1 obtained in Production Example 1, and then coated on both sides with the polyurethane resin PU1 obtained in Production Example 1 and dried at room temperature. It was. Next, the silane-modified polyurethane resin composition C1 obtained in Production Example 2 was applied to both surfaces, and dried at room temperature. Furthermore, the polyurethane resin PU1 obtained in Production Example 1 was applied to both surfaces and dried at room temperature, so that the total thickness was about 0.8 mm with 7 layers in total, and 4 silane-modified polyurethane resin layers were formed. A soundproof sheet was prepared. The thickness of each layer is about 0.1 mm.

Example 3
After impregnating the same glass cloth as used in Example 1 with the polyurethane resin C5 obtained in Production Example 5 so as not to include bubbles, the resin C5 is applied to both surfaces of the resin and dried at room temperature. It was. Subsequently, the polyurethane resin PU1 obtained in Production Example 1 was applied to both surfaces, and dried at room temperature. Furthermore, the resin C5 was applied to both surfaces and dried at room temperature to prepare a soundproof sheet having a total of 7 layers and a total thickness of about 0.8 mm and having 4 silane-modified polyurethane resin layers. The thickness of each layer is about 0.1 mm.

Example 4
An 80 cm × 80 cm glass cloth (single fiber diameter 9 μm, cloth weight 312 g / m ² , cloth density (number of single fibers per 2.5 cm) of 32 × 25) was obtained in Production Example 2. After impregnating the silane-modified polyurethane resin composition C1 so as not to contain bubbles, the resin composition C1 was applied to both surfaces of the resin composition C1 and dried at room temperature. Next, the polyurethane resin C5 obtained in Production Example 5 was applied to both surfaces, and dried at room temperature. Furthermore, by applying the resin composition C1 to each of the both surfaces and drying at room temperature, a total of 7 layers and a total thickness of about 0.8 mm and a 6-layer silane-modified polyurethane resin layer are prepared. did. The thickness of each layer is about 0.1 mm.

Comparative Example 2
In Comparative Example 1, a soundproof sheet having a total thickness of about 0.8 mm with a total of 7 layers was obtained in the same manner as in Comparative Example 1, except that it was replaced with a different glass cloth (the same one used in Example 4). Obtained. The thickness of each layer is about 0.1 mm.

(Measurement of sound insulation)
It measured based on JISZ8732. That is, the soundproof material (double-sided coated sheet) obtained above was placed in a semi-acoustic room with a humidity of 56% and a temperature of 26 ° C. so as to be vertical, and the sound wave ( The intensity of incident sound and transmitted sound at 2500 HZ was measured by irradiating with a sound pressure level of 80 dB and a center frequency of the input wave of 2.5 KHz. Thereby, the transmittance (τ) was obtained from the following equation. Transmittance (τ) = transmitted sound intensity / incident sound intensity

Further, transmission loss (R) was determined from the transmittance (τ) according to the following equation.
R = ₁₀ log ₁₀ 1 / τ

The obtained transmission loss is shown in Table 1. Larger transmission loss means better soundproofing.

As is clear from comparison between Example 1 and Comparative Example 1, it is recognized that the soundproofing material according to the present invention is superior in soundproofing effect. Similarly, as is clear from comparison between Examples 2 and 3 and Comparative Example 1, it is recognized that the soundproofing material according to the present invention is superior in soundproofing effect. Further, as apparent from the comparison between Example 4 and Comparative Example 2, it is recognized that the soundproofing material according to the present invention is superior in soundproofing effect.

Production Example 6 (Production of silane-modified polyurethane resin composition C1)
100 parts of polyurethane solution (PU1) obtained in Production Example 1, tetramethoxysilane partial condensate (S1) (manufactured by Tama Chemical Co., Ltd., trade name “methyl silicate 51”, Si average number is 4) 6.86 Part and 0.06 part of tin octylate were mixed to prepare a silane-modified polyurethane resin composition C1-2. The Si content in the solid content in the silane-modified polyurethane resin was 12.3% in terms of silica weight.

Production Example 7 (Production of polyurethane resin composition)
To 100 parts of the polyurethane solution (PU1) obtained in Production Example 1, 5.83 parts of silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name “MEK-ST”, silica content: 30% by weight) is added at room temperature. The polyurethane resin composition PU2 was prepared by stirring and mixing in the above. The silica content in the polyurethane resin composition (as a solid content) is 6.5%.

Example 5 (Preparation of soundproof molding)
An 80 cm × 80 cm glass cloth (single fiber diameter 6.5 μm, cloth weight 343 g / m ² , cloth density (number of single fibers per 2.5 cm) of 29 × 32) obtained in Production Example 2 The impregnated silane-modified polyurethane resin composition C1 was impregnated so as not to contain bubbles, and then the silane-modified polyurethane resin composition C1 was applied on one side to prepare a soundproof sheet having six silane-modified polyurethane resin layers. . The thickness of each layer is about 0.1 mm.

Example 6
In Example 5, in place of the silane-modified polyurethane resin composition C1 obtained in Production Example 2, the polyurethane resin C1-2 obtained in Production Example 6 was used. A soundproof sheet having six modified polyurethane resin layers was prepared. The thickness of each layer is about 0.1 mm.

Comparative Example 3
In Example 5, in place of the silane-modified polyurethane resin composition C1 obtained in Production Example 2, the polyurethane resin PU1 obtained in Production Example 1 was used, and a total of 7 layers were obtained in the same manner as in Example 5. Thus, a soundproof sheet having an overall thickness of about 0.7 mm was obtained. The thickness of each layer is about 0.1 mm.

Comparative Example 4
In Example 5, in place of the silane-modified polyurethane resin composition C1 obtained in Production Example 2, the polyurethane resin composition PU2 obtained in Production Example 7 was used. A soundproof sheet having a total thickness of about 0.7 mm with seven layers was obtained. The thickness of each layer is about 0.1 mm.

Using each of the soundproof sheets obtained in Example 5, Example 6, Comparative Example 3 and Comparative Example 4, the same as described above (however, the humidity at the time of measurement was 45%, the temperature was 23 ° C.) and the soundproofing property was obtained. It was measured. The results are shown in Table 2.

A comparison between Example 1 in Table 1 and Example 5 in Table 2 shows that there are some differences in the soundproofing data due to the types of glass cloth and the difference in humidity and temperature during measurement. Similar to the difference between Example 1 and Comparative Example 1 (the soundproofing material according to the present invention is superior in soundproofing effect), the difference between Example 5 and Comparative Example 3 in Table 2 is the same tendency (soundproofing according to the present invention). It was confirmed that the material is superior in soundproofing effect). Further, as apparent from the comparison between Example 5 and Comparative Example 4 in Table 2, it was recognized that the soundproofing material according to the present invention is superior in soundproofing effect. That is, it was confirmed that silane-modified polyurethane (having a silica-forming site in the molecule) was superior in soundproofing effect compared to a mixture of polyurethane and silica. Further, as apparent from the comparison between Example 6 and Comparative Examples 3 and 4, it is recognized that the soundproofing material according to the present invention is superior in soundproofing effect.

Claims (16)

A soundproofing material obtained by impregnating glass fiber or the cloth with a silane-modified polyurethane resin. 2. The glass fiber according to claim 1, wherein the glass fiber is at least one selected from the group consisting of a single fiber, a strand, a yarn, and a roving, and the glass fabric is made of the glass fiber and has a thickness of 0.03 to 0.5 mm. Soundproof material. The silane-modified polyurethane resin is a polyurethane obtained by reacting a polyoxyalkylene diol having 3 or more carbon atoms of an alkylene group, a polyisocyanate, and, if necessary, a chain extender, and has a contact angle with water of 70 degrees. The soundproofing material according to claim 1 or 2, which is a composition (C1) comprising the above (PU1) and hydrolyzable alkoxysilane (S1). The soundproofing material according to claim 1 or 2, wherein the silane-modified polyurethane resin is a composition (C2) comprising polyurethane (PU2) having alkoxysilyl groups at both ends and hydrolyzable alkoxysilane (S1). A compound obtained by subjecting a silane-modified polyurethane resin to a dealcoholization reaction between polyurethane (PU3) having a polymer polyol and polyisocyanate as main constituents and having hydroxyl groups at both ends and hydrolyzable alkoxysilane (S1) The soundproofing material according to claim 1 or 2, which is (C3). After the silane-modified polyurethane resin reacts with the polymer polyol and the polyisocyanate, it reacts with at least one selected from the group consisting of a hydroxyl group-containing polyamine, a primary and a secondary amino group-containing polyamine as a chain extender. It is obtained and comprises a polyurethane (PU4) having a hydroxyl group and / or an amino group in the molecule and having a total hydroxyl value and amine value of 1 or more, and a hydrolyzable alkoxysilane (S1). The soundproofing material according to claim 1 or 2, which is a composition (C4). A silane-modified polyurethane resin comprising a polymer polyol and polyisocyanate as main components and having reactivity with an epoxy group (PU5), an epoxy compound having one hydroxyl group in one molecule, and a hydrolyzable alkoxysilane The soundproofing material according to claim 1 or 2, which is obtained (C5) by reacting with an epoxy group-containing alkoxysilane partial condensate (S2) obtained by a dealcoholization reaction. The soundproofing material according to claim 4, wherein the polyurethane (PU2) is a reaction product of a polyurethane having an isocyanate group at both ends and an alkoxysilane having an amino group. The soundproofing material according to claim 5, wherein the polyurethane (PU3) uses polyoxyalkylene glycol as the polymer polyol. The soundproofing material according to claim 7, wherein the polyurethane (PU5) uses a polyester polyol and / or a polycarbonate polyol as the polymer polyol. The hydrolyzable alkoxysilane (S1) has the general formula (a):

The soundproofing material according to any one of claims 1 to 10, which is poly (tetramethoxysilane) represented by the formula (wherein Me represents a methyl group and n is an integer of 0 to 8). The soundproofing material according to any one of claims 1 to 11, further comprising a filler. The soundproofing material according to claim 12, wherein the filler is silica. A molded article comprising a layer (A) comprising the soundproofing material according to any one of claims 1 to 13. The molded product according to claim 14, wherein a pattern layer and / or a top coat layer are provided on one side or both sides of the layer (A). The molded product according to claim 15, wherein the molded product is a sheet.