JP2005281074A - Curable composition for interlayer film of laminated glass and laminated glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition for an interlayer film of laminated glass, which is prevented from whitening, maintains weather-resistant adhesivity for a long period, can reduce breakages of glass, and can prevent scattering of glass at the time of breakage of the glass; and to provide the laminated glass using the same. <P>SOLUTION: The curable composition for the interlayer film of the laminated glass contains a polymer (A) whose main chain includes an alkyl acrylate monomer unit and/or an alkyl methacrylate monomer unit and which contains at least one group including hydrolyzable silicon per one molecule, a silane coupling agent (B) and a tin catalyst and/or a titanium catalyst (C). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curable composition for a laminated glass interlayer film and a laminated glass using the same.

Conventionally, laminated glass has been widely used as window glass for automobiles, buildings and the like. As this laminated glass, one having an intermediate film formed by forming a plasticized polyvinyl acetal resin such as a polyvinyl butyral resin plasticized with a plasticizer between at least a pair of glasses is known (for example, Patent Document 1).
Such a laminated glass resin for laminated glass generally has good transparency, weather resistance and adhesiveness, and is excellent in penetration resistance. Therefore, when an impact is applied to such laminated glass, Although the glass is broken, the intermediate film interposed between the glasses is not easily broken, and the glass remains adhered to the intermediate film even after the breakage, so that the fragments are hardly scattered. Therefore, when such laminated glass is used for window glass for automobiles or buildings, even if the glass is damaged due to an accident, typhoon, etc., the human body inside is damaged by the glass fragments. This has an excellent effect in terms of crime prevention and security measures.

In addition, as described above, a polyvinyl acetal resin is usually used as the interlayer film resin for laminated glass.
However, the laminated glass using a polyvinyl acetal resin as an intermediate film has the following problems. That is, when a metal salt is added to the polyvinyl acetal resin, the hygroscopicity of the composition is improved, and the composition becomes more susceptible to water. Had the disadvantage of becoming.

JP-A-11-106595

  Therefore, the present invention provides a curable composition for laminated glass interlayer film that prevents whitening, has weather resistant adhesion over a long period of time, reduces glass breakage, and further prevents glass scattering upon breakage. An object is to provide an object and a laminated glass using the object.

As a result of intensive studies to solve the above problems, the present inventor has found that the main chain includes an alkyl acrylate monomer unit and / or a methacrylic acid alkyl ester monomer unit, and one molecule of hydrolyzable silicon-containing group. A curable composition containing at least one polymer per unit, a silane coupling agent, a tin catalyst and / or a titanium catalyst prevents whitening and has a long-term weather-resistant adhesive, It discovered that it became a curable composition for laminated glass intermediate films which can reduce a breakage and can prevent scattering of the glass at the time of a breakage, and completed this invention.
That is, this invention provides the curable composition for laminated glass intermediate films shown to the following (1)-(5), and the laminated glass shown to (6)-(8).

(1) a polymer (A) having a main chain containing an alkyl acrylate monomer unit and / or an alkyl methacrylate monomer unit and having at least one hydrolyzable silicon-containing group per molecule;
A silane coupling agent (B);
A curable composition for a laminated glass interlayer film containing a tin catalyst and / or a titanium catalyst (C) (first embodiment).

  (2) The laminated glass interlayer film according to (1), further comprising a polymer (D) having a main chain containing an alkylene oxide monomer unit and having at least one hydrolyzable silicon-containing group per molecule. Curable composition.

  (3) 0.1 to 20 parts by mass of the silane coupling agent (B) and 0.01 to 20 parts by mass of the catalyst (C) are contained with respect to 100 parts by mass of the polymer (A). The curable composition for laminated glass interlayer films according to (1) above.

  (4) 0.1-100 mass parts of said silane coupling agents (B) are contained with respect to a total of 100 mass parts of said polymer (A) and said polymer (D), and said catalyst (C) is contained. The curable composition for laminated glass interlayer films according to (2), containing 0.01 to 20 parts by mass.

  (5) The silane coupling agent (B) is obtained by reacting aminosilane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, ketimine silane, or a mixture or reaction thereof, or an epoxy resin or polyisocyanate. The curable composition for laminated glass interlayer films according to any one of (1) to (4), which is a compound.

  (6) A laminated glass having a cured product of the curable composition for laminated glass interlayer film according to any one of (1) to (5) described above (second aspect).

  (7) The laminated glass according to (6), wherein the intermediate film has an inner layer sandwiched between the cured products.

  (8) The laminated glass according to (7), wherein the inner layer is made of at least one selected from the group consisting of an alkyl acrylate rubber, a conjugated diene rubber, and a polyvinyl acetal resin.

  As described below, according to the present invention, it is possible to prevent whitening, to have long-term weather-resistant adhesiveness, to reduce glass breakage, and to prevent glass scattering at the time of breakage. This is useful because it can provide a curable composition for glass interlayer film and a laminated glass using the same.

The present invention is described in detail below.
In the curable composition for glass interlayer film according to the first aspect of the present invention (hereinafter also simply referred to as “the curable composition of the present invention”), the main chain is an alkyl acrylate monomer unit and / or A polymer (A) containing an alkyl methacrylate ester monomer unit and having at least one hydrolyzable silicon-containing group per molecule, a silane coupling agent (B), a tin catalyst and / or a titanium catalyst (C And a curable composition containing
Further, the main chain may contain a polymer (D) containing an alkylene oxide monomer unit and having at least one hydrolyzable silicon-containing group per molecule.
Next, the polymer (A), the silane coupling agent (B), the catalyst (C), and the polymer (D) that can be optionally used will be described in detail for the curable composition of the present invention.

<Polymer (A)>
The polymer (A) used in the present invention has a main chain containing an alkyl acrylate monomer unit and / or an alkyl methacrylate monomer unit, and at least one hydrolyzable silicon-containing group per molecule. It is a polymer having. In the present invention, the hydrolyzable silicon-containing group may be present at the terminal in the molecule of the polymer, may be present in the side chain, or may be present in both.

Examples of the acrylic acid alkyl ester monomer unit include, for example, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-t-butyl, and acrylic acid-n. -Hexyl, heptyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, lauryl acrylate, tridecyl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, behenyl acrylate, Biphenyl acrylate is mentioned.
Examples of the methacrylic acid ester monomer unit include, for example, methyl methacrylate, ethyl methacrylate, methacrylate-n-propyl, methacrylate-n-butyl, methacrylate-isobutyl, methacrylate-t-butyl, methacrylate- n-hexyl, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, myristyl methacrylate, cetyl methacrylate, stearyl methacrylate, behenyl methacrylate And biphenyl methacrylate.
These may be used alone or in combination of two or more.

  The main chain of the polymer (A) is not particularly limited as long as it contains an acrylic acid alkyl ester monomer unit and / or a methacrylic acid alkyl ester monomer unit, but the proportion of these monomer units is 50. It is preferable to exceed mass%, and it is more preferable that it is 70 mass% or more.

The main chain of the polymer (A) may contain, in addition to the acrylic acid alkyl ester monomer unit and / or the methacrylic acid alkyl ester monomer unit, a monomer unit copolymerizable therewith. . For example, a monomer unit containing a carboxy group such as acrylic acid or methacrylic acid; a monomer unit containing an amide group such as acrylamide, methacrylamide, N-methylolacrylamide, or N-methylolmethacrylamide; glycidyl acrylate, glycidyl Monomer units containing epoxy groups such as methacrylate; monomer units containing amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether; polyoxyethylene acrylate, polyoxyethylene methacrylate, etc. are moisture A copolymerization effect can be expected in terms of curability and internal curability.
In addition, monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like can be mentioned.

The monomer composition of the polymer (A) is appropriately selected depending on the application, purpose, etc. in which the laminated glass according to the second aspect of the present invention (hereinafter also simply referred to as “laminated glass of the present invention”) is used. .
For example, when the alkyl chain of the alkyl ester part of the monomer is long, the glass transition temperature is low, and the physical properties of the cured product are soft rubbery elastic bodies. On the other hand, when it is short, the glass transition temperature becomes high and the physical properties of the cured product become hard.
On the other hand, the physical properties after curing largely depend on the molecular weight of the polymer.
Therefore, the monomer composition of the polymer (A) may be appropriately selected according to the desired viscosity, physical properties after curing, and the like while considering the molecular weight.

The main chain of the polymer (A) can be obtained by a controlled vinyl polymerization method or the like. For example, it can be obtained by performing a solution polymerization method, a bulk polymerization method or the like by a chain transfer agent method, a living radical polymerization method or the like, but is not particularly limited to these methods.
In the chain transfer agent method, it is also possible to obtain a polymer having a functional group at the terminal by performing polymerization using a chain transfer agent having a specific functional group.
In the living radical polymerization method, a polymer having a molecular weight almost as designed can be obtained by growing the polymerization growth terminal without causing a termination reaction or the like.
The chain transfer agent method is a free radical polymerization and thus has a wide molecular weight distribution and only a polymer having a high viscosity can be obtained. However, the living radical polymerization method has a narrow molecular weight distribution (Mw / Mn is 1) because a termination reaction is unlikely to occur. About 1.5 to 1.5), a polymer having a low viscosity can be obtained, and a monomer having a specific functional group can be introduced at almost any position of the polymer. In the present invention, the method described in JP-A-2003-313397 is preferably used.
The reaction is usually carried out by mixing the above-mentioned monomer units, radical initiator, chain transfer agent, solvent and the like and reacting them at 50 to 150 ° C.

Examples of the radical initiator include azobisisobutyronitrile and benzoyl peroxide.
Examples of the chain transfer agent include mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, lauryl mercaptan; and halogen-containing compounds.
Suitable examples of the solvent include non-reactive solvents such as ethers, hydrocarbons and esters.

  The hydrolyzable silicon-containing group has 1 to 3 hydroxy groups and / or hydrolyzable groups bonded to silicon atoms, and in the presence of moisture or a crosslinking agent, a catalyst or the like is used as necessary. It is a silicon-containing group that can be crosslinked by causing a condensation reaction to form a siloxane bond. Examples thereof include an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, and an amidosilyl group. Specifically, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, an amidosilyl group and the like exemplified by the following formula are preferably used.

Among these, an alkoxysilyl group is preferable because it is easy to handle.
Although the alkoxy group couple | bonded with the silicon atom of an alkoxy silyl group is not specifically limited, Since acquisition of a raw material is easy, a methoxy group, an ethoxy group, or a propoxy group is mentioned suitably.
The group other than the alkoxy group bonded to the silicon atom of the alkoxysilyl group is not particularly limited. For example, a hydrogen atom or an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group An alkenyl group or an arylalkyl group is preferable.

  The number of hydrolyzable silicon-containing groups possessed by the polymer (A) is at least one per molecule. Further, the bonding position of the hydrolyzable silicon-containing group is preferably at the end of the main chain, and more preferably only at the end of the main chain.

The method for introducing a hydrolyzable silicon-containing group into the main chain of the polymer (A) is not particularly limited. For example, (i) in the presence of a mercaptan containing a hydrolyzable silicon-containing group as a chain transfer agent, (Ii) a compound having a mercapto group and a reactive functional group other than the hydrolyzable silicon-containing group as a chain transfer agent (for example, a method of polymerizing monomer units and introducing a hydrolyzable silicon-containing group at the molecular end (for example, In the presence of acrylic acid, the monomer unit is polymerized, and the resulting copolymer is a compound having a hydrolyzable silicon-containing group and a functional group capable of reacting with a Y group (for example, an isocyanate group and -Si). (OCH ₃₎ a method of introducing a hydrolyzable silicon-containing group to the compound) is reacted with molecular end and a ₃ group, compounds containing (iii) a hydrolyzable silicon-containing group (e.g., Azobisunitori Compound, disulfide compound) as an initiator to polymerize the monomer unit to introduce a hydrolyzable silicon-containing group at the molecular end, (iv) to polymerize the monomer unit by a living radical polymerization method A method of introducing a hydrolyzable silicon-containing group at the terminal, (v) a compound having a polymerizable unsaturated bond and a hydrolyzable silicon-containing group and the monomer unit, wherein one molecule of hydrolyzable silicon-containing group A method of copolymerizing by selecting polymerization conditions such as the use ratio of monomer units, the amount of chain transfer agent, the amount of radical initiator, the polymerization temperature, etc. so that at least one is introduced per unit can be mentioned.

  Among these, it is preferable that the polymer (A) is produced by adding hydrosilane having a hydrolyzable silicon-containing group to a (meth) acrylic polymer having an alkenyl group at the terminal by hydrosilylation. One.

The (meth) acrylic polymer having an alkenyl group at the end includes, for example, an organic halogen compound or a sulfonyl halide compound as an initiator and a catalyst as the group 8, 9, 10, or 11 of the periodic table. It can be produced by converting a terminal halogen group of a (meth) acrylic polymer obtained by polymerization using a metal complex having a group element as a central metal to an alkenyl group.
Here, a (meth) acrylic polymer having a halogen group at a terminal is conventionally polymerized using a halogen compound such as carbon tetrachloride, carbon tetrabromide, methylene chloride, methylene bromide as a chain transfer agent. Has been manufactured by.
However, with this method, it has been difficult to reliably introduce halogen to both ends of the polymer.

In contrast, JP-A-1-247403 discloses a method for producing an acrylic polymer having an alkenyl group at both ends by using dithiocarbamate or diallyl disulfide having an alkenyl group as a chain transfer agent. Has been described. Japanese Patent Application Laid-Open No. Hei 6-221922 discloses that an acrylic polymer having a hydroxyl group at the terminal is produced using a hydroxyl group-containing polysulfide or an alcohol compound as a chain transfer agent, and alkenyl at the terminal using a hydroxyl group reaction. A method for producing an acrylic polymer having a group is described.
However, in these methods, it is usually difficult to reliably introduce an alkenyl group at the end of the polymer.

On the other hand, as a method for obtaining a (meth) acrylic polymer having a hydrolyzable silicon-containing group without passing through an alkenyl group, Japanese Patent Publication No. 3-14068 discloses a (meth) acrylic monomer containing hydrolyzable silicon. A method of polymerizing in the presence of a radical polymerization initiator having a group-containing mercaptan, a hydrolyzable silicon-containing group-containing disulfide and a hydrolyzable silicon-containing group is described. Japanese Patent Publication No. 4-55444 discloses a method of polymerizing an acrylic monomer in the presence of a hydrolyzable silicon-containing group-containing hydrosilane compound or a tetrahalosilane compound. Further, in JP-A-5-97921, an acrylic monomer is anionically polymerized using a stable carbanion having a hydrolyzable silicon-containing group as an initiator, and the terminal of the polymerization is reacted with a bifunctional electrophilic compound. Describes a method for producing an acrylic polymer having a hydrolyzable silicon-containing group.
However, these methods have problems such as introduction of a functional group into the side chain. That is, it was difficult to reliably introduce a hydrolyzable silicon-containing group at the terminal. In addition, the polymers obtained by these radical polymerizations have a problem that the molecular weight distribution is wide and the viscosity is high.

Therefore, in recent years, living radical polymerization has attracted attention as a method for reliably introducing a functional group to the terminal of an acrylic polymer. Living radical polymerization is described in JP-A-9-272714.
In particular, JP 2000-154205 A and JP 2000-178456 A detail the atom transfer radical polymerization method among the living radical polymerization methods. Here, an organic halide or a sulfonyl halide compound having a particularly highly reactive carbon-halogen bond is used as the initiator, and a periodic table, group 8, group 9, group 10 or group 11 is used as the catalyst. A metal complex having the above metal as a central metal is used. Further, in order to obtain a (meth) acrylic polymer having a functional group at the terminal, an organic halide or sulfonyl halide compound having two or more starting points is used as an initiator.

  Japanese Patent Laid-Open No. 2003-96106 discloses radical polymerization of (meth) acrylate monomers using 2,2′-azobis (dimethylvaleronitrile) as an initiator and n as a chain transfer agent. -Dodecyl mercaptan, t-dodecyl mercaptan and the like are described. Here, when 2-propanol, isobutanol or the like is used as a polymerization solvent, since it has a hydrogen atom bonded to a tertiary carbon atom, it also acts as a chain transfer agent and reduces the amount of chain transfer agent used. It is described that it is preferable in that it can be produced, and that the molecular weight distribution can be controlled more narrowly than in the case of using an aromatic solvent.

  As described above, the polymer produced from the (meth) acrylic polymer obtained by any of the polymerization methods has a molecular weight distribution of 2.0 (meth) acrylic polymer obtained by ordinary polymerization. On the other hand, since it can be controlled to be as narrow as 1.5 or less, the viscosity is low and the functional group introduction rate at the terminal is extremely high.

  The molecular weight of the polymer (A) is not particularly limited, but the number average molecular weight in terms of polystyrene in gel permeation chromatography (GPC) is 500 to 100,000, the degree of difficulty during polymerization, compatibility, It is preferable in terms of handling viscosity. Among them, those having a number average molecular weight of 1,000 to 50,000 are preferable from the viewpoint of balance between strength and viscosity, and those having a number average molecular weight of 2,000 to 30,000 are points such as ease of handling such as workability and adhesiveness. And more preferable.

  A polymer (A) is used individually or in mixture of 2 or more types.

  As such a polymer (A), a well-known thing can be used. Specific examples include SMAP (Kaneka Telechelic Polyacrylate) SA100S, SA110S, SA120S and SA200SX manufactured by Kaneka Chemical Co., Ltd. and Kaneka MS Polymer S943 manufactured by Kaneka Chemical Co., Ltd.

  The curable composition of the present invention containing such a polymer (A) has a weather-resistant adhesive property for a long period of time when the cured product of the curable composition is used for an intermediate film, and has an appropriate elasticity. Therefore, it is possible to reduce breakage of the glass and to prevent scattering of the glass at the time of breakage.

<Silane coupling agent (B)>
The silane coupling agent (B) used for this invention improves the adhesiveness to glass of the curable composition of this invention.
Such a silane coupling agent is not particularly limited, but can be obtained by reacting aminosilane, vinylsilane, epoxysilane, methacrylsilane, isocyanate silane, ketimine silane, or a mixture or reaction thereof, or an epoxy resin or polyisocyanate. It is preferable that it is a compound obtained.

  The aminosilane is not particularly limited as long as it is a compound having an amino group or imino group and a hydrolyzable silicon-containing group. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyl Dimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2- (aminoethyl) -3- Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3 -Ami Propyl ethyl diethoxy silane, and the like.

Examples of vinyl silane include vinyl trimethoxy silane, vinyl triethoxy silane, and tris- (2-methoxy ethoxy) vinyl silane.
Examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethylmethyl. Examples include dimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.
Examples of methacrylic silane include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.
Examples of the isocyanate silane include isocyanate propyl triethoxysilane.
Examples of the ketimine silane include ketiminated propyltrimethoxysilane.

The content of the silane coupling agent (B) is preferably 0.1 to 20 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymer (A). Moreover, when it contains the polymer (D) mentioned later, content of a silane coupling agent (B) is 0.1 with respect to a total of 100 mass parts of a polymer (A) and a polymer (D). It is preferably ˜20 parts by mass.
If the content of the silane coupling agent (B) is within this range, when the obtained cured product of the curable composition of the present invention is used as an intermediate film, the adhesion between the intermediate film and glass is good. Therefore, it is preferable.

<Catalyst (C)>
The catalyst (C) used in the present invention is a tin catalyst and / or a titanium catalyst, and conventionally known catalysts can be used.
Examples of the tin catalyst include tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; reaction products of dibutyltin oxide and phthalate; dibutyltin diacetylacetonate.
Examples of the titanium catalyst include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate.
These may be used alone or in combination of two or more.

The content of the catalyst (C) is preferably 0.01 to 20 parts by mass and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer (A). Moreover, when it contains the polymer (D) mentioned later, content of a catalyst (C) is 0.01-20 mass with respect to a total of 100 mass parts of a polymer (A) and a polymer (D). Part.
When the content of the catalyst (C) is within this range, when the cured product of the resulting curable composition of the present invention is used for an intermediate film, an appropriate pot life and cured physical properties (for example, mechanical strength) , Elongation, etc.) is preferable because it is easy to ensure.

<Polymer (D)>
The polymer (D) that can be optionally used in the present invention is a polymer having a main chain containing an alkylene oxide monomer unit and at least one hydrolyzable silicon-containing group per molecule. In the present invention, the hydrolyzable silicon-containing group may be present at the terminal in the molecule of the polymer, may be present in the side chain, or may be present in both.
Here, the hydrolyzable silicon-containing group is the same as in the case of the polymer (A).

  The main chain of the polymer (D) is not particularly limited as long as it contains an alkylene oxide monomer unit, but the proportion of this monomer unit is preferably more than 50% by mass, and 70% by mass or more. Is more preferable.

Examples of the alkylene oxide monomer unit contained in the polymer (D) include —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, —CH ₂ CH (C ₂ H ₅ ) O—. _{, -CH (CH 3) CH 2} O -, - CH (C 2 H 5) CH 2 O -, - expressed CH ₂ CH ₂ CH ₂ O- or -CH ₂ CH ₂ CH ₂ CH ₂ O- in Repeat units are mentioned.
The main chain of the polymer (D) may consist of only one kind of these repeating units, or may consist of two or more kinds.
The main chain of a polymer (D) may be used independently and may use 2 or more types together.

  As such a polymer (D), a well-known thing can be used. Specifically, for example, MS polymer (S810, S203, S303, S943, all manufactured by Kaneka Chemical Co., Ltd.) can be mentioned.

The content of the polymer (D) that can be used as desired is preferably 50/50 or more in terms of mass ratio to the polymer (A) (polymer (A) / polymer (D)). 70/30 or more is more preferable.
By using the polymer (D) together with the polymer (A), the polymer (A) has superior weather resistance, heat resistance, oil resistance, etc., compared to the case where the polymer (A) is used alone. While maintaining the above, curing characteristics, physical properties after curing, and adhesion to glass are improved.

The curable composition of this invention can contain another hardening | curing agent in the range which does not impair the objective of this invention.
For example, amine curing agents, acid or acid anhydride curing agents, basic active hydrogen compounds, imidazoles, polymercaptan curing agents, phenol resins, urea resins, melamine resins, isocyanate curing agents, latent curing agents, An ultraviolet curing agent is mentioned.

  The curable composition of the present invention can contain various additives as necessary in addition to the above-mentioned various components within a range not impairing the object of the present invention. Examples of additives include fillers, plasticizers, softeners, thixotropic agents, pigments, dyes, anti-aging agents, antioxidants, antistatic agents, flame retardants, adhesion promoters, dispersants, solvents, Antibacterial and antifungal agents are mentioned.

  As the filler, those having various shapes can be used. For example, calcium carbonate; fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; magnesium carbonate, zinc carbonate; Examples include kaolin clay, calcined clay; organic or inorganic fillers such as carbon black; these fatty acids, resin acids, fatty acid ester-treated products, and fatty acid ester urethane compound-treated products.

  Examples of the plasticizer or softener include diisononyl phthalate (DINP), dioctyl phthalate, dibutyl phthalate; dioctyl adipate, isodecyl succinate; diethylene glycol dipenzoate, pentaerythritol ester; butyl oleate, acetylricinoleic acid Examples include methyl; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol polyester adipate; petroleum softeners such as paraffinic oil, naphthenic oil, and aroma oil.

Examples of the thixotropic property-imparting agent include dry silica, white carbon, hydrogenated castor oil, calcium carbonate, and Teflon (registered trademark).
Examples of the pigment include titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum oxide or hydroxide, hydrochloride, sulfate, etc .; azo pigment, copper phthalocyanine Examples thereof include organic pigments such as pigments.

Examples of the antiaging agent include hindered phenol compounds and hindered amine compounds.
Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.
Examples of the adhesion imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and epoxy resins.
The above additives can be used in combination as appropriate.

  The method for producing the curable composition of the present invention from each component as described above is not particularly limited, but each component is stirred under a reduced pressure or an inert gas atmosphere such as nitrogen using a mixing device such as a mixing mixer. A method of sufficiently kneading and uniformly dispersing is preferred.

Such a curable composition of the present invention is a moisture curable composition and can be used as a one-component curable composition. Moreover, it can also be used as a 2 liquid type curable composition which made the polymer (A) the main ingredient (A liquid) side and made the catalyst (C) the hardening | curing agent (B liquid) side as needed.
When the curable composition of the present invention is exposed to moisture, the curing reaction proceeds by hydrolysis of the hydrolyzable silicon-containing group. In addition, the curing reaction can be advanced by appropriately supplying water.

The laminated glass which concerns on the 2nd aspect of this invention is a laminated glass which has the hardened | cured material of the curable composition for laminated glass intermediate films which concerns on the 1st aspect of this invention mentioned above in an intermediate film.
Here, an example of the suitable embodiment of the laminated glass of this invention is demonstrated using FIG. FIG. 1 is a schematic cross-sectional view showing an example of the laminated glass of the present invention. As shown in FIG. 1, the laminated glass 1 is obtained by laminating two glass plates 11a and 11b with an intermediate film 12 made of a cured product of the curable composition of the present invention.

Moreover, the laminated glass of this invention may have the inner layer pinched | interposed into the hardened | cured material of the curable composition of this invention in the said intermediate film. By having an inner layer in the intermediate film, the degree of freedom of design such as soundproofing, attenuation, strength, and refractive index of the laminated glass obtained can be increased.
An example of a specific preferred embodiment having an inner layer will be described with reference to FIG. FIG. 2 is a schematic cross-sectional view showing an example of the laminated glass of the present invention. As shown in FIG. 2, the laminated glass 2 includes an interlayer film 24 having a multilayer structure in which two glass plates 21a and 21b each have an inner layer 23 between cured products 22a and 22b of the curable composition of the present invention. Are stacked.

  Such an inner layer is preferably made of at least one selected from the group consisting of alkyl acrylate rubbers, conjugated diene rubbers, and polyvinyl acetal resins.

  Here, examples of the acrylic acid alkyl ester rubber include, for example, butyl acrylate, acrylic acid-n-hexyl, acrylic acid-2-ethylhexyl, acrylic acid-n-octyl; a copolymer of these compounds with a vinyl monomer, and the like. A polymer; Of these, butyl acrylate and -2-ethylhexyl acrylate are practical from the viewpoint of cost quality.

  Examples of the conjugated diene rubber include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), Examples include chloroprene rubber (CR), butyl rubber (IIR), and ethylene-propylene-diene rubber (EPDM).

  As the polyvinyl acetal resin, a polyvinyl acetal resin generally used as a main component of an interlayer film for laminated glass can be used, and specifically, a polyvinyl butyral resin (PVB) having a butyralization degree of 60 to 70 mol% is preferably exemplified. Is done.

  As such PVB, commercially available products such as ELEX manufactured by Sekisui Chemical Co., Ltd., Denkabutchiral manufactured by Denki Kagaku Kogyo Co., Ltd., Butvar manufactured by Monsanto Co., Mowital manufactured by Hoechst Co., and Piloform manufactured by Wacker Chemie Co. can be used. .

  The method for producing the laminated glass of the present invention is not particularly limited. For example, when the laminated glass 1 shown in FIG. 1 is produced, the curable composition of the present invention is applied onto the glass plate 11a, and an appropriate method is produced. After taking an open time (about 5 to 30 minutes), that is, after curing has progressed to some extent, the glass plate 11b can be pressure-bonded from above so as to overlap the glass plate 11a.

Since the laminated glass of the present invention has the cured product of the above-described curable composition of the present invention in the intermediate film, it has weather resistance adhesion over a long period of time and has moderate elasticity, so that the glass is not damaged. It can reduce, can prevent scattering of the glass at the time of breakage, and also becomes a laminated glass which has sound insulation.
In addition, the interlayer film itself is highly resistant to light degradation due to sunlight, does not whiten even when left in a high temperature atmosphere, and does not emit low molecular silicone, so it does not pollute the glass surface and the periphery of the glass surface. This is also very useful.
Furthermore, in the production, the curable composition of the present invention can be cured by moisture at room temperature as described above, and thus has an advantage in terms of production cost.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
(Examples 1 and 2 and Comparative Examples 1 and 2)
The components shown in Table 1 below were mixed and dispersed using the stirrer with the composition (parts by mass) shown in Table 1 to obtain the curable compositions shown in Table 1.
About the obtained curable composition, initial adhesiveness and weather resistance adhesiveness were evaluated as follows, and the suitability as a curable composition for laminated glass intermediate films was investigated.

(1) Initial adhesiveness The curable compositions of Examples 1 and 2 and Comparative Example 1 have a thickness of 1 mm on the surface of a glass plate (width 50 mm × 50 mm, thickness 3 mm) to which T-type aluminum is attached. It was applied as follows. After application, an open time (30 minutes) was taken, glass plates of the same size were bonded together, and pressure-bonded 5 times with a 5 kg roller load to produce a laminated glass.
Immediately after the production, two glass plates were pulled in the vertical direction at a pulling speed of 200 mm / min, a peel test of the adhesive surface was performed, and the state of peel was visually observed to evaluate “initial adhesiveness”.
The results are shown in Table 1. In Table 1, the peeled state is indicated by CF (cohesive failure) and AF (interface peeling). In Comparative Example 2, an intermediate film was not provided, and as described later, a laminated glass in which two glass plates were held with a gap therebetween was indicated as “−”.

(2) Weather-resistant adhesiveness A laminated glass produced by the same method as described above was irradiated with a sunshine weatherometer for a predetermined time (500 hours, 5000 hours) so that light was incident from the direction perpendicular to the glass surface.
After irradiation, the same peeling test as described above was performed, and the state of peeling was visually observed to evaluate “weather resistance”.
The results are shown in Table 1.

(3) Sound insulation The curable compositions of Examples 1 and 2 and Comparative Example 1 were applied to the surface of a glass plate (width 250 mm × 250 mm, thickness 3 mm) to a thickness of 1 mm. After application, an open time (30 minutes) was taken, glass plates of the same size were bonded together, and pressure-bonded 5 times with a 5 kg roller load to produce a laminated glass.
Moreover, in the comparative example 2, the laminated glass which hold | maintained two glass plates (width 250mm x 250mm, thickness 3mm) at intervals of 1 mm was produced.
The glass surface of the produced laminated glass was tapped lightly with an iron rod (diameter 8 mm, length 100 mm), and the sound hearing was evaluated.
The results are shown in Table 1. In Table 1, those having a silencing effect were evaluated as ◯, and those without were evaluated as ×.

The components shown in Table 1 are as follows.
-Polymer (A): SMAP SA100S, manufactured by Kaneka Chemical Co., Ltd.-Polymer (D): MS polymer S203, manufactured by Kaneka Chemical Co., Ltd.-Plasticizer: Bifunctional PPG (Exenol 3020, manufactured by Asahi Glass Co., Ltd., molecular weight) 3000)
Hindered piperidine: Sanol LS-765, Sankyo Co., Ltd. Hindered phenol: Irganox 1010, Ciba Specialty Chemicals Co., Ltd. Vinyl silane: Vinyl trimethoxy silane, A171, Nihon Unicar Co., Ltd. Ethoxysilane, A1110, manufactured by Nihon Unicar Co., Ltd. Tin catalyst: Dibutyltin diacetylacetonate, U-220, manufactured by Nitto Kasei

  As is apparent from Table 1, the curable compositions of the present invention (Examples 1 and 2) have a weather resistant adhesiveness as compared with the curable composition not using the polymer (A) (Comparative Example 1). It turned out to be very good. Moreover, the laminated glass which has the cured | curing material of the curable composition obtained in Example 1 and 2 in an intermediate film has sound-insulating property, Furthermore, it is one week under high temperature atmosphere (50 degreeC, 95% RH). Even if left untreated, it was not whitened.

FIG. 1 is a schematic cross-sectional view showing an example of the laminated glass of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the laminated glass of the present invention.

Explanation of symbols

1, 2 Laminated glass
11a, 11b, 21a, 21b Glass plate 12, 24 Intermediate film 22a, 22b Cured product

Claims (8)

A polymer (A) having a main chain containing an alkyl acrylate monomer unit and / or an alkyl methacrylate monomer unit and having at least one hydrolyzable silicon-containing group per molecule;
A silane coupling agent (B);
A curable composition for a laminated glass interlayer film comprising a tin catalyst and / or a titanium catalyst (C).   The curable composition for laminated glass interlayer film according to claim 1, further comprising a polymer (D) having a main chain containing an alkylene oxide monomer unit and having at least one hydrolyzable silicon-containing group per molecule. Stuff.   The silane coupling agent (B) is contained in an amount of 0.1 to 20 parts by mass and the catalyst (C) is contained in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the polymer (A). The curable composition for laminated glass interlayer films according to 1.   0.1-20 mass parts of said silane coupling agents (B) are contained with respect to a total of 100 mass parts of said polymer (A) and said polymer (D), and said catalyst (C) is 0.01. The curable composition for laminated glass interlayer films according to claim 2, which is contained in an amount of ˜20 parts by mass.   The silane coupling agent (B) is an aminosilane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, ketimine silane, or a mixture or reaction product thereof, or a compound obtained by reacting these with an epoxy resin or polyisocyanate. The curable composition for laminated glass interlayer films according to any one of claims 1 to 4.   The laminated glass which has a hardened | cured material of the curable composition for laminated glass intermediate films in any one of Claims 1-5 in an intermediate film.   The laminated glass according to claim 6, wherein the intermediate film includes an inner layer sandwiched between the cured products.   The laminated glass according to claim 7, wherein the inner layer is made of at least one selected from the group consisting of an alkyl acrylate rubber, a conjugated diene rubber, and a polyvinyl acetal resin.

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