JP2011240676A - Poly(vinyl acetal) laminate having superior interlayer adhesion and its application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which comprises a poly(vinyl acetal)-containing layer and a hydrocarbon polymer-containing layer and has superior interlayer adhesion.SOLUTION: An A layer consisting of a composition A containing poly(vinyl acetal) and a B layer consisting of a composition B containing the hydrocarbon polymer, 8-30C carboxylic acid and/or a salt originated from the 8-30C carboxylic acid are laminated to form the laminate. Further in the laminate, the composition B includes 8-30C carboxylic acid and/or the salt originated from the 8-30C carboxylic acid by 0.01 to 5 parts mass in total toward 100 parts mass of the hydrocarbon polymer.

Description

  The present invention relates to a polyvinyl acetal laminate excellent in interlayer adhesion and use thereof.

  Polyvinyl acetal typified by polyvinyl butyral is excellent in adhesiveness and compatibility with various organic and inorganic substrates and solubility in organic solvents. Various adhesives, binders for ceramics, various inks, paints, etc. It is widely used as a safety glass interlayer.

  Among these, in laminated glass interlayer film applications, the laminated laminated glass interlayer is composed of a plasticized polyvinyl acetal layer and a styrene-diene block copolymer layer having high sound insulation performance for the purpose of imparting high sound insulation performance to the laminated glass interlayer film. Examination of a film (see Patent Documents 1 to 3) or a full-surface board for a pachinko machine (see Patent Document 4) that uses such a laminated glass and has high sound insulation properties has been conducted. However, in such a laminate of a plasticized polyvinyl acetal and a styrene-diene block copolymer, the adhesiveness between the plasticized polyvinyl acetal and the styrene-diene block copolymer is very weak, moisture absorption and external impact, Or, there is a problem that peeling easily occurs at the interface due to a stress caused by a difference in thermal expansion coefficient between the plasticized polyvinyl acetal and the styrene-diene block copolymer, and the function as a laminated glass is deteriorated or the appearance is impaired. .

JP 2007-09491 A JP-A-2005-306326 Special Table 2001-506198 JP 2007-136057 A

  The present invention solves the above-mentioned problem, and is a laminate of a layer containing polyvinyl acetal and a layer containing a hydrocarbon-based polymer, which is suitably used for laminated glass interlayer films and other applications. It aims at providing the laminated body which is excellent in adhesiveness.

  According to the present invention, the object is to provide a layer A composed of the composition A containing polyvinyl acetal, a hydrocarbon polymer, a carboxylic acid having 8 to 30 carbon atoms and / or a salt derived from a carboxylic acid having 8 to 30 carbon atoms. This is achieved by providing a laminate including a structure formed by laminating a B layer composed of the composition B. Furthermore, the composition B has a total of 0.01 to 5 parts by mass of a carboxylic acid having 8 to 30 carbon atoms and / or a salt derived from a carboxylic acid having 8 to 30 carbon atoms with respect to 100 parts by mass of the hydrocarbon polymer. This is achieved by providing a laminate comprising:

  The laminate of the present invention contains a carboxylic acid having 8 to 30 carbon atoms and / or a salt derived from a carboxylic acid having 8 to 30 carbon atoms as an essential component in the composition B. The carboxyl group and / or carboxylate group of the carboxylic acid having 8 to 30 carbon atoms and / or the salt derived from the carboxylic acid having 8 to 30 carbon atoms interacts with the hydroxyl group of the polyvinyl acetal contained in the A layer by hydrogen bonding. On the other hand, a relatively long chain hydrocarbon group contained in a carboxylic acid having 8 to 30 carbon atoms and / or a salt derived from a carboxylic acid having 8 to 30 carbon atoms is a hydrocarbon having a relatively close molecular polarity. It can also be compatible with and adhered to a polymer. Therefore, the laminate including the structure in which the A layer composed of the composition A of the present invention and the B layer composed of the composition B are laminated is excellent in interlayer adhesiveness between the A layer and the B layer. It is suitable when used for a laminated glass interlayer film.

It is the schematic showing an example of the solar cell module using the laminated body and crystal | crystallization type photovoltaic cell of this invention. It is the schematic showing an example of the solar cell module using the laminated body and thin film type photovoltaic cell of this invention.

  First, the composition A used in the present invention will be described. The composition A used in the present invention is not particularly limited as long as it contains polyvinyl acetal, and the content of polyvinyl acetal is not particularly limited, but may be 30% by mass or more based on the mass of the composition A. More preferably, it is 40% by mass or more, and most preferably 50% by mass or more. If the content of the polyvinyl acetal in the composition A is lower than 30% by mass, the physical properties inherent in the polyvinyl acetal may not be expressed.

  Next, the polyvinyl acetal used in the present invention will be described. The polyvinyl acetal used in the present invention is usually produced using a vinyl alcohol polymer as a raw material. The vinyl alcohol polymer can be obtained by a conventionally known method, that is, by polymerizing a vinyl ester monomer and saponifying the obtained polymer. As a method for polymerizing the vinyl ester monomer, a conventionally known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method can be applied. As the polymerization initiator, an azo initiator, a peroxide initiator, a redox initiator, or the like is appropriately selected depending on the polymerization method. As the saponification reaction, a conventionally known alcoholysis or hydrolysis using an alkali catalyst or an acid catalyst can be applied. Among them, a saponification reaction using methanol as a solvent and a caustic soda (NaOH) catalyst is simple and most preferable.

  Examples of vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, and palmitic acid. Vinyl, vinyl stearate, vinyl oleate, vinyl benzoate and the like can be mentioned, with vinyl acetate being particularly preferred.

  In addition, when the vinyl ester monomer is polymerized, it can be copolymerized with another monomer as long as it does not contradict the gist of the present invention. Examples of other monomers include α-olefins such as ethylene, propylene, n-butene, and isobutylene; methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, and n-butyl acrylate. Acrylates such as i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i -Methacrylic acid esters such as propyl, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate; acrylamide, N-methylacrylamide, N- ethyl Acrylamide derivatives such as chloramide, N, N-dimethylacrylamide, diacetone acrylamide, acrylamide propane sulfonic acid and salts thereof, acrylamidopropyldimethylamine and salts thereof, quaternary salts thereof, N-methylolacrylamide and derivatives thereof; -Methacrylamide derivatives such as methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid and salts thereof, methacrylamideamidopropylamine and salts thereof, quaternary salts thereof, N-methylolmethacrylamide and derivatives thereof; methyl vinyl ether , Ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t- Vinyl ethers such as butyl vinyl ether, dodecyl vinyl ether and stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl acetate; Examples include, but are not limited to, allyl compounds such as allyl chloride; maleic acid esters or maleic anhydride, vinylsilyl compounds such as vinyltrimethoxysilane; and isopropenyl acetate. These monomers are usually used in a proportion of less than 10 mol% with respect to the vinyl ester monomer.

  The viscosity average degree of polymerization of the vinyl alcohol polymer used as a raw material for the polyvinyl acetal used in the present invention is appropriately selected according to the use, but preferably 150 to 3,000, more preferably 200 to 2,000. More preferred. If the viscosity average polymerization degree of the vinyl alcohol polymer is less than 150, the strength of the A layer tends to be insufficient, and if it is greater than 3,000, the handleability during the molding of the A layer tends to be poor.

  The polyvinyl acetal used in the present invention can be obtained, for example, by the following method, but is not limited thereto. First, an aqueous solution of a vinyl alcohol polymer having a concentration of 3 to 30% by mass is adjusted to a temperature range of 80 to 100 ° C., and the temperature is gradually cooled over 10 to 60 minutes. When the temperature is lowered to −10 to 30 ° C., an aldehyde and an acid catalyst are added, and an acetalization reaction is performed for 30 to 300 minutes while keeping the temperature constant. Thereafter, the reaction solution is heated to a temperature of 30 to 80 ° C. over 30 to 200 minutes, and the temperature is maintained for 1 to 6 hours. Next, the reaction solution is preferably cooled to room temperature and washed with water, then neutralized with an alkali or the like as necessary, neutralized, washed with water and dried to obtain the polyvinyl acetal used in the present invention.

  The acid catalyst used in the acetalization reaction is not particularly limited, and any of organic acids and inorganic acids can be used. Examples thereof include acetic acid, paratoluenesulfonic acid, nitric acid, sulfuric acid, hydrochloric acid and the like. Of these, hydrochloric acid, sulfuric acid, and nitric acid are preferably used.

  Although the aldehyde used for the acetalization reaction of this invention is not specifically limited, It is preferable to use the polyvinyl acetal acetalized with the C1-C8 aldehyde. Examples of the aldehyde having 1 to 8 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, n-octylaldehyde, 2-ethylhexylaldehyde, benzaldehyde and the like. These may be used alone or in combination of two or more. Among these, aldehydes having 4 to 6 carbon atoms, particularly n-butyraldehyde are preferably used. That is, as the polyvinyl acetal, polyvinyl butyral is particularly preferable.

  The average degree of acetalization of the polyvinyl acetal is not particularly limited, but is preferably 40 to 85 mol%, preferably 48 to 82 mol%, and more preferably 55 to 81 mol%. By using a polyvinyl acetal having an acetalization degree in this range, an A layer having excellent transparency and appropriate mechanical strength can be obtained. In order to achieve the object of the present invention more suitably, the vinyl ester unit content (usually vinyl acetate unit content) of polyvinyl acetal is 0.01 to 30 mol%, preferably 0.05 to It is preferably 15 mol%, more preferably 0.1 to 5 mol%. The vinyl alcohol unit content is preferably 10 to 50 mol%, preferably 12 to 40 mol%, and most preferably 15 to 35 mol%. In addition, the value of the said acetalization degree, vinyl ester unit content, and vinyl alcohol unit content is a value with respect to the total amount of acetalization degree (vinyl acetal unit content), vinyl ester unit content, and vinyl alcohol unit content. is there.

  The composition A used in the present invention may contain an antioxidant, an ultraviolet absorber, a plasticizer, an adhesion improver, and other additives, as long as it is not contrary to the gist of the present invention. Hereinafter, these will be described in order.

  When the antioxidant is added to the composition A used in the present invention, the kind thereof is not particularly limited, and examples thereof include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like. Of these, phenolic antioxidants are preferred, and alkyl-substituted phenolic antioxidants are particularly preferred.

  Examples of phenolic antioxidants include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl Acrylate compounds such as -6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate, 2,6-di-t-butyl-4-methylphenol, 2,6 -Di-t-butyl-4-ethylphenol, octadecyl-3- (3,5-) di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6- t-butylphenol), 4,4'-butylidene-bis (4-methyl-6-t-butylphenol), 4,4'-butylidene-bis (6-t-butyl-m-cresol), 4,4 ' Thiobis (3-methyl-6-t-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, 3,9-bis (2- (3- (3-t-butyl-4-) Hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4 -Hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis (methylene-3) -(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate) methane, triethylene glycol bis (3- (3-t-butyl-4-hydroxy-5-methyl) Alkyl-substituted phenolic compounds such as (ruphenyl) propionate), 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis-octylthio-1,3,5-triazine, 6- (4 -Hydroxy-3,5-dimethylanilino) -2,4-bis-octylthio-1,3,5-triazine, 6- (4-hydroxy-3-methyl-5-t-butylanilino) -2,4- Contains triazine groups such as bis-octylthio-1,3,5-triazine, 2-octylthio-4,6-bis- (3,5-di-t-butyl-4-oxyanilino) -1,3,5-triazine There are phenolic compounds.

  Examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, and tris (2-t-butyl). -4-methylphenyl) phosphite, tris (cyclohexylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy -9,10-dihydro-9-oxa-10-phosphine Monophosphite compounds such as phenanthrene, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecylphosphite), 4,4′-isopropylidene-bis (phenyl-di) -Alkyl (C12-C15) phosphite), 4,4'-isopropylidene-bis (diphenylmonoalkyl (C12-C15) phosphite), 1,1,3-tris (2-methyl-4-di-tri) Examples thereof include diphosphite compounds such as decyl phosphite-5-t-butylphenyl) butane and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene phosphite. Of these, monophosphite compounds are preferred.

  Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, lauryl stearyl 3,3′-thiodipropionate, pentaerythritol-tetrakis- (Β-lauryl-thiopropionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane.

  These antioxidants can be used alone or in combination of two or more. The addition amount of the antioxidant is 0.001 to 5% by mass, preferably 0.01 to 1% by mass with respect to the mass of the composition A. When the amount of the antioxidant is less than 0.001% by mass, a sufficient effect may not be obtained, and when the amount is more than 5% by mass, a remarkable effect cannot be expected.

  When adding a ultraviolet absorber to the composition A used by this invention, the kind is not specifically limited. Examples of the ultraviolet absorber used include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α′dimethylbenzyl) phenyl] -2H-benzo. Triazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- Benzotriazole ultraviolet absorbers such as (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2,2,6,6-tetramethyl- 4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5- Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 4- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) -1- (2- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -2,2,6,6-tetramethylpiperidine and other hindered amine ultraviolet absorbers, 2,4-di- Benzoate UV absorbers such as t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate Etc., and the like.

  The addition amount of these ultraviolet absorbers is preferably 0.001 to 5% by mass and more preferably 0.01 to 1% by mass with respect to the mass of the composition A. If the ultraviolet absorber is less than 0.001% by mass, a sufficient effect may not be obtained, and if it exceeds 5% by mass, no remarkable effect can be expected. These ultraviolet absorbers may be used alone or in combination of two or more.

  In addition, when a plasticizer is added to the composition A used in the present invention, the plasticizer includes carboxylic acid ester plasticizers such as monovalent carboxylic acid ester type and polyvalent carboxylic acid ester type, and phosphoric acid ester type plasticizer. In addition to agents, organic phosphite ester plasticizers, hydroxycarboxylic acid ester plasticizers, etc., polymer plasticizers such as carboxylic acid polyesters, carbonated polyesters, and polyethers can also be used. These can be appropriately selected according to the purpose, but generally, when a laminated body is formed, the layer A shifts from the layer B to impair the strength and transparency of the layer B or the interlayer adhesion between the layers A and B. It is often not preferable to use various types of plasticizers and to add such an amount that causes such harmful effects.

  Examples of monovalent carboxylic acid ester plasticizers include monovalent carboxylic acids such as butanoic acid, isobutanoic acid, hexanoic acid, 2-ethylbutanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, lauric acid, and ethylene. Examples thereof include compounds obtained by a condensation reaction with a polyhydric alcohol such as glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol and glycerin. Specific examples of the compound include triethylene glycol di-2-ethylhexanoate, triethylene glycol diisobutanoate, triethylene glycol dihexanoate, triethylene glycol di-2-ethylbutanoate, triethylene glycol dilaurate, Ethylene glycol di-2-ethylhexanoate, diethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-2-ethylhexanoate, tetraethylene glycol diheptanoate, PEG # 400 di-2-ethylhexanoate, tri Examples include ethylene glycol mono-2-ethylhexanoate and glycerin tri-2-ethylhexanoate. Here, PEG # 400 represents polyethylene glycol having an average molecular weight of 350 to 450.

  Examples of the polyvalent carboxylic acid ester plasticizer include polyvalent carboxylic acids such as adipic acid, succinic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and trimet acid, and methanol, ethanol, butanol, hexanol, Examples thereof include compounds obtained by a condensation reaction with a monohydric alcohol having 1 to 12 carbon atoms such as 2-ethylbutanol, heptanol, octanol, 2-ethylhexanol, decanol, dodecanol, butoxyethanol, butoxyethoxyethanol, and benzyl alcohol. Examples of specific compounds include dihexyl adipate, di-2-ethylbutyl adipate, diheptyl adipate, dioctyl adipate, di-2-ethylhexyl adipate, di (butoxyethyl) adipate, di (butoxyethoxyethyl adipate) ), Mono (2-ethylhexyl) adipate, dibutyl phthalate, dihexyl phthalate, di (2-ethylbutyl) phthalate, dioctyl phthalate, di (2-ethylhexyl) phthalate, benzylbutyl phthalate, didodecyl phthalate, etc. However, it is not limited to this.

  Examples of phosphoric acid plasticizers and phosphorous acid plasticizers include phosphoric acid or phosphorous acid and methanol, ethanol, butanol, hexanol, 2-ethylbutanol, heptanol, octanol, 2-ethylhexanol, decanol, dodecanol, Examples thereof include compounds obtained by a condensation reaction with an alcohol having 1 to 12 carbon atoms such as butoxyethanol, butoxyethoxyethanol, and benzyl alcohol. Specific examples include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tri (butoxyethyl) phosphate, tri (2-ethylhexyl) phosphite. ) And the like.

  Hydroxycarboxylic acid ester plasticizers include hydroxycarboxylic acid monohydric alcohol esters; methyl ricinoleate, ethyl ricinoleate, butyl ricinoleate, methyl 6-hydroxyhexanoate, ethyl 6-hydroxyhexanoate, 6-hydroxyhexanoic acid Polybutyl alcohol ester of butyl, hydroxycarboxylic acid; ethylene glycol di (6-hydroxyhexanoic acid) ester, diethylene glycol di (6-hydroxyhexanoic acid) ester, triethylene glycol di (6-hydroxyhexanoic acid) ester, 3-methyl 1,5-pentanediol di (6-hydroxyhexanoic acid) ester, 3-methyl-1,5-pentanediol di (2-hydroxybutyric acid) ester, 3-methyl-1,5-pentanediol di (3- Hi Roxybutyric acid) ester, 3-methyl-1,5-pentanediol di (4-hydroxybutyric acid) ester, triethylene glycol di (2-hydroxybutyric acid) ester, glycerin tri (ricinoleic acid) ester, L-tartaric acid di (1 -(2-ethylhexyl)), castor oil and the like.

  Examples of the carboxylic acid polyester plasticizer include oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4 A polyvalent carboxylic acid such as cyclohexanedicarboxylic acid, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3- Butylene glycol, 1,4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1 , 5-pentanediol, 3-methyl-2 4-pentanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,9-nonanediol, 2-methyl -1,8-octanediol, 1,2-decanediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, By alternately copolymerizing polyhydric alcohols such as 1,4-cyclohexanediol, 1,2-bis (hydroxymethyl) cyclohexane, 1,3-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane The resulting carboxylic acid polyester or lactone compound such as ε-caprolactone is opened. Examples thereof include carboxylic acid polyesters obtained by ring polymerization. The terminal structure of these carboxylic acid polyesters is not particularly limited, and may be a hydroxyl group or a carboxyl group, or may be an ester bond obtained by reacting a terminal hydroxyl group or a terminal carboxyl group with a monovalent carboxylic acid or a monohydric alcohol.

  Examples of the carbonated plasticizer include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1 , 4-butylene glycol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentane Diol, 3-methyl-2,4-pentanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1, 9-nonanediol, 2-methyl-1,8-octanediol, , 2-decanediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1, Transesterification of polyhydric alcohols such as 2-bis (hydroxymethyl) cyclohexane, 1,3-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane and carbonates such as dimethyl carbonate and diethyl carbonate And carbonic acid polyester compounds obtained by alternating copolymerization. The terminal structure of these carbonic acid polyester compounds is not particularly limited, but is preferably a carbonic acid ester group or a hydroxyl group.

  Polyether plasticizers include polyethylene glycol, poly (1,2-propylene glycol), poly (1,3-propylene glycol), poly (1,2-butylene glycol), poly (1,3-butylene glycol) , Poly (1,4-butylene glycol), poly (2,3-butylene glycol), etc., ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1, Examples thereof include a random copolymer or a block copolymer of two or more compounds selected from 3-butylene glycol, 1,4-butylene glycol, and 2,3-butylene glycol.

  When using these plasticizers in this invention, these may be used independently and may use 2 or more types together. Although the usage-amount is not specifically limited, It is 1-100 mass parts with respect to 100 mass parts of polyvinyl acetal contained in the composition A, Preferably it is 5-70 mass parts, It is optimal to use 20-60 mass parts. preferable. If the amount of the plasticizer used is less than 1 part by mass relative to 100 parts by mass of the polyvinyl acetal contained in the composition A, a sufficient plasticizing effect may not be obtained. No significant plasticizing effect can be obtained.

  Moreover, when using the laminated body of this invention for the use which needs to adjust adhesiveness with glass appropriately, such as a laminated glass intermediate film and a solar cell module especially, it is adhesiveness to the composition A used by this invention. It is preferable that an improving agent is added. As the adhesion improver, for example, those disclosed in WO 03/033583 can be used, and it is preferable to add an alkali metal salt and / or an alkaline earth metal salt of an organic acid, Particularly preferred is potassium acetate and / or magnesium acetate. The addition amount is preferably 0.0001 to 1% by mass with respect to the mass of the composition A, more preferably 0.0005 to 0.1% by mass, and still more preferably 0.001 to 0.03% by mass. . The optimum addition amount of the adhesion improver varies depending on the additive used or the purpose, but from the viewpoint of appropriately adjusting the adhesion with glass, the laminate of the present invention has a surface in contact with the glass. When the laminate which is the A layer and the laminate obtained by bonding the glass are evaluated by a Pummel test (Pummel test; described in International Publication No. 03/033583 etc.), it is generally preferable to adjust to 3 to 10, particularly high. It is preferable to adjust to 3-6 when penetration resistance is required, and to 7-10 when high glass scattering prevention property is required. When high glass scattering prevention property is required, it is also a useful method not to add an adhesion improver.

  The composition A of the present invention can be obtained by mixing polyvinyl acetal and, if necessary, a plasticizer and additives by a conventionally known method. Specific examples of the mixing method include melt kneading using a mixing roll, plastoyl, an extrusion group, etc., or a method in which the components of the composition A are dissolved in a suitable organic solvent and then the solvent is distilled off. The invention is not particularly limited unless it is contrary to the gist of the present invention.

  The acid value of the composition A used in the present invention is not particularly limited, but preferably has an acid value of 10 mgKOH / g or less, more preferably 7 mgKOH / g or less, still more preferably 5 mgKOH / g or less. And good. The composition A used in the present invention has an acid value in the above range, which is preferable because deterioration during long-term use hardly occurs.

  The glass transition temperature of the composition A used in the present invention is not particularly limited and can be appropriately selected according to the purpose, but is preferably in the range of 0 to 50 ° C, more preferably 0 to 45 ° C. Preferably, it is 0-40 degreeC. When the glass transition temperature of the composition A used in the present invention satisfies the above range, the laminate obtained using the composition A is excellent in flexibility near normal temperature, which is preferable.

  Next, the composition B used in the present invention will be described. The composition B used in the present invention is not particularly limited as long as it contains a hydrocarbon polymer and a carboxylic acid having 8 to 30 carbon atoms and / or a salt derived from a carboxylic acid having 8 to 30 carbon atoms. The carboxyl group and / or carboxylate group of the carboxylic acid having 8 to 30 carbon atoms and / or the salt derived from the carboxylic acid having 8 to 30 carbon atoms interacts with the hydroxyl group of the polyvinyl acetal contained in the A layer by hydrogen bonding. On the other hand, a relatively long chain hydrocarbon group contained in a carboxylic acid having 8 to 30 carbon atoms and / or a salt derived from a carboxylic acid having 8 to 30 carbon atoms is a hydrocarbon having a relatively close molecular polarity. It can also be compatible with and adhered to a polymer. Therefore, a laminate including a configuration in which the A layer composed of the composition A of the present invention and the B layer composed of the composition B are laminated is preferable because of excellent interlayer adhesion between the A layer and the B layer. In particular, when the carboxylic acid is used in the present invention, it is suitable from the viewpoint of excellent compatibility with the B layer, and when the salt derived from the carboxylic acid is used in the present invention, the B layer is hardly deteriorated by an acid. It is suitable.

  The hydrocarbon polymer used in the present invention is not particularly limited as long as it is a polymer having a hydrocarbon component as a main component, and can be appropriately selected according to the purpose. It is a polymer of one or more kinds of compounds selected from saturated hydrocarbon compounds and aromatic unsaturated hydrocarbon compounds having 8 to 12 carbon atoms, or hydrogenated products thereof, interlayer adhesion and various mechanical properties It is preferable in that it is excellent and is easily available. Here, a polymer of one or more compounds selected from an aliphatic unsaturated hydrocarbon compound having 2 to 12 carbon atoms and an aromatic unsaturated hydrocarbon compound having 8 to 12 carbon atoms, or a hydrogenated product thereof, The proportion of the total amount of the aliphatic unsaturated hydrocarbon compound having 2 to 12 carbon atoms and the aromatic unsaturated hydrocarbon compound having 8 to 12 carbon atoms in the total monomer units contained in the polymer is 80% by mass or more. The polymer is preferably 95% by mass or more, and optimally 98% by mass or more, or a hydrogenated product thereof. The proportion of the total amount of the aliphatic unsaturated hydrocarbon compound having 2 to 12 carbon atoms and the aromatic unsaturated hydrocarbon compound having 8 to 12 carbon atoms in all the monomer units contained in the polymer is lower than 80% by mass. If it becomes, there exists a tendency for characteristics, such as the low water absorption which a hydrocarbon type polymer originally has, various mechanical characteristics, and the sound insulation which the block copolymer mentioned later has.

  Specific examples of the aliphatic unsaturated hydrocarbon compound having 2 to 12 carbon atoms include ethylene, propylene, butylene, 2-butylene, isobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, cyclohexene, Aliphatic monoene compounds such as cyclooctene, butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3,5-hexatriene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1, Aliphatic conjugated polyene compounds such as 3-cyclooctadiene, and aliphatic non-conjugated polyene compounds such as 1,4-pentadiene, 1,5-hexadiene, 1,5-cyclooctadiene, and the like can be given.

  Specific examples of the aromatic unsaturated hydrocarbon compound having 8 to 12 carbon atoms include styrene, α-methylstyrene, β-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4 -Aromatic monoene compounds such as ethylstyrene, 4-butylstyrene, 4-tert-butylstyrene, (1-naphthyl) ethylene, (2-naphthyl) ethylene, and aromatic conjugates such as 1-phenylbutadiene and 2-phenylbutadiene Examples include, but are not limited to, polyene compounds, aromatic non-conjugated polyene compounds such as 1-phenyl-1,4-pentadiene and 1-phenyl-1,3-cyclohexadiene.

  In addition to the compounds exemplified above, the following compounds may be copolymerized as long as the effects of the present invention are not impaired. For example, acrylic acid or a salt thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-acrylate Acrylic esters such as ethylhexyl, dodecyl acrylate, octadecyl acrylate; methacrylic acid and its salts, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, methacrylic acid Methacrylic acid esters such as i-butyl, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate; acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethyla Acrylamide derivatives such as rilamide, diacetone acrylamide, acrylamide propane sulfonic acid and salts thereof, N-methylol acrylamide and derivatives thereof; methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamide propane sulfonic acid and salts thereof, Methacrylamide derivatives such as N-methylol methacrylamide or derivatives thereof; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether Vinyl ethers such as nitriles such as acrylonitrile and methacrylonitrile; vinyl chloride And vinyl halides such as vinyl fluoride; vinylidene chloride such as vinylidene chloride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; maleic acid and salts thereof or esters or anhydrides thereof; vinyltrimethoxysilane , Vinylsilyl compounds such as 3-methacryloxypropyltrimethoxysilane; isopropenyl acetate.

  Specifically, a polymer of one or more compounds selected from an aliphatic unsaturated hydrocarbon compound having 2 to 12 carbon atoms and an aromatic unsaturated hydrocarbon compound having 8 to 12 carbon atoms or a hydrogenated product thereof is specifically exemplified. , High-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, polypropylene, polystyrene, polybutadiene, polyisoprene, ethylene-propylene copolymer, hydrogenated polybutadiene, hydrogenated polyisoprene, styrene-butadiene block copolymer, styrene -Block copolymers such as isoprene block copolymers and hydrogenated products thereof. These polymerization methods are not particularly limited, and for example, those polymerized by a conventionally known method can be used. In particular, when the laminate of the present invention is used as a sound insulating laminated glass intermediate film, a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, a styrene-butadiene-isoprene copolymer, and hydrogenated products thereof. And block (X) made of a polymer of an aromatic unsaturated hydrocarbon compound having 8 to 12 carbon atoms and block (Y) made of a polymer of an aliphatic conjugated polyene compound having 2 to 12 carbon atoms. A coalescence and a hydrogenated product thereof (hereinafter collectively referred to simply as a block copolymer) are preferably used because they have excellent vibration damping properties and sound insulation properties. This will be described below.

The block copolymer used in the present invention is not particularly limited as long as it has a block (X) portion and a block (Y) portion. For example, [(X)-(Y)] _k , [(X) Block copolymers such as-(Y)] _m- (X), (Y)-[(X)-(Y)] _n can be used. Here, k, m, and n are arbitrary natural numbers. Among these, a block copolymer having two or more blocks (X) and one or more blocks (Y) is preferable, and a triblock copolymer composed of (X)-(Y)-(X) Is particularly preferred. In addition, when the block copolymer used in the present invention contains two or more blocks (X) or two or more blocks (Y), the blocks (X) and (Y) are the same. It may be different or different.

  The content ratio of the block (X) and the block (Y) in the block copolymer is not particularly limited as long as it does not contradict the purpose of the present invention, but from the viewpoint of vibration damping properties and sound insulation properties, the total mass of the block copolymer The content of the block (X) with respect to is preferably 5 to 95% by mass, and more preferably 10 to 70% by mass.

  The weight average molecular weights of the block (X) and the block (Y) in the block copolymer are not particularly limited and can be appropriately selected according to the purpose of using the laminate of the present invention, but per block (X) The weight average molecular weight is preferably 2,500 to 75,000, and the weight average molecular weight per block (Y) is preferably 1,000 to 100,000. Moreover, as a weight average molecular weight of a block copolymer, it is preferable that it is 10,000-1,000,000, and it is more preferable that it is 15,000-200,000. When the weight average molecular weight of the block (X) and the block (Y) is too small, the performance as a block copolymer may not be exhibited. Also, if the weight average molecular weight of the block copolymer is too small, the mechanical strength when it is made into a laminate may be too low, and if the weight average molecular weight of the block copolymer is too large, the handling property at the time of molding will be reduced. Deteriorate.

  The glass transition temperature of the block copolymer used in the present invention is not particularly limited and can be appropriately selected according to the purpose, but is preferably −50 to 50 ° C., and is −45 to 30 ° C. More preferably, it is -40-20 degreeC. When the glass transition temperature of the block copolymer satisfies the above range, the mechanical properties and various characteristics of the laminate of the present invention are preferable.

  The peak temperature of tan δ of the block copolymer used in the present invention is not particularly limited and can be appropriately selected according to the purpose, but is preferably −40 to 30 ° C., and preferably −35 to 25 ° C. Is more preferable, and it is more preferable that it is -30-20 degreeC.

  The mechanical strength of the block copolymer used in the present invention is not particularly limited and can be appropriately selected depending on the purpose. For example, if the tensile strength at break is expressed as an index, it is preferably 0.1 MPa or more. More preferably, it is 0.5 MPa or more, and further preferably 1.0 MPa or more.

  The MFR value of the block copolymer used in the present invention is not particularly limited and can be appropriately selected according to the purpose. For example, according to ASTM D1238, the MFR value when measured at a load of 2.16 kg and a temperature of 190 ° C. It is preferably 0.1 to 100 g / 10 minutes, more preferably 0.1 to 70 g / 10 minutes, and further preferably 0.1 to 50 g / 10 minutes.

  The block copolymer used in the present invention may be hydrogenated or not hydrogenated in the block (Y) portion, but is preferably hydrogenated from the viewpoint of weather resistance, The hydrogenation rate is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 95 mol% or more.

  Such a block copolymer can be produced by a conventionally known method. For example, an organic lithium reagent is used as an initiator, and an aromatic unsaturated hydrocarbon compound having 8 to 12 carbon atoms and 2 to 12 carbon atoms are used. Although the method of adding an aliphatic conjugated polyene compound sequentially and making it react is mentioned, It is not limited to this.

  The content of the hydrocarbon-based polymer contained in the composition B used in the present invention is not particularly limited as long as it does not contradict the gist of the present invention, but is preferably 30% by mass or more with respect to the mass of the composition B, more preferably It is preferably 80% by mass or more, optimally 90% by mass or more. When the content of the hydrocarbon polymer is lower than 30% by mass with respect to the mass of the composition B, the interlayer adhesion is lowered, the low water absorption inherent in the hydrocarbon polymer, various mechanical properties, There exists a tendency for the characteristics, such as sound insulation property which the block copolymer mentioned later has to fall.

  Next, the carboxylic acid and / or carboxylic acid-derived salt used in the present invention will be described. The carboxylic acid used in the present invention is not particularly limited as long as it is a carboxylic acid having 8 to 30 carbon atoms. Moreover, the salt derived from carboxylic acid used by this invention will not be specifically limited if it is a salt derived from C8-C30 carboxylic acid. Here, the salt derived from a carboxylic acid having 8 to 30 carbon atoms is a carboxylate ion (carboxylate ion having 8 to 30 carbon atoms) obtained by removing a proton contained in a carboxyl group from a carboxylic acid having 8 to 30 carbon atoms. Represents a salt formed from a cation. The carboxylic acid having 8 to 30 carbon atoms and / or the salt derived from the carboxylic acid having 8 to 30 carbon atoms can be used alone or in combination of two or more kinds. It is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 3 parts by mass, and 0.05 to 2 parts by mass with respect to 100 parts by mass of the hydrocarbon polymer contained. Is more preferable. If the total addition amount is less than 0.01 parts by mass, sufficient interlayer adhesion may not be expressed, and even if it is more than 5 parts by mass, no significant effect can be expected from the viewpoint of improving interlayer adhesion, Further, it may be difficult to uniformly disperse the carboxylic acid and / or the carboxylic acid-derived salt in the composition B. Moreover, although carbon number of the carboxylic acid used by this invention and the salt derived from carboxylic acid is 8-30, it is preferable that it is 8-25, and it is more preferable that it is 8-20. When these carbon numbers are smaller than 8, the compatibility with the hydrocarbon polymer is deteriorated, the interlayer adhesion between the A layer and the B layer is lowered, and when the carbon number is larger than 30, the carboxyl group or the carboxylate group. And the interaction by the hydrogen bond with the hydroxyl group of the polyvinyl acetal contained in A layer becomes insufficient, and the interlayer adhesiveness of A layer and B layer falls.

  Specific examples of the carboxylic acid having 8 to 30 carbon atoms include octanoic acid, 2-ethylhexanoic acid (octylic acid), decanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, Examples include ricinoleic acid, 12-hydroxystearic acid, behenic acid, montanic acid, 4-butylbenzoic acid, 1-naphthylic acid, 2-naphthylic acid, and the like. Although what remove | excluded the proton contained in the carboxyl group of C8-C30 carboxylic acid is mentioned, It is not limited to this. Among these, octanoic acid, octylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, and octanoic acid, octylic acid, lauric acid, palmitic acid, stearic acid, olein Salts formed from carboxylate ions and cations excluding protons contained in the carboxyl groups of acids, linoleic acid, linolenic acid, and ricinoleic acid are preferred in terms of interlayer adhesion and compatibility with the B layer. .

  The cation constituting the salt derived from carboxylic acid is not particularly limited, but monovalent cation: lithium ion, sodium ion, potassium ion, ammonium ion, pyridinium ion, etc., divalent cation: barium ion, magnesium ion , Calcium ions, zinc ions, copper ions, iron (II) ions, etc., trivalent cations: aluminum ions, iron (III) ions, etc., tetravalent cations: titanium ions, etc. Among these, calcium ions are preferred from the viewpoint of interlayer adhesion and compatibility with the B layer.

  Specific examples of the salt formed from the carboxylate ion and cation include calcium octylate, magnesium octylate, barium octylate, calcium laurate, magnesium laurate, barium laurate, zinc laurate, calcium palmitate, Examples include, but are not limited to, lithium stearate, calcium stearate, magnesium stearate, barium stearate, zinc stearate, calcium oleate, and calcium ricinoleate. Among these, calcium octylate, calcium laurate, calcium palmitate, calcium stearate, calcium oleate, or calcium ricinoleate is preferable from the viewpoint of excellent interlayer adhesion between the A layer and the B layer.

  The melting point of the carboxylic acid having 8 to 30 carbon atoms and / or the salt derived from the carboxylic acid having 8 to 30 carbon atoms used in the present invention is not particularly limited, but is preferably 230 ° C. or lower, and 220 ° C. or lower. Is more preferable, and it is more preferable that it is 210 degrees C or less. In general, when preparing the composition B, a temperature higher than the melting point of the carboxylic acid and / or the salt derived from the carboxylic acid is required to uniformly disperse and dissolve the carboxylic acid and / or the salt derived from the carboxylic acid. When the melting point of the carboxylic acid and / or the salt derived from the carboxylic acid is higher than 230 ° C., it is not preferable from the viewpoint of productivity and from the viewpoint of preventing thermal deterioration during molding of the composition B.

  The composition B used in the present invention may contain an antioxidant, an ultraviolet absorber, and other conventionally known additives. This is explained below.

  When the antioxidant is added to the composition B used in the present invention, the kind thereof is not particularly limited, and examples thereof include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like. Of these, phenolic antioxidants are preferred, and alkyl-substituted phenolic antioxidants are particularly preferred.

  As a phenolic antioxidant, the compound illustrated as a phenolic antioxidant which may be added to the composition A is mentioned. As phosphorus antioxidant, the compound illustrated as the phosphorus antioxidant which may be added to the composition A is mentioned. Examples of the sulfur-based antioxidant include the compounds exemplified as the sulfur-based antioxidant that may be added to the composition A. These antioxidants can be used alone or in combination of two or more, and the amount added is 0.001 to 5% by mass, preferably 0.01 to 1% by mass with respect to the mass of the composition B. It is good to be in the range of%. If the addition amount of the antioxidant is less than 0.001% by mass, a sufficient effect may not be obtained, and if it is more than 5% by mass, no remarkable effect can be expected.

  When adding a ultraviolet absorber to the composition B used by this invention, the kind is not specifically limited. As an ultraviolet absorber used, the ultraviolet absorber illustrated as what may be added to the composition A is mentioned, for example. These ultraviolet absorbers can also be used in combination of two or more, and the addition amount is preferably 0.001 to 5% by mass, and 0.01 to 1% by mass with respect to the mass of the composition B. More preferably. If the addition amount of the ultraviolet absorber is less than 0.001% by mass, a sufficient effect may not be obtained, and if it is more than 5% by mass, no remarkable effect can be expected.

  The composition B of the present invention can be obtained by mixing a hydrocarbon polymer and, if necessary, an additive by a conventionally known method. Specific examples of the mixing method include melt kneading using a mixing roll, a plast mill, an extruder, or the like, or a method in which the components of the composition B are dissolved in a suitable organic solvent and then the solvent is distilled off. The invention is not particularly limited unless it is contrary to the gist of the present invention.

  The laminated body of the present invention may contain two or more of the A layer and the B layer as long as it includes a configuration in which the A layer and the B layer are laminated. They may be the same or different. Moreover, the layered product of the present invention may contain a layer other than the above (referred to as C layer). Specific examples of the C layer include, but are not limited to, a polyester layer, a polyamide layer, a polyimide layer, and a polycarbonate layer. Specific examples of the layer structure of the laminate of the present invention include A layer / B layer, A layer / B layer / A layer, A layer / B layer / A layer / B layer / A layer, B layer / A layer. / B layer, A layer / B layer / B layer / A layer, A layer / B layer / C layer / B layer / A layer, A layer / B layer / C layer and the like, but are not limited thereto.

  If the laminated body of this invention includes the structure formed by laminating | stacking A layer and B layer, the thickness of each layer will not be specifically limited, About A layer and B layer, 0.001-5 mm, Preferably it is 0 0.1-3 mm, optimally 0.1-1.6 mm. When two or more of these layers are included in the laminate of the present invention, their thicknesses may be the same or different. Moreover, the thickness of each of these layers may be uniform or non-uniform.

  The manufacturing method of the laminated body of this invention is not specifically limited, It can manufacture by a conventionally well-known method, such as co-extrusion molding, multilayer injection molding, dry lamination. For example, in the case of a laminate including a structure in which the A layer and the B layer are laminated, it is preferable to perform coextrusion molding, and the method may be in-die lamination in which each layer component is contacted in the die, or outside the die. It is also possible to use lamination outside the die to be brought into contact with. Moreover, although extrusion temperature is selected suitably, it is good in it being 150-300 degreeC, Preferably it is 180-250 degreeC.

  The laminated body of this invention is used suitably for a laminated glass intermediate film use. This will be described below. When using the laminate of the present invention as a laminated glass interlayer film, the glass used in that case is not particularly limited, in addition to inorganic glass such as float plate glass, polished plate glass, mold plate glass, mesh plate glass, heat ray absorbing plate glass, Conventionally known organic glasses such as polymethyl methacrylate and polycarbonate can be used, and these may be colorless, colored, transparent or non-transparent. These may be used alone or in combination of two or more. The thickness of the glass is not particularly limited, but is preferably 100 mm or less.

  When the laminate of the present invention is used as a laminated glass intermediate film, the configuration of the laminate is not particularly limited, but it is preferable that the outermost layer of the laminate of the present invention has a layer having an appropriate adhesion to glass, When inorganic glass is used as the glass, the outermost layer is preferably an A layer having excellent adhesion to glass. Specific examples of the laminate of the present invention in which the outermost layer is A layer include A layer / B layer / A layer, A layer / B layer / C layer / B layer / A layer, A layer / B layer / C. Layer / A layer and the like.

  When the laminate of the present invention is used as a laminated glass intermediate film, the shape of the outermost surface of the laminate is not particularly limited, but the outermost surface of the laminate is taken into consideration when handling (bubble removal) when laminating with glass. In addition, it is preferable to form a concavo-convex structure by a conventionally known method such as melt fracture or embossing.

  Furthermore, by using the laminate of the present invention as a filler for solar cell modules, it is suitably used in fields where sound insulation is required, in particular, building-integrated solar cells such as BIPV. This will be described below.

  The type of the solar battery cell used in the solar battery module of the present invention is not particularly limited, and there is no particular limitation. Examples thereof include thin film silicon types such as materials, thin film types such as compound semiconductor types using CIS, CIGS, CdTe, GaAs, and the like, and organic solar cell types.

  When the solar battery cell used in the solar battery module of the present invention is of a crystal type, for example, as shown in FIG. 1 (a), the crystal type solar battery cell 3 and the filler 2 and glass, a back sheet, etc. A structure as shown in FIG. 1B is obtained by laminating 1 after stacking 1) (referred to as glass or the like). If at least one filler 2 used in this case is the laminate of the present invention, other fillers, for example, a conventionally known crosslinkable ethylene-vinyl acetate copolymer composition can be used in combination. is there.

  Moreover, when the photovoltaic cell used for the photovoltaic module of this invention is a thin film type, as shown to Fig.2 (a), surface glass (ITO, ATO, FTO etc.) by which the photovoltaic cell 4 was vapor-deposited is shown, for example. A transparent electrode layer may be included), and the filler 2 and the glass 1 or the like 1 are stacked and then laminated, and the configuration shown in FIG. Also in this case, as the filler 2, a filler made of a composition made of a crosslinkable ethylene-vinyl acetate copolymer composition may be used in combination as necessary.

  The glass used in the solar cell module of the present invention is not particularly limited. For example, in addition to inorganic glass such as float plate glass, polished plate glass, mold plate glass, netted plate glass, and heat ray absorbing plate glass, polymethyl methacrylate, polycarbonate and the like A conventionally well-known organic glass etc. can be used. Also, the back sheet is not particularly limited, but those having excellent weather resistance and low moisture permeability are preferably used, and polyester films, fluorine resin films, laminates thereof, and inorganic compounds are laminated thereon. Can be used.

  In addition, the solar cell module of the present invention can be combined with a known frame, junction box, sealing agent, mounting jig and mount, antireflection film, various facilities using solar heat, rain gutter structure, and the like.

  The laminated glass and solar cell module of the present invention can be produced by a conventionally known method. For example, a method using a vacuum laminator device, a method using a vacuum bag, a method using a vacuum ring, and a method using a nip roll Etc. In addition, a method of adding to the autoclave process after provisional pressure bonding can be additionally performed.

In the case of using a vacuum laminator device, for example, a known device used for manufacturing a solar cell is used, and a vacuum of 1 × 10 ^{−6 to} 3 × 10 ⁻² MPa is used. Laminated at temperature. A method using a vacuum bag or a vacuum ring is described in, for example, European Patent No. 1235683, and is laminated at 130 to 145 ° C. under a pressure of about 2 × 10 ⁻² MPa, for example.

  In the case of using a nip roll, for example, there is a method in which after the first temporary press-bonding at a temperature not higher than the flow start temperature of the plasticized polyvinyl acetal resin, the temporary press-bonding is performed under a condition close to the flow start temperature. Specifically, for example, after heating to 30 to 70 ° C. with an infrared heater or the like, degassing with a roll, and further heating to 50 to 120 ° C., followed by pressure bonding with a roll and bonding or temporary bonding may be mentioned.

  The autoclave process that is additionally performed after the temporary pressure bonding depends on the thickness and configuration of the module and the laminated glass, but is, for example, 0.5 to 2 at a temperature of 130 to 145 ° C. under a pressure of 0.1 to 0.15 MPa. Implemented for hours.

  The haze value of the laminated glass thus obtained is not particularly limited, but is preferably 5% or less, more preferably 3% or less, and further preferably 1% or less.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In the following examples, “%” and “part” mean “% by mass” and “part by mass” unless otherwise specified.

The hydrocarbon polymers used in the present invention are as follows.
Hydrocarbon polymer-1;
Polystyrene-polyisoprene-polystyrene triblock copolymer (polyisoprene portion is completely hydrogenated), total content of polystyrene portion = 12%, glass transition temperature = −32 ° C., tan δ peak temperature = −17 ° C., MFR value (ASTM D1238, load 2.16 kg) at 190 ° C., 0.5 g / 10 min, tan δ = 1.0 at −20 ° C., tan δ = 0.8 at 0 ° C., tan δ = 20 ° C. = 0.3
Hydrocarbon polymer-2;
Polystyrene-polyisoprene-polystyrene triblock copolymer (polyisoprene portion is completely hydrogenated), polystyrene portion content = 22%, glass transition temperature = −12 ° C., tan δ peak temperature = −5 ° C., MFR value ( ASTM D1238, load 2.16 kg) at 190 ° C. 0.7 g / 10 min, tan δ = 0.15 at −20 ° C., tan δ = 1.05 at 0 ° C., tan δ = 20 ° C. = 0.4
Hydrocarbon polymer-3;
Polystyrene-polyisoprene-polystyrene triblock copolymer (polyisoprene portion not hydrogenated), polystyrene portion content = 20%, glass transition temperature-12 ° C., tan δ peak temperature = −1 ° C., MFR value (ASTM D1238, load 2.16 kg) is 3.8 g / 10 min at 190 ° C., tan δ = 0.08 at −20 ° C., tan δ = 1.05 at 0 ° C., tan δ = 20 at 20 ° C.

(Preparation of polyvinyl acetal PVB-1)
In a 10 L (liter) glass container equipped with a reflux condenser, thermometer, and squid-type stirring blade, ion-exchanged water 8100 g, polyvinyl alcohol (PVA-1) (viscosity average polymerization degree 1700, saponification degree 99 mol%) 660 g (PVA concentration 7.5%), and the contents were heated to 95 ° C. and completely dissolved. Next, after gradually cooling to 5 ° C. over about 30 minutes with stirring at 120 rpm, 384 g of butyraldehyde and 540 mL of 20% hydrochloric acid were added, and a butyralization reaction was performed for 150 minutes. Thereafter, the temperature was raised to 50 ° C. over 60 minutes, held at 50 ° C. for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water, an excessive amount of aqueous sodium hydroxide solution was added, washed again, and dried to obtain polyvinyl butyral (PVB-1). The resulting PVB-1 had a butyralization degree (average acetalization degree) of 69 mol%, a vinyl acetate group content of 1 mol%, and a vinyl alcohol group content of 30 mol%. The degree of butyralization of PVB-1 and the content of the remaining vinyl acetate groups were measured according to JIS K6728.

(Preparation of polyvinyl acetal PVB-2)
In a 10 L (liter) glass container equipped with a reflux condenser, thermometer, and squid-type stirring blade, ion-exchanged water 8100 g, polyvinyl alcohol (PVA-1) (viscosity average polymerization degree 1700, saponification degree 99 mol%) 660 g (PVA concentration 7.5%), and the contents were heated to 95 ° C. and completely dissolved. Next, after gradually cooling to 5 ° C. over about 30 minutes with stirring at 120 rpm, 330 g of butyraldehyde and 540 mL of 20% hydrochloric acid were added, and a butyralization reaction was performed for 150 minutes. Thereafter, the temperature was raised to 50 ° C. over 60 minutes, held at 50 ° C. for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water, an excessive amount of aqueous sodium hydroxide solution was added, washed again, and dried to obtain polyvinyl butyral (PVB-2). The resulting PVB-2 had a butyralization degree (average acetalization degree) of 60 mol%, a vinyl acetate group content of 1 mol%, and a vinyl alcohol group content of 39 mol%. The degree of butyralization of PVB-2 and the content of the remaining vinyl acetate groups were measured according to JIS K6728.

(Preparation of composition A-1)
40 g of PVB-1 and 16 g of polyester diol (copolymer of adipic acid and 3-methyl-1,5-pentanediol, number average molecular weight based on hydroxyl value = 500), 0.12 g of 2- (3 , 5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 0.04 g potassium acetate and 0.05 g 2,6-di-tert-butyl-4-methylphenol The mixture was melt-kneaded at 60 rpm for 5 minutes to obtain a composition A-1.
(Acid Value Measurement of Composition A-1)
According to JIS K6728, the acid value of composition A-1 was measured. The acid value of composition A-1 was 0.1 mgKOH / g.
(Measurement of glass transition temperature of composition A-1)
According to JIS K7198, the dynamic viscoelasticity of the composition A-1 was measured (frequency: 1 Hz) and determined from the peak temperature of tan δ. The glass transition temperature of Composition A-1 was 28 ° C.

(Preparation of composition A-2)
In the preparation of the composition A-1, the composition A-2 was prepared in the same manner except that PVB-2 was used instead of the PVB-1, and the same measurement was performed. The acid value of Composition A-2 was 0.1 mgKOH / g, and the glass transition temperature was 31 ° C.

(Adjustment of Composition B-1)
100 g of hydrocarbon polymer-1 and 1 g of stearic acid (melting point 69 ° C.) and 0.1 g of 2,6-di-tert-butyl-4-methylphenol were added to lab plastoyl (200 ° C., 60 rpm, 5 minutes). ) To obtain a composition B-1.

(Adjustment of Composition B-2)
In the preparation of the composition B-1, a composition B-2 was prepared in the same manner except that the hydrocarbon polymer-2 was used instead of the hydrocarbon polymer-1.

(Adjustment of Composition B-3)
In the preparation of the composition B-1, a composition B-3 was prepared in the same manner except that the hydrocarbon polymer-3 was used instead of the hydrocarbon polymer-1.

(Adjustment of Composition B-4)
Composition B-4 was prepared in the same manner as in the preparation of Composition B-1, except that the amount of stearic acid used was changed to 0.2 g.

(Adjustment of Composition B-5)
Composition B-5 was prepared in the same manner as in the preparation of Composition B-1, except that octanoic acid (melting point: 16 ° C.) was used instead of stearic acid.

(Adjustment of Composition B-6)
Composition B-6 was prepared in the same manner as in the preparation of Composition B-1, except that oleic acid (melting point: 13 ° C.) was used instead of stearic acid.

(Adjustment of Composition B-7)
Composition B-7 was prepared in the same manner as in the preparation of Composition B-1, except that ricinoleic acid (melting point: 5 ° C.) was used instead of stearic acid.

(Adjustment of Composition B-8)
Composition B-8 was prepared in the same manner as in the preparation of Composition B-1, except that calcium stearate (melting point: 150 to 160 ° C.) was used instead of stearic acid.

(Adjustment of Composition B-9)
The same as in the preparation of Composition B-1, except that calcium stearate (melting point: 150 to 160 ° C.) was used instead of stearic acid, and hydrocarbon polymer-2 was used instead of hydrocarbon polymer-1. Thus, Composition B-9 was prepared.

(Adjustment of Composition B-10)
In preparing the composition B-1, the same except that calcium stearate (melting point: 150 to 160 ° C.) was used instead of stearic acid, and hydrocarbon polymer-3 was used instead of hydrocarbon polymer-1. Thus, Composition B-10 was prepared.

(Adjustment of Composition B-11)
Composition B-11 was prepared in the same manner as in the preparation of Composition B-8, except that the amount of calcium stearate used was changed to 0.2 g.

(Adjustment of Comparative Example Composition-1)
Comparative Example Composition-1 was prepared in the same manner except that stearic acid was not used in the preparation of Composition B-1.

Example 1
A film (film A-1) obtained by hot-pressing composition A-1 in a 10 cm × 10 cm × 1 mm formwork (150 ° C., 12 kg / cm ² , 30 minutes) and 10 cm of composition B-1 A film (film B-1) obtained by hot pressing (200 ° C., 12 kg / cm ² , 5 minutes) in a mold of × 10 cm × 1 mm is stacked, and the pressure is 12 kg / cm ² at 135 ° C. for 30 minutes. It heat-processed and obtained the laminated body-1 (A layer / B layer).

(Adhesive evaluation)
Laminate-1 was cut into 1 cm × 10 cm strips and conditioned overnight at 23 ° C. and 50% RH. The long side of the strip is peeled about 2 cm from the end between the A layer and the B layer, and the peeling test is performed 5 times at 100 mm / min using an autograph (manufactured by Shimadzu Corporation, Autograph AG-IS). The average value of five times of interlayer adhesion was obtained. The evaluation results are shown in Table 2.

(Example 2)
Laminate-2 was prepared in the same manner as in Example 1 except that the composition A-2 was used instead of the composition A-1, and the same evaluation was performed. The results are shown in Table 2.

(Example 3)
Except having used composition B-2 instead of composition B-1, laminated body-3 was created by the same method as Example 1, and the same evaluation was performed. The results are shown in Table 2.

Example 4
A laminate 4 was prepared in the same manner as in Example 1 except that the composition B-3 was used instead of the composition B-1, and the same evaluation was performed. The results are shown in Table 2.

(Example 5)
A laminate-5 was prepared in the same manner as in Example 1 except that the composition B-4 was used instead of the composition B-1, and the same evaluation was performed. The results are shown in Table 2.

(Example 6)
A laminate-6 was prepared in the same manner as in Example 1 except that the composition B-5 was used instead of the composition B-1, and the same evaluation was performed. The results are shown in Table 2.

(Example 7)
A laminate 7 was prepared in the same manner as in Example 1 except that the composition B-6 was used instead of the composition B-1, and the same evaluation was performed. The results are shown in Table 2.

(Example 8)
A laminate-8 was prepared in the same manner as in Example 1 except that the composition B-7 was used instead of the composition B-1, and the same evaluation was performed. The results are shown in Table 2.

Example 9
A laminate 9 was prepared in the same manner as in Example 1 except that the composition B-8 was used instead of the composition B-1, and the same evaluation was performed. The results are shown in Table 2.

(Example 10)
A laminate 10 was prepared in the same manner as in Example 1 except that the composition B-9 was used instead of the composition B-1, and the same evaluation was performed. The results are shown in Table 2.

(Example 11)
A laminate 11 was prepared in the same manner as in Example 1 except that the composition B-10 was used instead of the composition B-1, and the same evaluation was performed. The results are shown in Table 2.

(Example 12)
Laminate-12 was prepared in the same manner as in Example 1 except that the composition B-11 was used instead of the composition B-1, and the same evaluation was performed. The results are shown in Table 2.

(Example 13)
A film (film A-1) obtained by hot-pressing composition A-1 in a 10 cm × 10 cm × 0.3 mm mold (150 ° C., 12 kg / cm ² , 30 minutes), and composition B-1 A film (film B-1) obtained by hot pressing (200 ° C., 12 kg / cm ² , 5 minutes) in a 10 cm × 10 cm × 0.2 mm mold (film A-1 / film B-1 / Stacked in the order of film A-1), heat-treated at 135 ° C. for 30 minutes under a pressure of 12 kg / cm ^{2 in} a 10 cm × 10 cm × 0.8 mm mold, and laminated body-13 (A layer / B layer / A layer) )

(Evaluation of laminated glass)
Laminated product-13 sandwiched between two 10 cm × 10 cm × 3 mm glasses was degassed by nip roll treatment at 50 ° C. and then autoclaved (140 ° C., 12 kg / cm ² , 2 hours), laminated glass— 1 was obtained. The haze of the laminated glass was evaluated with a haze meter manufactured by Suga Test Instruments Co., Ltd. Further, the haze after the laminated glass-1 was treated at 80 ° C. and 30% RH for 1000 hours was similarly evaluated. The evaluation results are shown in Table 2.

(Example 14)
Laminate-14 and laminated glass-2 were prepared in the same manner as in Example 13 except that the composition B-8 was used instead of the composition B-1, and the same evaluation was performed. The results are shown in Table 2.

(Comparative Example-1)
Comparative Example Laminate-1 was prepared in the same manner as in Example 1 except that Comparative Example Composition-1 was used instead of Composition B-1, and the same evaluation was performed. The results are shown in Table 2.

  The laminate of the present invention contains a carboxylic acid having 8 to 30 carbon atoms and / or a salt derived from a carboxylic acid having 8 to 30 carbon atoms as an essential component in the composition B. The carboxyl group and / or carboxylate group of the carboxylic acid having 8 to 30 carbon atoms and / or the salt derived from the carboxylic acid having 8 to 30 carbon atoms and the hydroxyl group of polyvinyl acetal contained in the A layer are mutually bonded by hydrogen bonding. On the other hand, a relatively long chain hydrocarbon group of a carboxylic acid having 8 to 30 carbon atoms and / or a salt derived from a carboxylic acid having 8 to 30 carbon atoms is carbonized having a relatively close molecular polarity. It can also be compatible with and bonded to a hydrogen-based polymer. Therefore, the laminate including the structure in which the A layer composed of the composition A of the present invention and the B layer composed of the composition B are laminated is excellent in interlayer adhesiveness between the A layer and the B layer. It is suitable when used for a laminated glass interlayer film.

1 Glass etc. 2 Filler 3 Solar cell (crystalline)
4 Solar cells (thin film type)

Claims (15)

A layer consisting of composition A containing polyvinyl acetal, and B layer consisting of a hydrocarbon polymer and a composition B containing a carboxylic acid having 8 to 30 carbon atoms and / or a salt derived from a carboxylic acid having 8 to 30 carbon atoms A laminate including a structure formed by laminating The composition B includes a total of 0.01 to 5 parts by mass of a carboxylic acid having 8 to 30 carbon atoms and / or a salt derived from a carboxylic acid having 8 to 30 carbon atoms with respect to 100 parts by mass of the hydrocarbon-based polymer. The laminate according to claim 1. The hydrocarbon polymer is a polymer composed of one or more monomer units selected from the group consisting of aliphatic unsaturated hydrocarbons having 2 to 12 carbon atoms and aromatic unsaturated hydrocarbons having 8 to 12 carbon atoms. The laminate according to claim 1 or 2, which is a coalescence or a hydrogenated product of the polymer. The hydrocarbon polymer is a polymer block (X) comprising an aromatic unsaturated hydrocarbon unit having 8 to 12 carbon atoms and a polymer block (Y) comprising an aliphatic conjugated polyene unit having 2 to 12 carbon atoms. The laminated body of Claim 1 or 2 which is a block copolymer containing these, or the hydrogenated product of this block copolymer. The aromatic unsaturated hydrocarbon having 8 to 12 carbon atoms is styrene, and the aliphatic conjugated polyene having 2 to 12 carbon atoms is butadiene, isoprene, or a mixture of butadiene and isoprene. Laminated body. The laminated body in any one of Claims 1-5 whose melting | fusing point of the said carboxylic acid is 230 degrees C or less. The laminated body in any one of Claims 1-6 whose melting | fusing point of the said carboxylic acid-derived salt is 230 degrees C or less. The laminate according to any one of claims 1 to 7, wherein the carboxylic acid-derived salt is a calcium salt. The laminate according to any one of claims 1 to 8, wherein the polyvinyl acetal is obtained by acetalizing polyvinyl alcohol having a viscosity average polymerization degree of 150 to 3000. The laminate according to any one of claims 1 to 9, wherein the polyvinyl acetal is polyvinyl butyral. The laminated body in any one of Claims 1-10 whose average acetalization degree of the said polyvinyl acetal is 40-85 mol% and whose average vinyl acetate group amount is 0.01-30 mol%. The laminate according to any one of claims 1 to 11, wherein the A layer contains 1 to 100 parts by mass of a plasticizer with respect to 100 parts by mass of polyvinyl acetal. The laminated glass containing the laminated body in any one of Claims 1-12. The laminated glass of Claim 13 whose haze is 5% or less. The solar cell module containing the laminated body in any one of Claims 1-12.

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