JP2014105330A - Resin composition for joining laminate sheets - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for joining laminate sheets excellent in terms not only of curing reactivity but also of post-curing-reaction adhesiveness and post-curing-reaction durability and, preferably, of weather resistance; a solar cell rear surface protective sheet prepared by using the resin composition for joining laminate sheets; and a solar cell module.SOLUTION: The provided resin composition for joining laminate sheets is a resin composition for joining laminate sheets including: a copolymer (A); and a reactive compound (B) possessing a functional group which can be reacted with an active hydrogen group (hereafter referred to as the "reactive functional group") wherein the copolymer (A) is obtained by polymerizing an α,β-unsaturated compound (a-1) possessing a functional group such as a carboxyl group, etc. and the like.

Description

The present invention relates to a resin composition for bonding laminated sheets used for bonding plastic films, metal foils and the like.

  In recent years, for outdoor industrial applications, for example, as barrier sheets, roofing materials, solar cell panel materials, window materials, outdoor flooring materials, lighting protection materials, automobile members, signboards, stickers, etc., laminated sheets such as aluminum, copper, Alternatively, a metal foil such as a steel plate, a metal plate, or a metal vapor-deposited film and a plastic film such as a polypropylene resin, a polyvinyl chloride resin, a polyester resin, a fluorine resin, or a propenoic acid resin are laminated and laminated. (Laminated) has been used. In these laminated sheets, as a resin composition for joining laminated sheets, a metal foil, a metal plate, or a metal vapor-deposited film, and a plastic film, a polyepoxy resin laminated sheet joining resin composition, or polyurethane series Resin compositions for joining resin laminated sheets are known.

  On the other hand, solar cells are rapidly spreading as clean energy. A simple solar battery module used for a solar battery has a configuration in which a filler and a glass plate are sequentially laminated on both surfaces of a solar battery cell which is a solar battery element. Since a glass plate is excellent in transparency, weather resistance, and scratch resistance, it is still generally used as a sealing sheet on the solar light receiving surface side. However, on the non-light-receiving surface side (back surface) that does not require transparency, back surface protection sheets for solar cells other than glass plates (hereinafter referred to as back surface protection sheets) have been developed by various companies in terms of cost, safety, and workability. These are being replaced by glass plates.

  An example of a method for manufacturing a back surface protective sheet for solar cells and an example of a back surface protective sheet for solar cells will be described. The manufacturing method and configuration of the back surface protective sheet for solar cells are heat resistance, weather resistance, water vapor permeability, and electrical insulation. Various manufacturing methods and configurations are employed according to the purpose and needs such as sex.

  Examples of the plastic film member used for the back surface protection sheet for solar cells include polyester resin film, polyethylene resin film, polypropylene resin film, polyvinyl chloride resin film, polycarbonate resin film, polysulfone resin film, poly (2 -Methyl) propenoic acid resin film, fluorine resin film, etc., various substrates are used, metal oxide or non-metal inorganic oxide deposited film, aluminum foil, copper foil, etc. metal film Is used.

  Among these, polyethylene terephthalate, polynaphthalene terephthalate, etc. that have resistance to temperature in order to satisfy performance such as weather resistance, water vapor permeability, electrical insulation, mechanical properties, mounting workability when used as a solar cell module Polyester-based resin film, polycarbonate-based resin film, and plastic film or aluminum on which a metal oxide having a water vapor barrier property or a non-metallic inorganic oxide is deposited in order to prevent a decrease in output due to the influence of water on the solar battery cell In order to prevent appearance defects due to light deterioration, such as a metal foil such as a foil, a back protective sheet for a solar cell in which a fluorine resin film having good weather resistance is laminated is used.

  These solar cell back surface protection sheets are produced by using solar cells such as ethylene vinyl acetate resin (EVA), glass, and a sealing agent for adhering the back surface protection sheet. At that time, heat resistance is required for pressure bonding under vacuum at high temperature. Moreover, the back surface protection sheet for solar cells needs to have excellent adhesiveness even after being exposed to the outdoors for a long time, and it is required to have excellent hydrolysis resistance as well as adhesive strength after curing. It is done. Moreover, when using the back surface protection sheet for solar cells using a transparent film, a color difference change is very small and the outstanding weather resistance is calculated | required.

  Examples of the configuration of the back surface protection sheet for solar cells include, from the cell layer side, an insulating film / bonding agent / film having water vapor barrier properties / bonding agent / weather resistant film. Examples of the film having a water vapor barrier property include a silica-deposited PET film, an aluminum oxide-deposited PET film, and an aluminum foil. The outermost layer includes a fluororesin film, A PET film, a polyethylene film, etc. are mentioned, The resin composition for laminated sheet joining is calculated | required the adhesiveness outstanding with respect to these various base materials.

Patent Document 1 discloses a polyester resin in consideration of balance that can give excellent initial cohesion and adhesion, and a polyurethane-based resin laminated sheet bonding resin composition using the same.

Patent Document 2 discloses a polyurethane resin-based laminated sheet bonding resin composition that is excellent in hot water resistance during retort sterilization in food packaging.

Patent Document 3 discloses a resin composition for joining a polyurethane resin-based laminated sheet using a tin catalyst in automobile applications.

Patent Document 4 discloses the use of a polyurethane resin-based laminated sheet bonding resin composition having hydrolysis resistance in a solar cell back surface protective sheet.

Furthermore, Patent Document 5 discloses a solar cell back surface protective sheet provided with an adhesion improving layer composed of a polyester resin or a polyester polyurethane resin-based laminated sheet bonding resin composition.

Patent Documents 6 and 7 disclose a solar cell back surface protective sheet using a propenoic acid resin-based laminated sheet bonding resin composition.

On the other hand, in recent years, efforts to combat global warming have become an urgent issue, and members such as solar cell back surface protection sheets and laminated sheets are required to develop and provide materials with long-term durability. Since these laminates are exposed to the outdoors for a long period of time, excellent durability performance is required for the outdoor laminated sheet joining resin composition.

  However, when the polyurethane-based laminated sheet bonding resin composition using the polyester-based resin is used, the cohesive force of the laminated sheet-bonding resin composition after the curing reaction is reduced due to hydrolysis of the ester skeleton, and the solar cell. There is a possibility that a plurality of films constituting the back protective sheet will be peeled off.

  In addition, the polyurethane resin laminated sheet bonding resin composition is designed with an excess of isocyanate groups, the isocyanate group curing reaction is not completed, and the remaining isocyanate groups undergo decarboxylation due to reaction with moisture, resulting in durability. There is a risk of foaming during testing. At that time, an attempt can be made to accelerate the curing reaction using an organotin catalyst or the like to suppress the remaining isocyanate group, but the catalyst has a strong promoting effect on the curing reaction and it may be difficult to control pot life and the like. .

  In addition, in the resin composition for bonding laminated sheets using propenoic acid resin, the curing reaction of the isocyanate group requires 5 days at 50 ° C., and the completion of the curing reaction becomes an issue, and the ethylene-vinyl acetate copolymer resin (EVA) ) Foaming may occur during sheet bonding and wet heat test.

  In addition, there is a need to increase productivity by shortening the process time, but there is an issue of extending the curing reaction time, and from the standpoint of stable production, the completion of the isocyanate group curing reaction is also an issue. ing.

JP-A-10-218978 Japanese Patent Laid-Open No. 06-116542 Special table 2007-536422 gazette JP 2008-4691 A JP 2007-136911 A JP 2010-263193 A JP 2012-142349 A

The present invention has been made in order to solve such problems, and the problems are excellent in curing reactivity, excellent in adhesion after curing reaction and durability after curing reaction, preferably excellent in weather resistance. It is providing the solar cell back surface protection sheet and solar cell module which use the resin composition for laminated sheet joining, and the resin composition for laminated sheet joining.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above-mentioned goal can be achieved by the following laminated sheet bonding resin composition, and further completes the present invention by the sheet bonding resin composition. It came to.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention provides a copolymer (A),
A resin composition for joining laminated sheets comprising a reactive compound (B) having a functional group capable of reacting with an active hydrogen group (hereinafter referred to as “reactive functional group”),
The copolymer (A) has an activity of 0.01 to 10 parts by weight of an α, β-unsaturated compound (a-1) having a functional group selected from the group consisting of a carboxyl group, an amino group, and an amide group; [Alpha], [beta] -unsaturated compound (a-2) having a hydrogen group (excluding those which are (a-1)) 0.01-20 parts by weight, and other copolymerizable [alpha], [beta] -unsaturated compounds (A-3) A resin composition for joining laminated sheets, which is obtained by copolymerizing 70 to 99.98 parts by weight (excluding those which are (a-1) and (a-2)). About.

  Furthermore, the present invention relates to the above-mentioned resin composition for joining laminated sheets, wherein the active hydrogen group in the α, β-unsaturated compound (a-2) is a hydroxyl group.

  Furthermore, the present invention is characterized in that the copolymer (A) has a number average molecular weight of 1,000 to 500,000 and a molecular weight distribution (weight average molecular weight / number average molecular weight) of 2.0 to 8. The above-mentioned resin composition for joining laminated sheets.

  Furthermore, the present invention relates to the above-mentioned resin composition for joining laminated sheets, wherein the reactive compound (B) is polyisocyanate (b-1).

  Furthermore, the present invention is characterized in that the polyisocyanate (b-1) is an aliphatic polyisocyanate (b-1-1) and / or an alicyclic polyisocyanate compound (b-1-2). The present invention relates to a resin composition for bonding laminated sheets.

  Furthermore, the present invention provides an equivalent ratio of the active hydrogen group contained in the copolymer (A) and the reactive functional group contained in the reactive compound (B) (the reactive functional group of the reactive compound (B)). The equivalent of group] / [equivalent of active hydrogen group in copolymer (A)]) is in the range of 0.2 to 10. The present invention relates to the laminated sheet bonding resin composition described above.

  Furthermore, the present invention relates to an α, β-unsaturated compound in which 0.1% by weight to 50% by weight in 100% by weight of the α, β-unsaturated compound (a-3) has a cyclic structure having two or more rings. It is a-3-1) It is related with said joining resin composition for laminated sheets characterized by the above-mentioned.

  Furthermore, this invention contains 0.1-5 weight part of silane coupling agents (C) with respect to 100 weight part of copolymers (A), Said laminated sheet bonding resin composition characterized by the above-mentioned. About.

  Furthermore, this invention relates to the laminated body formed by laminating | stacking said resin composition for laminated sheet bonding on a film.

  Furthermore, this invention relates to the solar cell back surface protection sheet which uses said resin composition for laminated sheet joining.

Furthermore, this invention relates to the solar cell module formed using said solar cell back surface protection sheet.

By using the resin composition for bonding laminated sheets of the present invention, a curing reaction time can be shortened, and a laminated sheet that can be stably produced with high productivity can be provided. Moreover, since it is the lamination sheet excellent in the adhesiveness after hardening reaction, and the durability after hardening reaction, the laminated sheet suitable for a solar cell back surface protection sheet and a solar cell module can be provided.

Hereinafter, preferred embodiments of the present invention will be described.

<Copolymer (A)>
The copolymer (A) of the present invention is selected from the group consisting of a carboxyl group, an amino group, and an amide group, which has an effect of promoting the catalytic effect of the curing reaction with the reactive group in the reactive compound (B). Α, β-unsaturated compound (a-1) having a functional group and α, β-unsaturated compound (a) having an active hydrogen group capable of undergoing a curing reaction with the reactive group in reactive compound (B) -2) (except for those that are (a-1)) and α, β-unsaturated compounds (a-3) (except those that are (a-1) and (a-2)) Is a copolymer obtained by copolymerization.

  The number average molecular weight of the copolymer (A) is preferably from 1,000 to 500,000, and preferably from 5,000 to 200,000 in order to ensure both the coating suitability of the resin composition for bonding laminated sheets and the cohesive strength of the resin. It is preferable that it is 10000-150,000. If the number average molecular weight is less than 1000, the cohesive strength of the resin may be insufficient and the adhesive strength may be reduced. If the number average molecular weight is 500,000 or more, the viscosity of the copolymer (A) is high and the coating property is deteriorated. May end up. A number average molecular weight in the range of 10,000 to 150,000 makes it easy to achieve a balance between cohesive force and viscosity.

  The molecular weight distribution (weight average molecular weight / number average molecular weight) of the copolymer (A) is preferably in the range of 2.0 to 8.0, more preferably 3 to 6. If the molecular weight distribution (weight average molecular weight / number average molecular weight) is less than 2.0, the low molecular weight component is small, so the adhesion to the film during lamination may be reduced, and the molecular weight distribution (weight average molecular weight / number). When the average molecular weight) exceeds 8.0, thixotropy is high, and unevenness may occur during coating, resulting in poor appearance of the coating film.

The copolymer (A) has a glass transition point (hereinafter referred to as Tg) of the copolymer (A) from the balance of adhesion to the film during lamination and the cohesive strength of the resin composition for bonding laminated sheets. It is preferable to adjust to the range of 50-30 degreeC, -30-20 degreeC is more preferable, and -15-15 degreeC is further more preferable. When Tg is less than −50 ° C., the cohesive force of the laminated sheet bonding resin composition may be insufficient and the adhesive strength may be reduced. When the Tg exceeds 30 ° C., there is no tack of the laminated sheet bonding resin composition. In some cases, the adhesion to the film during lamination may be reduced.
If the Tg of a homopolymer that can be formed from each monomer that is a constituent component of the copolymer (A) is known, the copolymer is based on the Tg of each homopolymer and the constituent ratio of each monomer. The Tg of the polymer (A) can be determined theoretically.

For example, Tg can be theoretically calculated by the following FOX equation.
<FOX type> 1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wi / Tgi + ... + Wn / Tgn
[In the above FOX formula, the glass transition temperature of the homopolymer of each monomer constituting the polymer composed of n types of monomers is Tgi (K), the mass fraction of each monomer is Wi, and (W1 + W2 + ... + Wi +... Wn = 1). ]

The α, β-unsaturated compound (a-1) is a α, β-unsaturated compound (a-1) having a functional group such as a carboxyl group, an amino group, and an amide group that promotes the catalytic effect of the curing reaction of the reactive functional group of the reactive compound (B). A β-unsaturated compound is used, and among them, a carboxyl group and an amide group are more preferable. A copolymer using an α, β-unsaturated compound containing a carboxyl group and an amide group has a large effect of enhancing the interaction between the resins, and can also improve the cohesive strength of the coating film.
By incorporating these α, β-unsaturated compounds into the copolymer (A), it is possible to change the nucleophilicity and electrophilicity of the resin composition for joining laminated sheets. Then, the following effects are expected.

その中で、カルボキシル基は、イソシアネート基の共鳴を、Ｎ＝Ｃ⁺−Ｏ^-へ平衡を移動させることで、活性水素との硬化反応を促進し、アミノ基およびアミド基は、Ｎ^-−Ｃ⁺＝Ｏへ平衡を移動させることで、活性水素との硬化反応を促進すると考えられる。 It is known that the isocyanate group exhibits a resonance structure as represented by the general formula (1).

Among them, the carboxyl group promotes the curing reaction with active hydrogen by shifting the resonance of the isocyanate group to N = C ⁺ —O ⁻ , and the amino group and the amide group are N ⁻ —C ^It is considered that the curing reaction with active hydrogen is promoted by moving the equilibrium to ⁺ = O.

  It is preferable that 0.01 to 10% by weight of α, β-unsaturated compound (a-1) is contained in 100% by weight of α, β-unsaturated compound used for copolymerization of copolymer (A). More preferably, it is contained in an amount of 1 to 5% by weight, more preferably 0.2 to 2% by weight. If the amount is less than 0.01% by weight, the catalytic effect may not be obtained, and the curing reaction of the reactive compound (B) may not be completed. If the amount is more than 10% by weight, the catalytic effect is too high. The curing reaction may proceed immediately after the addition of the reactive compound (B) described later, causing a problem in pot life. In the range of 0.2 to 2% by weight, it is easy to achieve both a catalytic effect and a pot life.

Among the α, β-unsaturated compounds (a-1) having a functional group selected from the group consisting of a carboxyl group, an amino group, and an amide group, as the α, β-unsaturated compound containing a carboxyl group,
For example, (2-methyl) propenoic acid [propenoic acid and 2-methylpropenoic acid are collectively referred to as “(2-methyl) propenoic acid”. The same applies below. ], 2-methylenesuccinic acid, propylene-1,2-dicarboxylic acid, 2-butenedicarboxylic acid, 2-butenoic acid, 4-ethenylbenzoic acid, phthalic acid-2-hydroxyethyl-2-((2-methyl) 2-propenyloxy) ethyl ester [phthalic acid-2-hydroxyethyl-2-propenyloxy) ethyl ester and phthalic acid-2-hydroxyethyl-2-methyl-2-propenyloxy) ethyl ester -2-Hydroxyethyl-2-((2-methyl) 2-propenyloxy) ethyl ester ". The same applies below. ], Tetrahydrophthalic acid-2-hydroxyethyl-2-((2-methyl) 2-propenyloxy) ethyl ester, hexahydrophthalic acid-2-hydroxyethyl-2-((2-methyl) 2-propenyl Examples include carboxy group-containing α, β-unsaturated compounds such as oxy) ethyl ester and succinic acid-2-hydroxyethyl-2-((2-methyl) 2-propenyloxy) ethyl ester.

As an α, β-unsaturated compound containing an amino group,
For example, N-methylaminoethyl (2-methyl) propenoate, N-tributylaminoethyl (2-methyl) propenoate, N, N-dimethylaminoethyl (2-methyl) propenoate, (2-methyl) propenoic acid Amino group-containing (2-methyl) propenoic acid esters having a chain amino group such as N, N-diethylaminoethyl;

  For example, containing a cyclic amino group having one nitrogen atom such as morpholinoethyl (2-methyl) propenoate, pentamethylpiperidinyl (2-methyl) propenoate, tetramethylpiperidinyl (2-methyl) propenoate ( 2-methyl) propenoic acid esters;

  For example, 2- [2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxyethylphenyl] -2H-benzotriazole [, 2- [2′-hydroxy-5′-propane-2- [Enoyloxyethylphenyl] -2H-benzotriazole and 2- [2′-hydroxy-5′-2-methyl-2-propane-2-enoyloxyethylphenyl] -2H-benzotriazole together with “ , 2- [2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxyethylphenyl] -2H-benzotriazole ”. The same applies below. ], 2- [2'-hydroxy-5 '-(2-methyl) propane-2-enoyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-( 2-Methyl) propane-2-enoyloxypropylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxypropylphenyl] -5-chloro -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(2-methyl) propane-2-enoyloxyethylphenyl] -2H-benzotriazole, (2-methyl) Propenoic acid-3- (2H-1,23-benzotriazol-2-yl) -4-hydroxyphenethyl, 2- (2′-hydroxy-3′-tert-butyl-5 ′-(2-methyl) Having a cyclic amino group with a benzene ring having three-2- enoyl oxyethyl phenyl) -5-chloro -2H- benzotriazole benzotriazole nitrogen atom of the (2-methyl) propenoic acid derivatives;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methylphenyl) ) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2 -Hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- ( 2- (2-Methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2- (2-methyl) ) Propan-2-enoyloxyethoxy)]-S-to Azine, 2,4-bis (2,4-dimethoxyphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2, 4-Bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis ( 2,4-diethoxylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2,4 -Diethylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-diamino-6-methacryloyloxyethyl-s -Triazine nitrogen sources such as triazine The having three having cyclic amino group (2-methyl) propenoic acid derivatives;

For example, 2-ethenylpyridine, 4-ethenylpyridine, 2-ethenylpiperazine, 2-ethenylpyrimidine, N-ethenylimidazole, 4-ethenylpiperazine, ethenyloxazole, N-ethenylcarbazole, N- Ethenylindole, N-ethenylpyrrolidene, methylethenylimidazolium chloride, 2,4-diamino-6-ethenyl-s-triazine, 2-ethenylpyrrole, 1-benzyl-2-ethenyl-1H-pyrrole, 2- (1-pyrrolyl) ethyl vinyl ether, 1- (4-vinylphenyl) -1H-pyrrole-2,5-dione, 2-ethenylthiophene, 2- (2-nitroethenyl) thiophene, 5-formyl-2- Ethenylthiophene, 3-bromo-4- (1-iodo-2-perfluorobutyl-ethenyl) Offene, 3-bromo-4- (1-bromo-2-pentafluorosulfanyl-ethenyl) -thiophene, 5- [2- [4-diphenylaminophenyl-phenyl] -ethenyl] -phenyl] -thiophen-2-rubo Cyclic amino group-containing heterocyclic ethenyls having a nitrogen atom such as aldehyde, bis (2-diphenylethenyl) thiophene, 4- [2- (4-diphenylamino-phenyl) -ethenyl] -benzaldehyde, diethenylethylurea ;
And an α, β-unsaturated compound containing an amino group such as

As an α, β-unsaturated compound containing an amide group,
For example, (2-methyl) 2-propenamide, 2-methylprop-2-enoylamide, N, N-dimethyl-2-propenamide, N, N-diethyl-2-propenamide, N-methoxymethyl-2-propene Amide, N-ethoxymethyl (2-methyl) propenamide, N- (n-, iso-) butoxymethyl (2-methyl) propenamide, N-methoxyethyl (2-methyl) propenamide, N-ethoxyethyl ( 2-methyl) propenamide, N- (n-, iso-) butoxyethyl (2-methyl) propenamide, N- [3- (N ′, N′-dimethylamino) propyl] -2-propenamide, N -Isopropyl-2-propenamide, N-ethenylmethaneamide, N-ethenylacetamide, N-ethenyl-α-methylthioacetoa Ethenyls containing aliphatic amide groups such as amide and N-ethenylformamide;

For example, cyclic amide group-containing ethenyls such as 4-propenoylmorpholine, N-ethenyl-2-pyrrolidone, N-ethenyl-2-azehan-2-one;
And an amide group-containing α, β-unsaturated compound.

Other,
For example, 2-ethenylpyridine, 4-ethenylpyridine, 2-ethenylpiperazine, 2-ethenylpyrimidine, N-ethenylimidazole, 4-ethenylpiperazine, ethenyloxazole, N-ethenylcarbazole, N- Ethenylindole, N-ethenylpyrrolidene, methylethenylimidazolium chloride, 2,4-diamino-6-ethenyl-s-triazine, 2-ethenylpyrrole, 1-benzyl-2-ethenyl-1H-pyrrole, 2- (1-pyrrolyl) ethyl vinyl ether, 1- (4-vinylphenyl) -1H-pyrrole-2,5-dione, 2-ethenylthiophene, 2- (2-nitroethenyl) thiophene, 5-formyl-2- Ethenylthiophene, 3-bromo-4- (1-iodo-2-perfluorobutyl-ethenyl) Offene, 3-bromo-4- (1-bromo-2-pentafluorosulfanyl-ethenyl) -thiophene, 5- [2- [4-diphenylaminophenyl-phenyl] -ethenyl] -phenyl] -thiophen-2-rubo Nitrogen atom-containing heterocyclic ethenyls such as aldehyde, bis (2-diphenylethenyl) thiophene, 4- [2- (4-diphenylamino-phenyl) -ethenyl] -benzaldehyde, diethenylethylurea;

For example, 3-pyrroline-2,5-dione, 1-methyl-1H-pyrrole-2,5-dione, 1-ethyl-1H-pyrrole-2,5-dione, 1-propyl-1H-pyrrole-2, 5-dione, 1-butyl-1H-pyrrole-2,5-dione, 1-octyl-1H-pyrrole-2,5-dione, 1-dodecyl-1H-pyrrole-2,5-dione, 1-stearyl- Nitrogen-containing 3-pyrroline-2,5 such as 1H-pyrrole-2,5-dione, 1-phenyl-1H-pyrrole-2,5-dione, 1-cyclohexyl-1H-pyrrole-2,5-dione -Dione derivatives;
And a nitrogen atom-containing α, β-unsaturated compound that has the same catalytic activity as that of an amino group or an amide group.

  Among these, as the α, β-unsaturated compound (a-1), (2-methyl) propenoic acid, 2-methylenesuccinic acid, 2-ethenylpyridine, (2- Methyl) pentamethylpiperidinyl propenoate, 2- [2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxyethylphenyl] -2H-benzotriazole, 2,4-diphenyl-6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, (2-methyl) propenoic acid N, N-dimethylaminoethyl, (2-methyl) N, N-diethylaminoethyl propenoate and (2-methyl) 2-propenamide are preferred, and among these, (2-methyl) propenoic acid, (2-methyl) 2-propenamide, (2-methyl) ) Propenoic acid N, N-dimethylaminoethyl has high catalytic efficiency, further preferred.

The α, β-unsaturated compound (a-2) having an active hydrogen group has an active hydrogen group capable of undergoing a curing reaction with the reactive functional group of the reactive compound (B) (provided that ( excluding a-1)). The α, β-unsaturated compound (a-2) undergoes a curing reaction with the reactive functional group of the reactive compound (B), improves the cohesive strength of the laminated sheet bonding resin composition, and is stable without causing cohesive failure. Heat resistance and heat-and-moisture resistance can be imparted by expressing the adhesive force or by increasing the molecular weight of the laminated sheet-bonding resin composition by a curing reaction.
Examples of the active hydrogen group used in the α, β-unsaturated compound (a-2) include a hydroxyl group, a sulfonic acid group, a phosphonyl group, and an active methylene group. Among them, a hydroxyl group is preferably contained.

Among the α, β-unsaturated compound (a-2) having an active hydrogen group, the hydroxyl group-containing monomer is
For example, 2-hydroxyethyl (2-methyl) propenoate, 1-hydroxypropyl (2-methyl) propenoate, 2-hydroxypropyl (2-methyl) propenoate, 2-methoxyethyl (2-methyl) propenoate, (2-methyl) propenoic acid 2-ethoxyethyl, (2-methyl) propenoic acid 2-hydroxybutyl, (2-methyl) propenoic acid 4-hydroxybutyl (2-methyl) propenoic acid polyethene oxide, (2-methyl) ) Hydroxyl-containing (2-methyl) propenoic acid esters such as propenoic acid polypropene oxide;

  For example, (2-methyl) propenoic acid polyethene oxide, (2-methyl) propenoic acid polypropene oxide, (2-methyl) propenoic acid polytetramethine oxide, (2-methyl) propenoic acid polyhexamethine oxide methyl, etc. Polyalkylene glycol-containing (2-methyl) propenoic acid derivatives;

For example, 2-hydroxy-4- [2- (2-methyl) propane-2-enoyloxy] ethoxydiphenylmethanone, 2-hydroxy-4- [2-((2-methyl) propane-2-enoyloxy) butoxydiphenyl Methanone, 2,2′-dihydroxy-4- [2- (2-methyl) propane-2-enoyloxy] ethoxydiphenylmethanone, 2-hydroxy-4- [2- (2-methyl) propan-2-enoyloxy ] Diphenylmethanone-based hydroxyl group-containing (2-methyl) propenoic acid derivatives such as ethoxy-4 '-(2-hydroxyethoxy) diphenylmethanone;
And other hydroxyl-containing α, β-unsaturated compounds.

Among (a-2), as the α, β-unsaturated compound containing a sulfonic acid group,
For example, sulfones such as ethenylbenzenesulfonic acid, ethenylsulfonic acid, allylsulfonic acid, allyloxybenzenesulfonic acid, methallylsulfonic acid, methallyloxybenzenesulfonic acid, alkenyl group-containing sulfonic acid compounds such as vinyl sulfate, etc. Examples include acid group-containing α, β-unsaturated compounds.

  For example, 2- (1,3-dioxobutoxy) ethyl (2-methyl) propenoate, 2- (1,3-dioxobutoxy) propyl (2-methyl) propenoate, 3- (2-methyl) propenoate 3- ( 1,3-dioxobutoxy) propyl, 2- (1,3-dioxobutoxy) butyl (2-methyl) propenoate, 3- (1,3-dioxobutoxy) butyl (2-methyl) propenoate, (2- Examples include α, β-unsaturated compounds containing active methylene groups such as β-diketone structure-containing (2-methyl) propenoic acid esters such as methyl) propenoate 4- (1,3dioxobutoxy) butyl.

Examples of the phosphonyl group-containing monomer in (a-2) include (2-methyl) propenoic acid acid phosphooxyethyl, (2-methyl) propenoic acid acid phosphooxypropyl, and (2-methyl) propene. Acid acid phosphooxybutyl, (2-methyl) propenoic acid-3-chloro-2-acid phosphooxyethyl, (2-methyl) propenoic acid-3-chloro-2-acid phosphooxypropyl, (2-methyl) propene Acid-3-chloro-2-acid phosphooxybutyl, (2-methyl) propenoic acid phosphooxyethene oxide (ethene oxide addition moles: 4 to 10), (2-methyl) propenoic acid phosphooxypropene oxide ( (2-Meth) containing phosphonyl groups such as propene oxide addition moles: 4 to 10) Examples include α, β-unsaturated compounds containing a phosphonyl group such as (til) propenoic acid esters.

  Among these, α, β-unsaturated compounds having a hydroxyl group are preferable, and among them, 2-hydroxyethyl (2-methyl) propenoate and 4-hydroxybutyl (2-methyl) propenoate are preferable.

  The α, β-unsaturated compound (a-2) having an active hydrogen group is contained in 0.01 to 20% by weight in 100% by weight of the α, β-unsaturated compound used for copolymerization of the copolymer (A). The content is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight. When the content is less than 0.01% by weight, the effect of improving the molecular weight due to the curing reaction when the reactive compound (B) described below is added and blended is difficult to obtain, and the cohesive force of the resin composition for bonding laminated sheets is insufficient. In some cases, the strength cannot be obtained. When the amount is more than 20% by weight, the shrinkage due to the curing reaction becomes remarkable, and the adhesive strength may not be obtained. A range of 0.2 to 5% by weight is more preferable because the effect of improving the molecular weight is high and curing shrinkage hardly occurs.

  In addition, α, β-unsaturated compounds copolymerizable with (a-1) and (a-2) are used as the copolymerizable α, β-unsaturated compound (a-3). Among these, an α, β-unsaturated compound (a-3-1) having a cyclic structure of two or more rings is more preferably used.

  The α, β-unsaturated compound (a-3-1) having a cyclic structure of two or more rings is characterized by having an aliphatic or aromatic cyclic structure of two or more rings, and the polarity of the resin Used for control. When used as a laminated sheet bonding resin composition by copolymerizing an α, β-unsaturated compound (a-3-1) having a cyclic structure of two or more rings, polyethylene or polyfluoride having a low polarity is used. While improving the adhesive force with nonpolar base materials, such as vinylidene, the water absorption of resin can be lowered | hung and the adhesive force fall at the time of a wet heat test can be suppressed.

  As a compound suitably used for (a-3-1), for example, (2-methyl) propenoic acid iso-bonyl, (2-methyl) propenoic acid 2-oxo-1,2-diphenylethyl, (2- Methyl) propenoic acid-p-cumylphenol, (2-methyl) propenoic acid dicyclopentenyl, (2-methyl) propenoic acid-1,4-dioxaspiro [4,5] -dec-2-ylmethyl ester, ( 2-methyl) propenoic acid dicyclopentanyloxyethyl, (2-methyl) propenoic acid tricyclopentenyl, (2-methyl) propenoic acid-1-adamantyl, (2-methyl) propenoic acid-2-methyl-2- (2-methyl) propenoic acid cyclic esters such as adamantyl and (2-methyl) propenoic acid-2-ethyl-2-adamantyl;

  Ethenylbenzenes such as ethenylnaphthalene and ethenylanthracene:

Di (2-methyl) propenoic acid tricyclodecane dimethylol, di (2-methyl) propenoic acid tricyclodecane dimethylol dicaprolactonate, di (2-methyl) propenoic acid-2,2-bis (hydroxyphenyl) Tetraethene oxide adduct of propane, di (2-methyl) propenoic acid-2,2-bis (hydroxyphenyl) methane tetraethene oxide adduct, di (2-methyl) propenoic acid-4,4′-sulfonyldi Tetraethene oxide adduct of phenol, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) propane tetraethene oxide adduct, di (2-methyl) propenoic acid-water-added 2,2 -Tetraethene oxide adduct of bis (hydroxyphenyl) methane, di (2-methyl) propenoic acid-water addition , 2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water addition 2,2-bis (hydroxyphenyl) methane, di (2-methyl) propenoic acid-2,2-bis (hydroxyphenyl) Propylene tetraethylene oxide adducts-dicaprolactonate, di (2-methyl) propenoic acid-2,2-bis (hydroxyphenyl) methane tetraethene oxide adducts-dicaprolactonate, etc. (2-methyl) Propenoic acid-based bifunctional derivatives;
And α, β-unsaturated compounds having an aliphatic or aromatic ring structure of two or more rings. Is mentioned.

  Among other copolymerizable α, β-unsaturated compounds (a-3), α, β-unsaturated compounds (a-3-1) having an aliphatic or aromatic cyclic structure of two or more rings ) In the α, β-unsaturated compound (a-3) 100% by weight of the α, β-unsaturated compound (a-3), the α, β-unsaturated compound (a- The content of 3-1) is preferably 0.1 to 50% by weight, and more preferably 10 to 30% by weight. If it is less than 0.1% by weight, it is difficult to obtain the effect of lowering the polarity of the copolymer (A), and the adhesive force with the nonpolar substrate may not be improved. ) And (a-2), the copolymerization deteriorates and the appearance of the laminated sheet bonding resin composition becomes poor due to white turbidity.

  Among the α, β-unsaturated compounds (a-3), other copolymerizable α, β-unsaturated compounds (a-3-2) other than (a-3-1) include (a-1 And α and β unsaturated compounds copolymerizable with (a-2).

  Examples of the α, β-unsaturated compound (a-3-2) include, for example, methyl (2-methyl) propenoate, ethyl (2-methyl) propenoate, 1-propyl (2-methyl) propenoate, 2-propyl (2-methyl) propenoate, n-butyl (2-methyl) propenoate, sec-butyl (2-methyl) propenoate, iso-butyl (2-methyl) propenoate, (2-methyl) propene Tert-butyl acid, n-amyl (2-methyl) propenoate, iso-amyl (2-methyl) propenoate, n-hexyl (2-methyl) propenoate, 2-ethylhexyl (2-methyl) propenoate, 2-Methyl) propenoate n-octyl, (2-methyl) propenoate iso-octyl, (2-methyl) propenoate n-nonyl, (2-methyl) propenoate iso-noni (2-methyl) propenylate decyl, (2-methyl) propenoate dodecyl, (2-methyl) propenoate octadecyl, (2-methyl) propenoate lauryl, (2-methyl) propenoate stearyl (2- Methyl) propenoic acid alkyl esters;

  For example, (2-methyl) propenoic acid cyclic esters such as cyclohexyl (2-methyl) propenoate and benzyl (2-methyl) propenoate;

  For example, (2-methyl) propenoic acid polyethene oxide methyl, (2-methyl) propenoic acid polyethene oxide ethyl, (2-methyl) propenoic acid polyethene oxide propyl, (2-methyl) propenoic acid polyethene oxide butyl, (2-methyl) propenoate polyethene oxide pentyl, (2-methyl) propenoate polyethene oxide phenyl, (2-methyl) propenoate polyethene oxide phenyl nonyl, (2-methyl) propenoate polyethene oxide phenyl paracumyl , (2-methyl) propenoic acid polypropene oxide methyl, (2-methyl) propenoic acid polypropene oxide ethyl, (2-methyl) propenoic acid polypropene oxide propyl, (2-methyl) propenoic acid polypropene oxide butyl (2-methyl) propenoic acid polypropene oxide n-pentyl, (2-methyl) propenoic acid polypropene oxide phenyl, (2-methyl) propenoic acid polypropene oxide phenylnonyl, (2-methyl) propenoic acid polypropene oxide phenyl Contains alkoxypolyalkylene glycols such as paracamyl, polytetramethine oxide methyl (2-methyl) propenoate, polytetramethine oxide phenyl (2-methyl) propenoate, polyhexamethine oxide methyl (2-methyl) propenoate (2 -Methyl) propenoic acid derivatives;

  For example, allyl (2-methyl) propenoate, 1-methylallyl (2-methyl) propenoate, 2-methylallyl (2-methyl) propenoate, 1-butenyl (2-methyl) propenoate, (2-methyl) propene 2-butenyl acid, 3-butenyl (2-methyl) propenoate, 1,3-methyl-3-butenyl (2-methyl) propenoate, 2-chloroallyl (2-methyl) propenoate, (2-methyl) propene Acid 3-chloroallyl, (2-methyl) propenoic acid-o-allylphenyl, (2-methyl) propenoic acid 2- (allyloxy) ethyl, (2-methyl) propenoic acid allyl lactyl, (2-methyl) propenoic acid citronellyl, (2-methyl) geranyl propenoate, (2-methyl) rosinyl propenoate, cinnamil (2-methyl) propenoate, (2-methyl) (2) (2-methyl) propenoic acid esters further containing an unsaturated group such as ethenyl propenoate;

For example, (2-methyl) propenoic acid perfluoromethyl, (2-methyl) propenoic acid perfluoroethyl, (2-methyl) propenoic acid perfluoropropyl, (2-methyl) propenoic acid perfluorobutyl, (2-methyl) ) Perfluorooctyl propenoate, trifluoromethyl methyl (2-methyl) propenoate, 2-trifluoromethyl ethyl (2-methyl) propenoate, diperfluoromethyl methyl (2-methyl) propenoate, (2-methyl) ) 2-perfluoroethylethyl propenoate, 2-perfluoromethyl-2-perfluoroethylmethyl (2-methyl) propenoate, (2-methyl) propenoic acid triperfluoromethylmethyl, (2-methyl) propenoic acid 2-perfluoroethyl-2-perfluorobutylethyl, (2-methyl) 2-perfluorohexylethyl lopentate, 2-perfluorodecylethyl (2-methyl) propenoate, 2-perfluorohexadecylethyl (2-methyl) propenoate, (2-methyl) propenoic acid-2,6- Dibromo-4-butylphenyl, (2-methyl) propenoic acid-2,4,6-tribromophenoxyethyl, (2-methyl) propenoic acid-2,4,6-tribromophenol ethene oxide adduct (ethene oxide) Halogen-containing (2-methyl) propenoic acid alkyl esters such as addition mole number: 4 to 12);

  For example, glycidyl (2-methyl) propenoate, (2-methyl) propenoate (3,4-epoxycyclohexyl) methyl, (2-methyl) propenoate (3-methyl-3-oxetanyl) methyl, (2-methyl) ) Oxygen atom-containing heterocycle-containing (2-methyl) propenoates such as tetrahydrofurfuryl propenoate;

  For example, 3- (2-methylpropane-2-enoyloxypropyl) trimethoxysilane, 3- (2-methylpropane-2-enoyloxypropyl) triethoxysilane, 3- (2-methylpropan-2- Enoyloxypropyl) triisopropoxysilane, 3- (2-methylpropane-2-enoyloxypropyl) methyldimethoxysilane, 3- (2-methylpropane-2-enoyloxypropyl) methyldiethoxysilane, 3 -(2-methyl) propenoic acid esters containing alkoxysilyl groups such as (propane-2-enoyloxypropyl) trimethoxysilane;

  For example, as a bifunctional monomer, di (2-methyl) propenoic acid ethene oxide, di (2-methyl) propenoic acid triethene oxide, di (2-methyl) propenoic acid tetraethene oxide, di (2-methyl) ) Propenoic acid polyethene oxide, di (2-methyl) propenoic acid propene oxide, di (2-methyl) propenoic acid dipropene oxide, di (2-methyl) propenoic acid tripropene oxide, di (2-methyl) propenoic acid Polypropene oxide, di (2-methyl) propenoic acid butene oxide, di (2-methyl) propenoic acid pentenoxide, di (2-methyl) propenoic acid 2,2-dimethylpropyl, di (2-methyl) propenoic acid hydroxy Pivalyl hydroxypivalate (commonly called Manda), di (2-methyl) propenoic acid hydride Roxypivalyl hydroxypivalate dicaprolactonate, 1,6-hexanediol di (2-methyl) propenoate, 1,2-hexanediol di (2-methyl) propenoate, di (2-methyl) propenoate 1 , 5-hexanediol, di (2-methyl) propenoic acid 2,5-hexanediol, di (2-methyl) propenoic acid 1,7-heptanediol, di (2-methyl) propenoic acid 1,8-octanediol Di (2-methyl) propenoic acid 1,2-octanediol, di (2-methyl) propenoic acid 1,9-nonanediol, di (2-methyl) propenoic acid 1,2-decanediol, di (2- Methyl) propenoic acid 1,10-decanediol, di (2-methyl) propenoic acid 1,2-decanediol, di (2-methyl) propenoic acid 1,12-dodecane All, di (2-methyl) propenoic acid 1,2-dodecanediol, di (2-methyl) propenoic acid 1,14-tetradecanediol, di (2-methyl) propenoic acid 1,2-tetradecanediol, di (2 -Methyl) propenoic acid 1,16-hexadecanediol, di (2-methyl) propenoic acid 1,2-hexadecanediol, di (2-methyl) propenoic acid 2-methyl-2,4-pentanediol, di (2- Methyl) propenoate 3-methyl-1,5-pentanediol, di (2-methyl) propenoate 2-methyl-2-propyl-1,3-propanediol, di (2-methyl) propenoate 2,4- Dimethyl-2,4-pentanediol, di (2-methyl) propenoic acid 2,2-diethyl-1,3-propanediol, di (2-methyl) propenoic acid 2,2, 4-trimethyl-1,3-pentanediol, dimethyloloctane di (2-methyl) propenoate, 2-ethyl-1,3-hexanediol di (2-methyl) propenoate, di (2-methyl) propenoic acid 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol di (2-methyl) propenoate, 2-butyl-2-ethyl-1, di (2-methyl) propenoate, 3-propanediol, di (2-methyl) propenoic acid 2,4-diethyl-1,5-pentanediol, di (2-methyl) propenoic acid 1,2-hexanediol, di (2-methyl) propenoic acid 1 , 5-hexanediol, di (2-methyl) propenoic acid 2,5-hexanediol, di (2-methyl) propenoic acid 1,7-heptanediol, di (2-methyl) propenoic acid 1, Octanediol, 1,2-octanediol di (2-methyl) propenoate, 1,9-nonanediol di (2-methyl) propenoate, 1,2-decanediol di (2-methyl) propenoate, di (2-methyl) propenoic acid 1,10-decanediol, di (2-methyl) propenoic acid 1,2-decanediol, di (2-methyl) propenoic acid 1,12-dodecanediol, di (2-methyl) 1,2-dodecanediol propenoic acid, 1,14-tetradecanediol di (2-methyl) propenoate, 1,2-tetradecanediol di (2-methyl) propenoate, 1,16 di (2-methyl) propenoic acid -Hexadecanediol, di (2-methyl) propenoic acid-1,2-hexadecanediol, di (2-methyl) propenoic acid 2-methyl-2,4-pentane, (2-methyl) propenoic acid 3-methyl-1,5-pentanediol, di (2-methyl) propenoic acid 2-methyl-2-propyl-1,3-propanediol, di (2-methyl) propenoic acid 2 , 4-Dimethyl-2,4-pentanediol, 2,2-diethyl-1,3-propanediol di (2-methyl) propenoate, 2,2,4-trimethyl-1 di (2-methyl) propenoate , 3-pentanediol, dimethyloloctane di (2-methyl) propenoate, 2-ethyl-1,3-hexanediol di (2-methyl) propenoate, 2,5-dimethyl di (2-methyl) propenoate -2,5-hexanediol, 2-butyl-2-ethyl-1,3-propanediol di (2-methyl) propenoate, 2,4-diethyl-1,5-di (2-methyl) propenoate (2-methyl) propenoic acid bifunctional derivatives such as pentanediol, di (2-methyl) propenoic acid 1,1,1-trishydroxymethylethane;

  Trifunctional monomer glycerin tri (2-methyl) propenoate, tri (2-methyl) propenoic acid trimethylolpropane, tri (2-methyl) propenoic acid trimethylolpropane triethylene oxide, tri (2-methyl) Trimethylolpropane propenoate tricaprolactonate, trimethylolethane tri (2-methyl) propenoate, trimethylolhexane tri (2-methyl) propenoate, trimethyloloctane tri (2-methyl) propenoate, tri (2- Trifunctional (2) such as methyl) propenoic acid pentaerythritol, tri (2-methyl) propenoic acid 1,1,1-trishydroxymethylethane, tri (2-methyl) propenoic acid 1,1,1-trishydroxymethylpropane -Methyl) propenoic acid esters;

  Tetra (2-methyl) propenoic acid pentaerythritol, tetra (2-methyl) propenoic acid pentaerythritol tetracaprolactonate, tetra (2-methyl) propenoic acid diglycerin, tetra (2 -(Methyl) propenoic acid ditrimethylolpropane, tetra (2-methyl) propenoic acid ditrimethylolpropane tetracaprolactonate, tetra (2-methyl) propenoic acid ditrimethylolethane, tetra (2-methyl) propenoic acid ditrimethylolbutane, Tetra (2-methyl) propenoate ditrimethylolhexane, tetra (2-methyl) propenoate ditrimethyloloctane, tetra (2-methyl) propenoate dipentaerythritol, hexa (2-methyl) propenoate dipentaerythritol, hex (2-methyl) propenoic acid tripentaerythritol, hepta (2-methyl) propenoic acid tripentaerythritol, octa (2-methyl) propenoic acid tripentaerythritol, hepta (2-methyl) propenoic acid dipentaerythritol polyalkene oxide, etc. Polyfunctional (2-methyl) propenoic acid esters of

  For example, ethenyl phenyl pentyl ether, ethenyl phenyl hexyl ether, ethenyl phenyl heptyl ether, ethenyl phenyl octyl ether, ethenyl phenyl nonyl ether, ethenyl phenyl decyl ether, ethenyl phenyl undecyl ether, ethenyl phenyl dodecyl ether Ethenyl phenyl tridecyl ether, ethenyl phenyl tetradecyl ether, ethenyl phenyl pentadecyl ether, ethenyl phenyl hexadecyl ether, ethenyl phenyl heptadecyl ether, ethenyl phenyl octadecyl ether, ethenyl phenyl nonadecyl ether, Tenenylphenyl eicosyl ether, ethenylphenyl henecosyl ether, ethenylphenyl docosyl ether, ethenylphenyl Butyl butyl ether, ethenyl phenyl methyl pentyl ether, ethenyl phenyl methyl hexyl ether, ethenyl phenyl methyl heptyl ether, ethenyl phenyl methyl octyl ether, ethenyl phenyl methyl nonyl ether, ethenyl phenyl methyl decyl ether, ethenyl phenyl methyl ether Decyl ether, ethenyl phenyl methyl dodecyl ether, ethenyl phenyl methyl tridecyl ether, ethenyl phenyl methyl tetradecyl ether, ethenyl phenyl methyl pentadecyl ether, ethenyl phenyl methyl hexadecyl ether, ethenyl phenyl methyl heptadecyl ether, Ethenyl phenyl methyl octadecyl ether, ethenyl phenyl methyl nonadecyl ether, ethenyl phenyl methyl Lee waist ether, ethenyl phenylmethyl hen eicosyl ether, aromatic ethenyl ethers having a long-chain alkyl groups such as ethenyl phenylmethyl docosyl ether;

  For example, isopropenyl phenylmethyl butyl ether, isopropenyl phenyl methyl pentyl ether, isopropenyl phenyl methyl hexyl ether, isopropenyl phenyl methyl heptyl ether, isopropenyl phenyl methyl octyl ether, isopropenyl phenyl methyl nonyl ether, isopropenyl phenyl methyl decyl ether, Isopropenyl phenylmethyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl pentadecyl ether, isopropenyl phenyl methyl hexadecyl ether, isopropenyl phenyl Methyl heptadecyl ether, Isopropenyl phenyl having a long chain alkyl group such as sopropenyl phenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl henecosyl ether, isopropenyl phenyl methyl docosyl ether Kind;

  Hexyl 4-ethenylbenzenecarboxylate, octyl 4-ethenylbenzenecarboxylate, nonyl 4-ethenylbenzenecarboxylate, decyl 4-ethenylbenzenecarboxylate, dodecyl 4-ethenylbenzenecarboxylate, 4-ethenylbenzene Tetradecyl carboxylate, hexadecyl 4-ethenylbenzenecarboxylate, octadecyl 4-ethenylbenzenecarboxylate, eicosyl 4-ethenylbenzenecarboxylate, docosyl 4-ethenylbenzenecarboxylate, hexyl 4-isopropenylbenzenecarboxylate, 4 -Octyl isopropenylbenzenecarboxylate, nonyl 4-isopropenylbenzenecarboxylate, decyl 4-isopropenylbenzenecarboxylate, dodecyl 4-isopropenylbenzenecarboxylate, 4-isopropenylbenzenecarboxyl Ethenylbenzene having a long-chain alkyl group such as tetradecyl acid, hexadecyl 4-isopropenylbenzenecarboxylate, octadecyl 4-isopropenylbenzenecarboxylate, eicosyl 4-isopropenylbenzenecarboxylate, docosyl 4-isopropenylbenzenecarboxylate Carboxylate-based or isopropenylbenzenecarboxylic acid esters;

  For example, ethenylbenzene, α-isopropenylbenzene, β-isopropenylbenzene, 1-methylethenylbenzene, 2-methylethenylbenzene, 3-methylethenylbenzene, 1-butylethenylbenzene, 1-chloro- Aromatic ethenyls such as 4-isopropenylbenzene;

  For example, tetra (ethene oxide) ethenylphenyl ether, methyltetra (etheneoxide) ethenylphenylether, ethyltetra (etheneoxide) ethenylphenylether, propyltetra (etheneoxide) ethenylphenylether, n-butyltetra (etheneoxide) ) Ethenyl phenyl ether, n-pentyltetra (ethene oxide) ethenyl phenyl ether, tetra (propene oxide) ethenyl phenyl ether, methyl tetra (propene oxide) ethenyl phenyl ether, ethyl tetra (propene oxide) ethenyl phenyl ether, Propoxytetra (propene oxide) ethenyl phenyl ether, n-butyltetra (propene oxide) ethenyl phenyl ether, n Pentaxytetra (propene oxide) ethenyl phenyl ether, poly (ethene oxide) ethenyl phenyl ether, methyl poly (ethene oxide) ethenyl phenyl ether, ethyl poly (ethene oxide) ethenyl phenyl ether, poly (propene oxide) ethenyl phenyl Ether, methyl poly (propene oxide) ethenyl phenyl ether, ethyl poly (propene oxide) ethenyl phenyl ether, poly (ethene oxide) ethenyl benzyl ether, methyl poly (ethene oxide) ethenyl benzyl ether, ethyl poly (ethene oxide) ethenyl benzyl Ether, poly (propene oxide) ethenyl benzyl ether, methyl poly (propene oxide) ethenyl benzyl ether Ethyl poly (propene oxide) ethenyl benzyl ether, poly (ethene oxide) ethenyl phenyl ethyl ether, methyl poly (ethene oxide) ethenyl phenyl ethyl ether, ethyl poly (ethene oxide) ethenyl phenyl ethyl ether, poly (oxypropylene) vinyl phenyl Ethenylbenzenes having a long-chain polyalkene oxide moiety such as ethyl ether, methyl poly (propene oxide) ethenylphenyl ethyl ether, ethyl poly (propene oxide) ethenylphenyl ethyl ether;

  For example, poly (ethene oxide) isopropenyl phenyl ether, methyl poly (ethene oxide) isopropenyl phenyl ether, ethyl poly (ethene oxide) isopropenyl phenyl ether, poly (propene oxide) isopropenyl phenyl ether, methyl poly (propene oxide) isopropenyl phenyl Ether, ethyl poly (propene oxide) isopropenyl phenyl ether, poly (ethene oxide) isopropenyl benzyl ether, methyl poly (ethene oxide) isopropenyl benzyl ether, ethyl poly (ethene oxide) isopropenyl benzyl ether, poly (propene oxide) isopropenyl benzyl ether Ether, methylpoly (propene oxide) isopropenylbenzyl Isopropenyl compound having a polyalkene oxide moiety, such as ether;

  For example, fluorine-containing ethenyls such as perfluoroethene, perfluoropropene, perfluoro (propyl ethenyl ether), etenylidene fluoride;

  For example, ethenyls containing trialkyloxysilyl groups such as ethenyltrimethoxysilane and ethenyltriethoxysilane;

  For example, ethenyl ethanoate, ethenyl propanoate, ethenyl pivalate, ethenyl benzenecarboxylate, ethenyl 3-phenyl-2-propenoate, diallyl cis-butenedioate, diallyl 2-methylidene succinate, (E) -but-2- Ethenyl esters such as ethenyl enoate, (Z) -octadec-9-ethenoate ethenyl, (9Z, 12Z, 15Z) -octadeca-9,12,15-trienoate ethenyl;

  For example, ethenyl containing nitrile groups such as 2-propenenitrile, 2-methyl-2-propenenitrile, 2-cyanoethyl (2-methyl) propenoate;

  For example, glycidyl group-containing ethenyl esters such as glycidyl cinnamate, allyl glycidyl ether, ethenylcyclohexene monooxirane, 1,3-butadiene monooxirane;

  For example, ethene, propene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetraconten And alkenes such as mixtures thereof;

  For example, dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;

  Examples include chloroethene, 1,1-dichloroethene, allyl chloride, allyl alcohol, and the like, but are not particularly limited thereto.

  Also, for example, a copolymer of an α, β-unsaturated compound having at least one prop-2-enoyl group and 2-methylprop-2-enoyl group in the molecule, wherein α , Β-unsaturated double bonds, high molecular weight type polymerizable copolymers, so-called macromonomers are also included.

  These may be used alone or in combination of two or more, and are not particularly limited.

  Other copolymerizable α, β-unsaturated compound (a-3) contains 70 to 99.98% by weight in 100% by weight of α, β-unsaturated compound used for copolymerization of copolymer (A). It is preferable. If it is less than 70% by weight, the amount of addition of (a-1) and (a-2) increases, and it may be difficult to adjust the curing reaction rate and the curing reaction amount. If it exceeds, the α, β-unsaturated compounds (a-1) and (a-2) involved in the curing reaction are small, the effect of the curing reaction is thin, and the adhesive force may be insufficient.

Next, the polymerization initiator used for the synthesis of the copolymer (A) will be described.
The copolymer (A) in the present invention is 0.001 to 20 weights with respect to a total of 100 weight parts of various α, β-unsaturated compounds (a-1) to (a-3) as described above. It is synthesized by a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization using a part of the polymerization initiator. Preferably, it is synthesized by solution polymerization.

Examples of polymerization initiators include 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutanenitrile), 1,1′-azobis (cyclohexane 1-carbonitrile) 2,2′-azobis (2,4-dimethylpentalonitrile), 2,2′-azobis (2,4-dimethyl-4-methoxypentalonitrile) and dimethyl 2,2′-azobis (2-methyl) Propionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2- (2-imidazoline-2 And azo compounds such as -yl) propane].

  Dibenzoyldioxydan, tert-butyl perbenzoate, tert-butyl peroxypivalate, tert-hexyl peroxypivalate, octanoyl peroxide, lauroyl peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, diisopropyl -N-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate and tert-butylperoxybiba And organic peroxides such as rate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide.

  In the synthesis, mercaptans such as lauryl mercaptan and n-dodecyl mercaptan, and chain transfer agents such as α-methylstyrene dimer and limonene may be used.

  Among these, from the viewpoint of molecular weight control and molecular weight distribution control, 2,2′-azobisisobutyronitrile, dimethyl 2,2′-azobis (2-methylpropionate), dibenzoyldioxidane and tert-butyl are used. Perbenzoate, tert-butyl peroxypivalate, tert-hexyl peroxypivalate, octanoyl peroxide, lauroyl peroxide, tert-butylperoxy-2-ethylhexanoate are preferred.

  When the copolymer (A) is prepared by a solution polymerization method, examples of the solvent include aromatic solvents such as methylbenzene and 1,2-dimethylbenzene; alcohols such as ethanol, propan-2-ol, and 1-butanol. System solvents; ether solvents such as 1-methoxy-2-propanol, (2-methoxymethylethoxy) -propanol 2-ethoxyethanol, 2-butoxyethanol; ethyl ethanoate, butyl ethanoate, 2-ethoxyethanol acetate, etc. Ester solvents; ketone solvents such as 2-propanone, 2-butanone, 4-methyl-2-pentanone, 2,4-pentadione; and organic solvents such as amide solvents such as dimethylformamide. However, the present invention is not limited to such examples. These solvents may be used alone or in combination of two or more. The amount of the solvent is appropriately determined in consideration of the polymerization conditions, the composition of the α, β-unsaturated compounds (a-1) to (a-3), the viscosity and concentration of the resulting copolymer (A), and the like. That's fine.

What is necessary is just to set suitably the polymerization conditions at the time of producing a copolymer (A) according to the polymerization method, and it is not specifically limited. The polymerization temperature is preferably room temperature to 150 ° C, more preferably 40 to 120 ° C. What is necessary is just to set reaction time suitably so that the polymerization reaction of (alpha), (beta)-unsaturated compound (a-1)-(a-3) component may be completed.

<Reactive compound (B)>
Next, the reactive compound (B) will be described.
In the reactive compound (B), the reactive functional group in the reactive compound (B) undergoes a curing reaction with the active hydrogen group of the copolymer (A) to improve the molecular weight of the resin composition for bonding laminated sheets, Has the role of improving cohesion. Moreover, the reactive compound (B) can be expected to improve the interaction with the substrate surface described later. Furthermore, for a base material subjected to a physical treatment such as corona discharge treatment or a chemical treatment modified with an acid or the like, the reactive functional group in the reactive compound (B) is chemically reacted with the base material. Thus, it is possible to develop a strong interaction between the copolymer (A) and the base material.

Examples of the reactive compound (B) include a polyisocyanate compound, a polyfunctional epoxy compound, a high molecular weight polycarbodiimide compound, an N-methylol group-containing compound, a polyfunctional aziridine compound, and a metal chelate compound.
Among these, a compound having two or more functional groups in the molecule capable of reacting with active hydrogen in the copolymer (A) is preferably used so that the curing reaction of the reactive compound (B) works effectively. . In particular, the polyisocyanate compound is preferably used because it is excellent in the adhesiveness of the resin composition for bonding laminated sheets after the curing reaction.

  Of the reactive compounds (B), the polyisocyanate compound (b-1) is not particularly limited as long as it is a compound having a plurality of isocyanate groups in the molecule. Examples of polyisocyanate compounds include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane trisene. Polyisocyanate compounds such as isocyanate and polymethylene polyphenyl isocyanate, adducts of these polyisocyanate compounds and polyol compounds such as 2- (hydroxymethyl) -2-ethylpropane-1,3-diol, Burettes and isocyanurates, and these polyisocyanate compounds With known polyether polyols or polyester polyols, polypropene acid alkyl polyols, polybutadiene polyols, adducts, etc. and polyisoprene polyol and the like.

Among these, an aliphatic polyisocyanate (b-1-) from the viewpoints of pot life immediately after addition of the resin composition for bonding a laminated sheet, control of the reaction rate after coating, and improvement of transparency of the coating film. 1), a hexamethylene diisocyanate burette or isocyanurate, an adduct of hexamethylene diisocyanate with a known polyether polyol or polyester polyol, polypropenoic acid alkyl polyol, polybutadiene polyol, polyisoprene polyol, etc.
The alicyclic polyisocyanate compound (b-1-2), isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate burette or isocyanurate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane Adducts with known polyether polyols, polyester polyols, polypropenoic acid alkyl polyols, polybutadiene polyols, polyisoprene polyols and the like with any of the diisocyanate compounds are preferred.

  Furthermore, from the viewpoints of adhesiveness and heat-and-moisture resistance of the laminated sheet bonding resin composition, in particular, an adduct of hexamethylene diisocyanate and 2- (hydroxymethyl) -2-ethylpropane-1,3-diol, hexamethylene diisocyanate isocyanate Nurate trimer, hexamethylene diisocyanate burette (b-1-1), adduct of isophorone diisocyanate and 2- (hydroxymethyl) -2-ethylpropane-1,3-diol, isophorone diisocyanate isocyanurate trimer (B-1-2) is preferred.

  The polyfunctional epoxy compound is not particularly limited as long as it is a compound having a plurality of epoxy groups in the molecule. Examples of the polyfunctional epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy resin, N, N, N ′, N Examples include '-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyltoluidine, and the like.

  Examples of the high molecular weight polycarbodiimide compound include Nisshinbo's Carbodilite series. Among these, Carbodilite V-01, 03, 05, 07, 09 is preferable because of its excellent compatibility with organic solvents.

  Examples of the polyfunctional aziridine compound include 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane, and the like.

  Examples of the metal chelate compound include aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium, and 2,4-pentadione and ethyl-3-oxobuta And coordination compounds with noate.

  The reactive compound (B) can be used alone or in combination.

The amount of the reactive compound (B) added is the equivalent ratio of the active hydrogen group contained in the copolymer (A) and the reactive functional group contained in the reactive compound (B) ([reactive compound (B ) Equivalents of reactive functional groups] / [equivalents of active hydrogen groups in copolymer (A)]), 0.2 to 10 is preferable, 0.5 to 5 is more preferable, and 1 ~ 3 is more preferred.
If the equivalent ratio is less than 0.2, the amount of the reactive compound (B) added is small, the effect of improving the molecular weight due to the curing reaction cannot be obtained, the cohesive force is insufficient, and the adhesive strength may be reduced. When the equivalent ratio exceeds 10, there is a concern that excess reactive compound (B) remains in the laminated sheet-bonding resin composition and the adhesive force is lowered, and the reactive compound remaining after the durability test ( B) undergoes a curing reaction, and when the laminated sheet bonding resin composition is used for bonding two films, the laminated sheet bonding resin composition may be deteriorated such as being too hard. An equivalence ratio in the range of 1 to 3 is preferable because it is easy to improve the cohesive force and complete the reaction of the reactive compound.

Next, the silane coupling agent will be described.
<Silane coupling agent (C)>
By using a silane coupling agent, it can condense with a functional group such as a hydroxyl group or a carboxyl group on the surface of the substrate to improve the adhesive strength of the laminated sheet bonding resin composition. In particular, when used on the surface of an inorganic base material such as glass, metal foil, metal plate, or metal vapor-deposited film, since the interaction is high, the effect of improving the adhesive strength is high, and the silane coupling agent (C) is used. It is preferable to contain.

  Examples of the silane coupling agent (C) include, but are not limited to, ethenylsilanes such as ethenyltris (β-methoxyethoxy) silane, ethenylethoxysilane, and ethenyltrimethoxysilane;

  (2-methyl) propenoic acid-containing ester silanes such as (2-methyl) propenoic acid trimethoxysilylpropene, (2-methyl) propenoic acid triethoxysilylpropene, and (2-methyl) propenoic acid dimethoxysilylpropene;

  β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3, Epoxy silanes such as 4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane;

  N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-amino Aminosilanes such as propyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltriethoxysilane;

  and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. These may be used alone or in any combination of two or more.

  The addition amount of the silane coupling agent (C) is preferably 0.1 to 5 parts by weight and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the copolymer (A). If the amount is less than 0.1 parts by weight, the effect of improving the adhesive strength by adding the silane coupling agent is poor, and even if the amount exceeds 5 parts by weight, no further improvement in performance may be observed. In addition, the range of 1-3 weight part is more preferable from a viewpoint of the adhesive force improvement by addition of a silane coupling agent (C).

Next, the resin composition for joining laminated sheets will be described.
The resin composition for joining laminated sheets of the present invention may be a so-called two-component mixed resin composition for joining laminated sheets, in which the copolymer (A) and the reactive compound (B) are mixed at the time of use. Further, it may be a one-pack type laminated sheet bonding resin composition in which the main agent and the curing agent-reactive compound (B) are mixed in advance. Moreover, you may use a copolymer (A) and a reactive compound (B) by multiple types each independently. Usually, when used as a two-component mixed type, the first solution includes a copolymer (A), a silane coupling agent (C), an organic solvent, and other additives, and the second solution includes a reactive compound. (B), an organic solvent, and other additives are included.

  As other additives, the bonding resin composition for laminated sheets of the present invention includes a tackifier, a leveling agent, a phosphorus-based or phenol-based antioxidant, an ultraviolet-ray-stabilizing agent within the scope of the present invention. Various additives such as an agent, a metal deactivator, a flame retardant, a plasticizer, and an organic / inorganic pigment can be blended.

  When using a metal layer (metal foil, metal plate, etc.) as a film constituting the back protective sheet for solar cells, in order to improve the metal adhesion of the laminated sheet bonding resin composition of the present invention, a phosphoric acid compound, For example, phosphoric acid, metaphosphoric acid, pyrophosphoric acid, phosphorous acid, and esters thereof can be added.

  In addition, the resin composition for bonding laminated sheets of the present invention is preferably used as a bonding agent for manufacturing a back surface protection sheet for solar cells, and is a solar cell laminate that is thermocompression bonded at a high temperature of 100 ° C. or higher for 30 minutes or more after coating. It can also be used as an anchor coating agent for sheets. In that case, in order to eliminate tack after coating, it is preferable to add minerals such as talc, diatomaceous earth, calcium carbonate, feldspar, quartz, and antiblocking agents such as silica and PMMA beads.

  In addition, a well-known additive can be mix | blended without a restriction | limiting within the range which does not deviate from the meaning of this invention for the resin composition for laminated sheet joining. For example, for the purpose of improving the laminate appearance, a known leveling agent or antifoaming agent can be added to the resin composition for bonding laminated sheets.

  Examples of the leveling agent include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, and polyether-modified polymethyl. Examples include alkylsiloxane, (2-methyl) propenoic acid alkyl ester copolymer, lecithin, and mixtures thereof.

  As an antifoamer, well-known things, such as a silicone resin, the copolymer of an alkyl ethenyl ether and (2-methyl) propenoic acid alkyl ester, or mixtures thereof, are mentioned. When a leveling agent and an antifoaming agent are added, one type of compound may be used independently, or two or more types may be used in any combination.

  Moreover, as a known additive used in the present invention, for the purpose of further suppressing deterioration yellowing over time of the resin composition for joining laminated sheets due to ultraviolet rays or heat such as the sun, known phosphorous or phenolic compounds Antioxidants, ultraviolet stabilizers, and metal deactivators can be blended into the laminated sheet bonding resin composition. These may be used alone or in any combination of two or more. The phosphorus-based or phenol-based antioxidant, UV stabilizer, and metal deactivator used in the present invention are in the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the solid content of the copolymer (A). Is more preferable, and 0.1 to 1 part by weight is more preferable. If the addition amount is less than 0.05 weight, there is a possibility that a sufficient deterioration yellowing suppression effect may not be obtained, and if it is more than 5 parts by weight, the adhesive force of the laminated sheet bonding resin composition is greatly deteriorated. There is a risk.

  The nonvolatile content (hereinafter also referred to as solid content) of the resin composition for bonding laminated sheets of the present invention is preferably in the range of 10 to 50% by weight. The resin composition for joining laminated sheets of the present invention can be adjusted for solid content using a solvent as exemplified above.

Examples of the solvent used in the laminated sheet bonding resin composition include ester solvents such as ethyl ethanoate, butyl ethanoate, and 2-ethoxyethanol acetate; 2-propanone, 2-butanone, 4-methyl-2- Ketone solvents such as pentanone and 2,4-pentadione; aromatic solvents such as methylbenzene and 1,2-dimethylbenzene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; amide solvents such as dimethylformamide Is mentioned. As the solvent to be used, one type of solvent may be used, or two or more types may be used in any combination.

Next, the laminated body which uses the resin composition for laminated sheet bonding is demonstrated.
In order to produce a multilayer film, which is a typical laminate, using the laminated sheet bonding resin composition according to the present invention, a generally used method can be used. For example, a laminated sheet bonding resin composition is applied to one side of one film with a comma coater or a dry laminator, the solvent is stripped off as necessary, and the other film to be laminated is bonded to room temperature or heated. What is necessary is just to carry out the hardening reaction under temperature and to make it adhere. The resin composition for joining laminated sheets applied to the film is preferably about 1 to 50 g / m2. When setting it as the multilayered structure of 3 or more layers, the laminated sheet joining resin composition which concerns on this invention can be used for all or one part at the time of bonding between the films of each layer and adhere | attaching.

Next, the film used in the present invention will be described. Examples of the film include a plastic film (including a plastic sheet), a metal foil, and the like, which are appropriately selected from the characteristics required for the laminate.

  For example, insulation is achieved by using a polyester film, which will be described later, weather resistance is achieved by using a fluorine film, plastic film or metal foil on which an olefin film, a metal oxide, or a nonmetal inorganic oxide is deposited. The water vapor barrier property can be imparted by using.

Examples of the plastic film include polyester resin films such as polyethylene terephthalate, polybutylene terephthalate, and polynaphthalene terephthalate.
Fluorine resins such as polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, polyethylene tetrafluoroethylene, polytetrafluoroethylene, tetrafluoroethylene perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer Films Olefin films such as polyethylene resin films and polypropylene resin films Polyvinyl chloride resin films, polycarbonate resin films, polysulfone resin films, poly (2-methyl) propenoic acid resin films, and the like.

  The above plastic film has a surface with physical treatment such as corona discharge, plasma treatment, flame treatment, etc., chemical treatment that modifies the film surface with acid or alkali, etc. For the laminated sheet bonding resin composition, such as a film having an increased surface area, those that have been subjected to an easy adhesion treatment can be suitably used.

  Examples of the plastic film on which a metal oxide or a nonmetal inorganic oxide is deposited include, for example, oxides such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, and yttrium. The thing vapor-deposited on the plastic film is mentioned. As a plastic film used for vapor deposition, polyethylene terephthalate is preferably used.

  Examples of the metal foil include aluminum foil and copper foil.

  Regarding the film to be laminated, a film colored in black or white can be used for the purpose of improving the design property or improving the light reflectance and improving the conversion efficiency of the solar cell.

  When the laminated body has a multilayer structure, as a method for expressing the excellent adhesive force of the laminated sheet bonding resin composition according to the present invention, for example, an easy adhesion treatment of a polyester resin film or a fluorine resin film is performed. It is possible to enhance the interaction with the substrate in the heating and solvent removal process by coating from the surface that is not made or the film surface that is extremely difficult to adhere such as olefin substrate such as polypropylene Therefore, it is used more suitably.

  Next, a method for producing a back protective sheet for solar cells using the bonding resin composition for laminated sheets of the present invention and a back protective sheet for solar cells will be described. In addition, as described in the background art, the manufacturing method and configuration of the back surface protection sheet for solar cells are various manufacturing methods and configurations depending on purposes and needs such as heat resistance, weather resistance, water vapor permeability, and electrical insulation. Can be adopted.

  Among these, in order to satisfy the performance of weather resistance, water vapor permeability, electrical insulation, mechanical properties, mounting workability, etc. when used as a solar cell module, among the films exemplified above, it has resistance to temperature. Polyester resin films such as polyethylene terephthalate and polynaphthalene terephthalate, polycarbonate resin films, and olefin films, metal oxides with water vapor barrier properties, or non- A solar cell in which a metal foil such as a plastic film or aluminum foil on which a metal inorganic oxide is vapor-deposited, and an olefin-based film or a fluorine-based resin film with good weather resistance to prevent appearance defects due to light deterioration The back surface protective sheet for the use is preferable.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, parts represent parts by weight in terms of solid,% represents weight%, and the unit of active hydrogen value is mgKOH / g.

Production Example 1
(Synthesis Example 1)
<Production of copolymer (A)>
A polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, a polymerization reactor and a dropping device of a polymerization reaction apparatus equipped with a nitrogen introduction tube, from the group consisting of the following monomer, carboxyl group, amino group, and amide group Α, β-unsaturated compound (a-1) having functional group selected, α, β-unsaturated compound (a-2) having active hydrogen group, α, β-unsaturated compound (a-3) The polymerization initiator and the solvent were charged at the following ratios.

[Polymerization tank]
90 parts of ethyl ethanoate [Drip device]
2-methyl-2-propenoic acid (a-1-2) 1.5 parts 2-hydroxyethyl propenoate (a-2-2) 2 parts 2-methyl-2-propenoic acid dicyclopentenyl (a-3-) 1-2) 16 parts ethyl propenoate (a-3-2-2) 80.5 parts ethyl ethanoate 12.6 parts tert-butylperoxy-2-ethylhexanoate 2.6 parts

After the air in the polymerization tank was replaced with nitrogen gas, the dropping of the mixture was started from the dropping device at 78 ° C., which is the reflux temperature of ethyl ethanoate, in a nitrogen atmosphere with stirring. After dropping over 2 hours, the mixture was further aged and cooled for 6 hours while stirring to obtain a resin solution containing the copolymer (A-1).
This solution was colorless and transparent, had a nonvolatile content of 50.3% by weight and a viscosity of 800 mPa · s, and the copolymer (A-1) had a number average molecular weight of 28,000 and a molecular weight distribution of 5.2. The active hydrogen equivalent was 5960 g / mol.

<Measurement of measurement of number average molecular weight, weight average molecular weight, molecular weight distribution>
Further, the molecular weight and molecular weight distribution of the copolymer (A) were measured by GPC (gel permeation chromatography) using GPC-8020 manufactured by Tosoh Corporation. The molecular weight of the copolymer (A) is a polystyrene-equivalent number average molecular weight and weight average molecular weight, and the molecular weight distribution was calculated from the ratio of weight average molecular weight / number average molecular weight.

<Active hydrogen value equivalent>
The active hydrogen equivalent (g / mol) means the equivalent of active hydrogen groups in the copolymer (A) that can react with the reactive compound (B). Based on the equivalent ratio of the active hydrogen equivalent and the reactive group of the reactive compound (B), a resin composition for joining laminated sheets was designed and examined.
The active hydrogen equivalent was calculated from the following formula from the charging ratio of (a-2).
Active hydrogen equivalent (g / mol) = total solid charged part / ((a-2) charged part / (a-2) formula weight)
The total solid charge is the total charge of (a-1) + (a-2) + (a-3) + polymerization initiator.

(Synthesis Examples 2 to 22)
The synthesis was carried out in the same manner as in Synthesis Example 1 except that the raw materials and the charged parts described in Table 1 were used, and a 50% solid solution of the copolymers (A-2) to (A-22) was obtained.

Abbreviations in Table 1 are as follows.
Α, β-unsaturated compound having a functional group selected from the group consisting of a carboxyl group, an amino group, and an amide group (a-1): (a-1-1) propenoic acid, (a-1-2) 2-methyl-2-propenoic acid, (a-1-3) hexahydrophthalic acid-2-hydroxyethyl-2- (2-propenyloxy) ethyl ester, (a-1-4) 2-methyl-2- N, N-dimethylaminoethyl propenoate, (a-1-5) pentamethylpiperidinyl 2-methyl-2-propenoate, (a-1-6), 2-propenamide,
Α, β-unsaturated compound having active hydrogen group (a-2): (a-2-1) 2-hydroxyethyl propenoate (formula 116.1), (a-2-2) 2-propenoic acid 2- Hydroxybutyl (formula 144.2), (a-2-3) propenoic acid polyethene oxide (ethene oxide chain n = 10 (formula 512.6), (a-2-4) 2-methyl-propenoic acid 2- (1,3dioxobutoxy) ethyl (formula 214.2), (a-2-5) 2-hydroxyethyl 2-methyl-2-propenoate (formula 130.14)
Α, β-unsaturated compound (a-3-1) having a cyclic structure of two or more rings: (a-3-1-1) iso-bonyl propenoate, (a-3-1-2) 2-methyl -2-propenoic acid dicyclopentenyl, (a-3-1-3) dipropenoic acid-hydrogenated 2,2-bis (hydroxyphenyl) propane tetraethene oxide adduct,
α, β-unsaturated compound (a-3): (a-3-2-1) n-butyl propenoate, (a-3-2-2) ethyl propenoate, (a-3-2-2) Lauryl propenoate, (a-3-2-2-4) ethene oxide methyl propenoate, (a-3-2-5) methyl 2-methyl-2-propenoate, (a-3-2-6) 2-methyl Cyclohexyl-2-propenoate, (a-3-2-7) 2-propenenitrile, (a-3-2-8) ethenylbenzene, (a-3-2-9) (2-methyl) propenoic acid Glycidyl (polymerization initiator 1) 2,2′-azobis (2-methylpropionitrile), (polymerization initiator 2) tert-butylperoxy-2-ethylhexanoate, (polymerization initiator 3) tert-butyl Peroxypivalate, (polymerization initiator 4) lauroyl peroxide (Solvent) ethane ethyl

(Comparative Synthesis Examples 1 to 5)
The synthesis was performed in the same manner as in Synthesis Example 1 except that the raw materials and preparation amounts described in Table 2 were used, and a 50% solid solution of the copolymers (Comparative A-1) to (Comparative A-5) was prepared. Obtained.

  The abbreviations in Table 2 are the same as those in Table 1.

Example 1
As a reactive compound (B), 100 parts of the copolymer (A-1) obtained in Synthesis Example 1 isocyanurate trimer of 1,6-hexamethylene diisocyanate (b-1-1-2). ) (Sumika Bayer Urethane Sumidur N3300 NCO% 22.6%) 6.4 parts was added, and 1.0 part of γ-glycidoxypropyltrimethoxysilane was added as the silane coupling agent (C-1). . In order to make the nonvolatile content about 30%, ethyl acetate was added and stirred well to obtain a resin composition (S-1) for joining laminated sheets.

<Calculation of reactive compound groups / active hydrogen groups>
About the obtained resin composition for joining laminated sheets, the reactive compound group (Y) / active hydrogen group (X) was calculated from the charging ratio.
About Example 1, it computed as follows.
Reactive group mole (Y) in reactive compound (b-1-1-2)
: 21.8% (NCO%) / 42 (NCO molecular weight) * 6.4 (charged part) = 0.0332 mol
Active hydrogen group mole (X) in the charged amount of copolymer (A-1)
: 100 (preparation part) / 5960 (active hydrogen equivalent) = 0.167 mol
Reactive compound group (Y) / active hydrogen group (X) = 2.0

<Evaluation method of pot life>
About the obtained resin composition for bonding laminated sheets, the viscosity at 25 ° C. is 1 hour, 4 hours, 8 hours, and 24 hours later, using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 20 rpm for 2 minutes. The pot life was evaluated in four stages.
A: “There is no change in viscosity. The rate of increase in viscosity by 24 hours is less than 2 times. Very good.”
○: “A slight increase in viscosity is observed, and the rate of increase in viscosity up to 8 hours is less than twice. Good.”
Δ: “A sudden increase in viscosity was observed, and the rate of increase in viscosity was more than doubled in less than 4 hours”.
X: “Increased viscosity increase rate is 2 times or more in 1 hour of addition” has a practical problem.
In Example 1, the rate of increase in viscosity for 24 hours was 1.3 times, which was very good.

<Method for forming laminate>
The resin composition for bonding laminated sheets is dried on a corona-treated surface of a polyester film (Toray Industries, Lumirror X-10S, thickness 50 μm) (hereinafter, the corona-treated surface is indicated by corona treatment + film name). Coating amount: The laminated sheet bonding resin composition (S-1) was applied by a dry laminator in an amount of 5 to 7 g / m 2. And after volatilizing a solvent, after laminating to a corona treatment polyester film, it hardened | cured at 50 degreeC for 96 hours, and the laminated body 1 was formed.

In the same manner, laminate 2 [corona-treated polyester film / laminate sheet bonding resin composition layer / JIS1N30 soft aluminum foil], laminate 3 [corona-treated polyester film / laminate sheet bonding resin composition layer / silicon dioxide] Vapor-deposited PET film (Mitsubishi Resin Co., Ltd., trade name: Tech Barrier)], laminate 4 [Polyester film (Toray Industries, Lumirror X-10S, untreated surface with a thickness of 50 μm) / laminate sheet bonding resin composition Layer / ETFE film (Neoflon ^TM E-0050 manufactured by Daikin Industries, Ltd.)], laminate 5 [corona-treated polyester film / laminated sheet bonding resin composition layer / corona-treated LLDPE film (LL-XUM N, manufactured by Futamura Chemical Co., Ltd.) # 30)] was formed and the following evaluation was performed.

<Reactive compound reactivity evaluation method>
About the obtained laminated body 1, the reaction rate of the reactive compound after 50 degreeC 24 hours and 96 hours was evaluated. IR measurement was performed using Spectrum One manufactured by PerkinElmer, and the absorption spectrum of the reactive functional group of the reactive compound (isocyanate group: 2270 to 2250 cm ⁻¹ , epoxy group: 925 to 900 cm ⁻¹ ) and ester bond C = The reaction rate of the reactive compound before and after curing was evaluated from the peak height ratio of the absorption spectrum of O stretching vibration (1750 to 1725 cm ⁻¹ ). A specific formula was obtained as follows and evaluated in four stages. Reaction rate (%) = (Reactive functional group after curing (B) Reactive functional group absorption / Curing after C = O absorption spectrum) / (Reactive functional group before curing (B) reactive functional group (C = O absorption spectrum before absorption / curing) x 100
A: “Reaction rate after 24 hours of curing is 95% or more, and no absorption of reactive compounds is observed after 96 hours of curing. Curing reactivity is very good.”
○: “Reaction rate after 96 hours of curing, 95% or more, and curing reactivity is good”
Δ: “Reaction rate after 96 hours of curing, not less than 80% and not more than 95%, and curing reactivity is slightly insufficient”.
X: “Reaction rate after curing for 96 hours, less than 80%, insufficient curing reactivity” practically problematic.
In Example 1, the reaction rate was 99% at 24 hours after curing, and after 96 hours after curing, the absorption spectrum of the reactive functional group was not observed and the curing reactivity was very good.

<Evaluation method of coatability>
The state after curing of the obtained laminate 1 was visually observed and evaluated in three stages.
○: “Smooth coated surface was obtained. Very good.”
Δ: “Slight repellency and foaming are observed at the end of the coated surface, but good”
×: “Repelling, foaming and streaking are recognized on the coated surface, and there are practical problems.”
In Example 1, a smooth coated surface was obtained and was very good.

<Peeling strength test before curing>
The laminate 1 before curing is cut into a size of 200 mm × 15 mm, left to stand for 6 hours in an environment of 25 ° C. and a humidity of 65%, and using a tensile tester in accordance with the test method of ASTM-D1876-61. In an environment of 25 ° C. and 65% humidity, a 180 ° peel test was performed at a load rate of 100 mm / min, and evaluation was performed in four stages.
◎: Peel strength is 2N / 15mm or more Excellent adhesion ○: Peel strength 1N / 15mm or more, less than 2N / 15mm Excellent adhesion △: Peel strength 0.1N / 15mm or more, less than 1N / 15mm Practical problem Yes x: Peel strength less than 0.1 N / 15 mm There was a problem in practical use due to deviation during winding. Example 1 had a peel strength of 3.5 N / 15 mm and was excellent in adhesiveness.

<Peeling strength test after curing>
Each of the laminates 1 to 5 after curing is cut into a size of 200 mm × 15 mm, left to stand in an environment of 25 ° C. and a humidity of 65% for 6 hours, and then subjected to a tensile test according to the test method of ASTM-D1876-61. Using a machine, a 180 ° peel test was performed at a load speed of 100 mm / min in an environment of 25 ° C. and a humidity of 65%, and evaluation was performed in four stages.
◎: Peel strength is 8N / 15mm or more Excellent adhesion ○: Peel strength 5N / 15mm or more, less than 8N / 15mm Excellent adhesion △: Peel strength 3N / 15mm or more, less than 5N / 15mm Adhesiveness is slightly enough *: Peel strength is less than 3 N / 15 mm. Practical problem of poor adhesion. Although Example 1 is as shown in Table 3, the result was very excellent in adhesiveness.

<Peeling force test after wet heat resistance test>
Each of the laminates 1, 4, and 5 after curing was cut into a size of 200 mm × 15 mm and allowed to stand for 1000 hours and 3000 hours in an environment of 85 ° C. and humidity of 85%. Then, after standing for 6 hours in an environment of 25 ° C. and a humidity of 65%, in accordance with the test method of ASTM-D1876-61, using a tensile tester, the load speed is 300 mm in an environment of 25 ° C. and a humidity of 65%. A T-type peel test was conducted at / min.
◎: Peel strength is 8N / 15mm or more Excellent adhesion ○: Peel strength 5N / 15mm or more, less than 8N / 15mm Excellent adhesion △: Peel strength 3N / 15mm or more, less than 5N / 15mm Adhesiveness is slightly enough There are practical problems.
However, since the wet heat 3000 hour test was overestimated, it was judged to be practical even by Δ evaluation.
×: Peel strength is less than 3 N / 15 mm Practical problem with poor adhesiveness Although Example 1 is as shown in Table 3, the result is that the adhesiveness is very excellent and the wet heat resistance test is excellent. It was.

<Weather-proof yellowing test>
4). Evaluation of Yellowing by UV Irradiation With the polyolefin film side of the film laminate 4 as the irradiation surface, it is set on a U V irradiation tester (Isuper U V Tester W13 (trade name) manufactured by Iwasaki Electric Co., Ltd.), and the illuminance is 100 W / m 2. Irradiation was performed for 72 hours under the conditions of 60 ° C. and 50% RH. The color difference (Δb value) before and after irradiation was measured with a color difference meter, and the degree of yellowing was evaluated. The evaluation criteria are as follows.
：: Δb value is less than 3 Excellent in weathering yellowing ◯: Δb value is 3 or more and less than 6 Δ: Excellent in weathering yellowing Δ: Δb value is 6 or more and less than 10 Δb value is 10 or more Clear yellowing. In practice, Example 1 is as shown in Table 3, but it was found that Δb value was 2.1 and excellent in weathering yellowing.

.

(Examples 2 to 22)
Except having used the raw material and preparation amount which were described in Table 3, 4, it carried out similarly to Example 1, and obtained the resin composition (S-2)-(S-22) for laminated sheet joining. The result of having implemented evaluation similar to Example 1 is shown.

Abbreviations in Tables 3 and 4 are as follows.
Reactive compound (B)
Polyisocyanate (b-1): (b-1 [1]) Prepolymer of polymethylene polyphenylisocyanate Sumidur E21-1 (NCO%: 16.0% solid content 100%) manufactured by Sumika Bayer Urethane, (b -1 [2]) Adduct body of tolylene diisocyanate and 2- (hydroxymethyl) -2-ethylpropane-1,3-diol Sumika Bayer Urethane Desmodur L-75 (NCO%: 13.0% solids) 75%),
Aliphatic polyisocyanate (b-1-1): (b-1-1) Adduct body of hexamethylene diisocyanate and 2- (hydroxymethyl) -2-ethylpropane-1,3-diol Sumika Bayer Sumidur HT made of urethane (NCO%: 13.0% solid content 75%), (b-1-1-2) isocyanurate trimer of hexamethylene diisocyanate Sumidur N3300 made by Sumika Bayer Urethane (NCO%: 21 .8% solid content 100%)
Alicyclic polyisocyanate compound (b-1-2): (b-1-2-1) isocyanurate trimer of isophorone diisocyanate TOLONATERIDT 70B (NCO%: 12.3% solid content 70%) manufactured by Perstorp
Epoxy compound (b-2): N, N, N ′, N′-tetraglycidyl-m-xylenediamine (Ep equivalent 102)
Silane coupling agent (C): (c-1) γ-glycidoxypropyltrimethoxysilane, (c-2) γ-aminopropyltriethoxysilane (c-3)

(Comparative Examples 1-8)
Except having used the raw material and preparation amount which were described in Table 5, it carried out similarly to Example 1, and obtained the resin composition (Comparative-1)-(Comparison-8) for laminated sheet joining. The result of having implemented evaluation similar to Example 1 is shown.

The abbreviations in Table 5 are the same as in Tables 3 and 4, but the additives are as follows.
Tin catalyst: Tin (IV) dibutylbislaurate
Catalyst stabilizing additive: 2,4-pentanedione Compound 1: 2- [4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl] -4,6- [bis (2,4-dimethylphenyl) )]-1,3,5-triazine Compound 2: 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene

  As shown in Table 3, the laminated sheet bonding resin compositions of the examples are excellent in curing reactivity, excellent in initial adhesive strength and adhesive strength after a moist heat resistance test, and can maintain adhesive strength over a long period of time. I knew it was possible. Particularly in the moist heat test, in the comparative example, foaming due to decarboxylation reaction of isocyanate groups remaining after curing, and a decrease in adhesive force due to alteration such as the resin composition for joining laminated sheets becomes too hard, -1) is incorporated into the copolymer (A), and it is considered that the effect of improving the curing reactivity appears. Furthermore, since it is excellent in weather resistance, it is thought that the resin composition for joining laminated sheets of the examples is excellent in long-term wet heat resistance for outdoor use.

  In addition, in JIS C 8917 (environmental test method and durability test method for crystalline solar cell module), a moisture resistance test B-2 is defined that it is durable for 1000 hours at 85 ° C. and 85% humidity. It is known as a particularly harsh test method. In this example, it was shown that the adhesive strength can be maintained over a long period of 1000 hours exceeding 1000 hours, and it can be said that the resin composition for bonding laminated sheets of the present invention has sufficient long-term wet heat resistance. .

  The resin composition for joining laminated sheets according to the present invention is a multilayer laminated material for outdoor industrial applications such as buildings (barrier material, outer wall material, roofing material, solar cell panel material (back surface protection sheet for solar cell, solar cell surface protection sheet). ), A resin composition for joining laminated sheets for window materials, outdoor flooring materials, certification protective materials, automobile members, etc.) can provide strong adhesive strength. In addition, it is possible to suppress a decrease in adhesive strength over time due to hydrolysis or the like during outdoor exposure, and to maintain strong adhesive strength over a long period of time.

  Comparative Example 1 is an example in which (a-1) is not incorporated into the copolymer (A), and the curing reaction of the reactive compound (B) in the curing process cannot be completed without using a tin catalyst. I understand that. When the curing reaction is not completed, the residual isocyanate in the reactive compound (B) reacts with the moisture during the wet heat test to generate carbon dioxide, causing foaming, appearance defects, and the occurrence of floating, as well as adhesive strength. Results in a decline.

  Comparative Examples 2-3 are attempts to improve curing reactivity by adding a tin catalyst to Comparative Example 1. However, a slight change in the amount of tin catalyst added resulted in a significant change in curing reactivity, resulting in unstable adhesion. For this reason, the blur due to the amount added during production is large and is not suitable for industrial production.

  Comparative Examples 4 and 6 are examples in which (a-1) or (a-2) was excessively incorporated into the copolymer (A). There is an optimum value as the curing reaction rate and the amount of active hydrogen involved in the curing reaction. When the amount is excessive, the molecular weight improvement rate is high, which causes a problem with respect to pot life. In Comparative Example 4, forcible coating was attempted, but the area interacting with the film was reduced due to the effect of rough coating during coating, resulting in the adhesive strength being below the practical lower limit.

  Comparative Example 5 is an example in which (a-2) is not incorporated into the copolymer (A), but since it does not have an active hydrogen group, the isocyanate group in the reactive compound (B) is not consumed. As in Comparative Example 1, foaming was observed, no cohesive force was obtained, and the adhesive strength was low.

  Comparative Example 7 is an example in which (a-1) and (a-2) are excessively incorporated into the copolymer (A). Since Comparative Example 4 and 6 had a problem with respect to the pot life, the amount of the reactive compound (B) added was lowered and coating was attempted. Although the reactivity of the isocyanate group was good, the cohesive force of the coating film was insufficient and the adhesive force was low. From this, it can be seen that an optimum value exists as the copolymerization amount of (a-1) and (a-2).

  Although the comparative example 8 is an Example of patent document 6, since (a-1) is not incorporated, since sclerosis | hardenability is bad and (a-2) is outside this patent range, it depends on hardening reaction. The effect of cure shrinkage became significant, resulting in low adhesion.

  Although the comparative example 9 is an Example of patent document 7, since (a-1) is not incorporated, from the same cause as the comparative examples 1 and 8, carbon dioxide is reacted with moisture during the wet heat test. Occurred, and foaming occurred, resulting in poor appearance and floating, and decreased adhesive strength.

  The resin composition for joining laminated sheets according to the present invention is used for joining films of the same or different materials, and is suitably used for joining, for example, a multilayer laminate of a plastic material and a metal material. It is done. Of course, it is also suitable for joining plastic films and metal films. Moreover, since it has the outstanding curing reactivity, it can contribute to the process shortening by shortening of curing time, the electric power reduction required for the heating of a curing process, and environmental load reduction. The bonding resin composition for laminated sheets according to the present invention can maintain high adhesion even when exposed to a high temperature and high humidity environment. Therefore, multi-layer laminates for outdoor industrial applications such as buildings, and specific applications include barrier materials, outer wall materials, roofing materials, solar cell panel materials (back surface protection sheets for solar cells, solar cell surface protection sheets), window materials , Outdoor flooring material, lighting protection material, automobile member, etc.). Since the adhesive strength over time can be maintained over a long period of time, it is particularly suitable for applications where environmental resistance has been strongly demanded, for example, the formation of a back protective sheet for solar cells. In addition, the resin composition composition for bonding laminated sheets according to the present invention exhibits a high adhesive force particularly between laminated bodies including a surface-treated layer of a plastic film. (Including film).

Claims (11)

Copolymer (A);
A resin composition for joining laminated sheets comprising a reactive compound (B) having a functional group capable of reacting with an active hydrogen group (hereinafter referred to as “reactive functional group”),
The copolymer (A) is
0.01 to 10 parts by weight of an α, β-unsaturated compound (a-1) having a functional group selected from the group consisting of a carboxyl group, an amino group, and an amide group;
An α, β-unsaturated compound (a-2) having an active hydrogen group (excluding those which are (a-1)) 0.01 to 20 parts by weight;
Other copolymerizable α, β-unsaturated compounds (a-3) (excluding those which are (a-1) and (a-2)) 70 to 99.98 parts by weight are copolymerized. A resin composition for bonding laminated sheets. The resin composition for joining laminated sheets according to claim 1, wherein the active hydrogen group in the α, β-unsaturated compound (a-2) is a hydroxyl group. The number average molecular weight of the copolymer (A) is 1,000 to 500,000, and the molecular weight distribution (weight average molecular weight / number average molecular weight) is in the range of 2.0 to 8. 2. The resin composition for joining laminated sheets according to 2. Reactive compound (B) is polyisocyanate (b-1), The resin composition for laminated sheet joining in any one of Claims 1-3 characterized by the above-mentioned. The polyisocyanate (b-1) is an aliphatic polyisocyanate (b-1-1) and / or an alicyclic polyisocyanate compound (b-1-2). A resin composition for bonding laminated sheets. Equivalent ratio of active hydrogen group contained in copolymer (A) and reactive functional group contained in reactive compound (B) ([equivalent of reactive functional group of reactive compound (B)] / [ The resin composition for joining laminated sheets according to any one of claims 1 to 5, wherein the equivalent of active hydrogen groups in the copolymer (A)] is in the range of 0.2 to 10. α, β-unsaturated compound (a-3-1) in which 0.1% by weight to 50% by weight in 100% by weight of α, β-unsaturated compound (a-3) has a cyclic structure having two or more rings It is a resin composition for joining for laminated sheets according to any one of claims 1 to 6. The silane coupling agent (C) is contained in an amount of 0.1 to 5 parts by weight with respect to 100 parts by weight of the copolymer (A). Resin composition. The laminated body formed by laminating | stacking the resin composition for laminated sheet bonding in any one of Claims 1-8 on a film. The solar cell back surface protection sheet which uses the resin composition for laminated sheet joining in any one of Claims 1-8. The solar cell module which uses the solar cell back surface protection sheet of Claim 10.