KR101598503B1 - Sheet-adhesive resin composition, laminate, protective sheet for solar cell, and module for solar cell - Google Patents

Abstract

A resin composition for sheet bonding excellent in adhesiveness after curing reaction due to crosslinking and durability after curing reaction due to crosslinking, and the like.
The resin composition for sheet bonding according to the present invention comprises a main resin and a cross-linking agent (C), and the main resin is a copolymer having a glass transition point (Tg) of copolymerizing an?,? (B) (wherein the carboxyl group, the amide group, the carbonyl group and the N- (meth) acryloyl group, which is obtained by copolymerizing the?,? - unsaturated compound and the?,? - unsaturated compound having a glass transition point (Tg) And?,? - unsaturated compounds having at least one functional group selected from the group consisting of alkoxyalkyl groups.

Description

[0001] SHEET-ADHESIVE RESIN COMPOSITION, LAMINATE, PROTECTIVE SHEET FOR SOLAR CELL, AND MODULE FOR SOLAR CELL [0002] BACKGROUND OF THE INVENTION [0003]

The present invention relates to a resin composition for sheet bonding used for bonding plastic films, metal foils and the like, a laminate using the same, a solar cell protection sheet and a solar cell module.

Recently, a laminated sheet for use in an outdoor industrial application (for example, a barrier material, a roof material, a solar panel material, a window, an outdoor flooring, a lighting protection material, an automobile component material, a signboard, (Laminated) a plastic film such as a polypropylene resin, a polyvinyl chloride resin, a polyester resin, a fluorine resin or a polypropene ester resin has been used . As a resin composition for sheet bonding in which a metal foil, a metal plate or a metal evaporated film and a plastic film are laminated on these laminated sheets, a resin composition for bonding a polyepoxy resin sheet or a resin composition for bonding a polyurethane resin sheet is known.

On the other hand, solar cells are rapidly spreading as green energy. A solar cell module used in a solar cell has a configuration in which a filler and a glass plate are sequentially stacked on both sides of a solar cell, which is a solar cell element. Since the glass plate is excellent in transparency, weather resistance, and scratch resistance, it is used as a sealing sheet on the light receiving surface side of the sun and is still generally used today. However, solar cell protection sheets (hereinafter referred to as "protective sheets") other than glass substrates in terms of cost, safety and processability have been developed by various companies on the non-light- .

Hereinafter, a method of manufacturing a protective sheet and an example of a protective sheet will be described. The manufacturing method and construction of the protective sheet adopt various manufacturing methods and configurations depending on purposes and requirements such as heat resistance, weather resistance, water vapor permeability, electrical insulation and the like.

The protective sheet is generally a two-liquid cross-linkable adhesive using a combination of a main resin and a cross-linking agent. The two-liquid cross-linkable adhesive is applied to a film and dried, and then another film or metal foil is laminated on the adhesive layer after drying. Curing the laminate at about 20 to 60 DEG C for several days, and terminating the curing reaction upon crosslinking. Therefore, it is important that the two-liquid cross-linkable adhesive used for the protective sheet has sufficient initial adhesion to the film during lamination, sufficient adhesion strength to the film after curing, and excellent heat resistance, weather resistance, water vapor permeability and hydrolysis resistance.

As the member used for the protective sheet, a polyester resin film, a polyethylene resin film, a polypropylene resin film, a polyvinyl chloride resin film, a polycarbonate resin film, a polysulfone resin film, a poly (2-methyl) A propylene ester resin film, a fluorine resin film and the like, a film on which a metal oxide or a non-metal inorganic oxide is deposited, or a metal foil such as an aluminum foil or a copper foil is used.

Among them, in order to satisfy the properties such as weather resistance, water vapor permeability, electrical insulation, mechanical characteristics, and mounting workability when used as a solar cell module, it is preferable to use (i) polyethylene terephthalate (PET) A polyester resin film or a polycarbonate resin film such as phthalate (PEN), and (ii) a metal oxide or a non-metal inorganic oxide having vapor barrier property is deposited in order to prevent the power output of the solar cell due to the influence of water A protective film formed by laminating a metal foil such as a plastic film or an aluminum foil and a fluorine resin film is generally used.

The solar cell module is manufactured by joining, for example, a glass / solar cell / protective sheet through a sealing material such as ethylene-vinyl acetate (EVA). At that time, the protective sheet is required to have heat resistance because it is squeezed at a high temperature under vacuum. In addition, the protective sheet needs to have good adhesion even when exposed to the open air for a long time, and it is required to have an excellent resistance to degradation as well as adhesion after curing. When a protective sheet using a transparent film is used, the color difference change is extremely small, and excellent weather resistance is required.

As a constitutional example of such a protective sheet, for example, a laminate of an insulating film / a bonding agent / a film having a water vapor barrier property / a bonding agent / a weather resistant film can be exemplified from the solar battery cell side. The insulating film may be a fluorine resin film, a PET film, or an EVA film. The film having a water vapor barrier property may be a silica-deposited PET film, an aluminum oxide deposited PET film, an aluminum foil, Based film include a fluorine resin film, a PET film, a polyethylene film, and the like. As the adhesive, there is a demand for a resin composition for sheet bonding which has excellent adhesiveness to these various substrates.

Patent Document 1 discloses a resin composition for sheet bonding using a polyester-based resin and a polyurethane-based resin which can impart an excellent initial cohesive force and an adhesive force and is balanced.

Patent Document 2 discloses a resin composition for sheet bonding using a polyurethane resin having excellent heat resistance at the time of sterilization of retort in food packaging.

Patent Document 3 discloses an adhesive composition for optical parts used for adhering an optical film such as a polarizing film in which a polypropene acid ester resin is mixed.

Patent Document 4 discloses a resin composition for sheet bonding used in an optical element obtained by mixing a propenoic acid resin.

Patent Document 5 discloses the use of a resin composition for sheet bonding using a polyurethane resin having resistance to degradation in a back side protective sheet.

Patent Document 6 discloses a solar cell backing sheet having an adhesion improving layer composed of a resin composition for sheet bonding using a polyester resin or a polyester polyurethane resin.

In Patent Documents 7 and 8, a back side protective sheet using a resin composition for bonding a polypropene-based resin sheet is disclosed.

Japanese Patent Application Laid-Open No. 10-218978 Japanese Patent Application Laid-Open No. 06-116542 Japanese Patent Application Laid-Open No. 2005-298723 Japanese Patent Registration No. 4824544 Japanese Patent Application Laid-Open No. 2008-4691 Japanese Patent Application Laid-Open No. 2007-136911 Japanese Patent Application Laid-Open No. 2010-263193 Japanese Patent Application Laid-Open No. 12-142349

On the other hand, measures for global warming measures are urgently needed, and laminated sheets such as solar cell protection sheets are required to develop and provide materials with long-term durability. Such a laminate is exposed to the outside for a long period of time, and therefore, the resin composition for bonding an outdoor sheet requires excellent durability.

However, when a polyurethane-based resin composition for sheet bonding using a polyester-based resin is used, a two-component curing-type adhesive coating film using a cross-linking agent together is formed. However, by hydrolyzing an ester skeleton of a polyester- The cohesive force of the adhesive resin composition after the curing reaction is lowered and the film constituting the solar cell protective sheet may peel off.

In the resin composition for sheet bonding using a polyurethane resin, a two-part curing type adhesive coating film using a crosslinking agent containing an isocyanate group is formed. However, all of the isocyanate group is excessively designed and the curing reaction by crosslinking of the isocyanate group is completed , The remaining isocyanate group reacts with water to cause a decarboxylation reaction and sometimes cause foaming in the durability test.

In the resin composition for sheet bonding using the polypropene acid ester resin as the main component, the glass transition point of the resin is adjusted to improve the bonding strength. However, the adhesive strength to each substrate having different surface tension, It may not be obtained, and designing with only a single resin may narrow the application range for various substrates, and it may be difficult to secure the adhesive force.

The present invention has been made in order to solve such a problem, and it is an object of the present invention to provide a resin composition for sheet bonding excellent in adhesion and durability after curing reaction by crosslinking, a solar cell protective sheet using the resin composition for sheet bonding, .

DISCLOSURE OF THE INVENTION The inventors of the present invention have made intensive investigations to solve the above-mentioned problems, and as a result, found that the above-mentioned objectives can be achieved by the following resin composition for sheet bonding, and have completed the present invention.

[1] A resin composition for sheet bonding comprising a main resin and a crosslinking agent (C) for the main resin,

The main resin is a copolymer (A) and a copolymer (B) containing an active hydrogen group (provided that an α, β-unsaturated carboxylic acid having at least one functional group selected from the group consisting of carboxyl group, amide group, carbonyl group and N- (1) and (2) below, wherein the resin composition for sheet bonding comprises:

(1) the copolymer (A) is obtained by copolymerizing an?,? - unsaturated compound and has a glass transition point (Tg) of 40 ° C or more and less than 10 ° C,

(2) The copolymer (B) is obtained by copolymerizing an?,? - unsaturated compound and has a glass transition point (Tg) of 10 ° C or more and less than 110 ° C.

[2] The copolymer according to [1], wherein the copolymer (A) is an α, β-unsaturated compound (m-1) having at least one functional group selected from the group consisting of a carboxyl group, an amide group, a carbonyl group and an N-alkoxyalkyl group, (m-1) and the following (m-2) are excluded), wherein the? -unsaturated compound (m-

Wherein the copolymer (B) is an α, β-unsaturated compound (m-2) (excluding m-1) having an active hydrogen group and another copolymerizable α, , (m-1) and (m-2) are excluded) in the resin composition for sheet bonding according to [1].

[3] The thermoplastic resin composition according to any one of [1] to [3], wherein the copolymer (A) comprises 0.01 to 10 parts by weight of an?,? - unsaturated compound (m-1) in 100 parts by weight of an?,? The resin composition for sheet bonding according to [2], which is obtained by copolymerizing 90 to 99.99 parts by weight of an unsaturated compound (m-3).

Wherein the copolymer (B) is a copolymer of an α, β-unsaturated compound (m-2) (excluding (m-1)) in 100 parts by weight of an α, (Excluding m-1) and (m-2), which is copolymerizable with the?,? - unsaturated compound (m-3) ] Or [3].

[5] The polymer composition according to any one of [1] to [4], wherein the copolymer (A) is contained in an amount of 30 to 95 parts by weight in a total amount of 100 parts by weight of the copolymer (A) By weight based on the total weight of the resin composition.

[6] The sheet bonding method according to any one of [1] to [5], wherein the copolymer (A) has a weight average molecular weight of 50,000 to 1,000,000 and a weight average molecular weight of the copolymer (B) Resin composition.

The crosslinking agent (C) is preferably at least one selected from the group consisting of a polyisocyanate compound (c-1), a polyfunctional epoxy compound (c-2), a metal chelate compound (c-3), a carbodiimide compound (c- The resin composition for sheet bonding according to any one of [1] to [6], which comprises at least one compound selected from the group consisting of c-5)

[8] The resin composition for sheet bonding according to any one of [1] to [7], wherein the crosslinking agent (C) is a polyisocyanate (c-1).

[9] The sheet bonding method according to [8], wherein the polyisocyanate (c-1) is an aliphatic polyisocyanate (c-1-1) and / or an alicyclic polyisocyanate compound Resin composition.

[10] A laminate obtained by laminating a layer made of the resin composition for sheet bonding according to any one of [1] to [9] on one side or both sides of a substrate (G).

[11] A solar cell protection sheet using the laminate described in [10].

[12] A solar cell module using the solar cell protective sheet according to [11].

By using the resin composition for sheet bonding of the present invention, it is possible to provide a laminated sheet having excellent adhesion strength on various substrates, high durability, and excellent weather resistance. Furthermore, since the laminated sheet is excellent in adhesion and durability after the curing reaction due to crosslinking, a laminate suitable for a solar cell protection sheet and a solar cell module can be provided.

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

The resin composition for sheet bonding according to the present invention comprises a main resin and a cross-linking agent (C) for the main resin, wherein two kinds of resins different in glass transition point (hereinafter also referred to as "Tg & (A) and a copolymer (B). This will be described in detail below.

≪ Copolymer (A) >

The copolymer (A) of the present invention is a copolymer having a glass transition point (Tg) of not less than 40 ° C. and less than 10 ° C. by adjusting the composition ratio of an α, β-unsaturated compound obtained by copolymerizing an α, β-

The copolymer (A) is preferably a copolymer (A) of the copolymer (A) in view of the balance between (i) the adhesion to the film at the time of laminating and (ii) the wettability and cohesive force of the cured coating film after the curing reaction, It is preferable to adjust the glass transition point in the range of -40 占 폚 to less than 10 占 폚, more preferably -30 占 폚 or more and less than 0 占 폚, and more preferably -20 占 폚 or more and less than -5 占 폚. When the Tg is less than -40 占 폚, the cohesive force of the cured coating film of the resin composition for sheet bonding may be insufficient and the adhesive strength may be lowered. When the Tg exceeds 10 占 폚, the wettability of the resin composition for sheet bonding is lowered. There is a case that the adhesion to the substrate is lowered.

When the Tg of the homopolymer that can be formed of each monomer as the constituent component of the copolymer (A) is known, the Tg of the copolymer (A) is calculated from the theoretical values of the theoretical .

The glass transition point (Tg) can be calculated theoretically by the following FOX equation.

≪ FOX formula > 1 / Tg = W1 / Tg1 + W2 / Tg2 + + Wi / Tgi + ... + Wn / Tgn

(W1 + W2 + ... + Wi +.) Wherein the glass transition temperature of the homopolymer of each monomer constituting the polymer consisting of n kinds of monomers is Tgi (K), the mass fraction of each monomer is Wi, .Wn = 1).

The Tg of the homopolymer may be the value described in the literature. For example, reference can be made to the following documents: acrylic ester catalog (2001 edition), catalog of Mitsubishi Rayon company (2001 edition), Osaka Organic Chemical Industry catalog (2009 edition), fan catalog of Hitachi Chemical Co., Ltd. (2007 edition) ; And "POLYMER HANDBOOK" 3rd ed., Pp. 209-27, John Wiley & Published in 1989.

In the present specification, the glass transition point (占 폚) of the homopolymer of the following monomers is as follows.

Propenoic acid: 57 DEG C

2-methyl-2-propenoic acid: 144 < 0 &

2-methylenesuccinic acid: 283 DEG C

2-propenamide: 153 < 0 > C

2-methyl-2-propenoic acid 2- (l, 3-dioxobutoxy) ethyl:

Propenoic acid 2-hydroxyethyl: -15 C

2-methyl-2-propenoic acid 2-hydroxyethyl: 55 C

Propoxy 4-hydroxybutyl: -60 ° C

Methyl propenoate: 6 < 0 > C

Ethyl propenoate: -24 < 0 > C

N-butyl propene: -48 < 0 > C

Propenoic acid 2-ethylhexyl: -50 ° C

Propanoate: -54 < 0 > C

Methyl 2-propenoate: 105 < 0 > C

2-methyl-2-propenoate ethyl: 65 C

2-methyl-2-propane butyl: 20 C

2-methyl-2-propenecyclohexyl: 66 DEG C

2-propenyl dicyclopentenyl: 120 < 0 > C

2-propenenitrile: 105 DEG C

2-methyl-2-propenic acid N, N-dimethylaminoethyl: 18 C

The weight average molecular weight of the copolymer (A) is preferably from 50,000 to 1,000,000 (inclusive of the upper limit value and the lower limit value (hereinafter the same), more preferably from 100,000 to 500,000, in order to secure the cohesive force of the resin composition for sheet- When the weight average molecular weight is less than 50,000, the cohesive force of the cured coating film is insufficient and the cohesive strength is lowered to decrease the adhesive strength. When the weight average molecular weight exceeds 1,000,000, the copolymer (A) The weight average molecular weight in the range of 150,000 to 300,000 makes it easy to balance the wettability with the base material of the cured coating film and the balance of the cohesive force and the viscosity and to exhibit the stress relaxation property.

The molecular weight distribution (weight average molecular weight / number average molecular weight) of the copolymer (A) is preferably in the range of 2 to 8, more preferably 3 to 6. When the molecular weight distribution (weight average molecular weight / number average molecular weight) is less than 2, low level molecular weight components are small, so that the leveling property during lamination is deteriorated and the initial adhesive property to the film is lowered. Magnetic capacity) exceeds 8, the thixotropy property is high, and thus appearance defects may occur, such as occurrence of unevenness during coating.

The α, β-unsaturated compound to be used in the copolymer (A) is not particularly limited as long as it is a known one. Among them, α, β-unsaturated compounds having at least one functional group selected from the group consisting of carboxyl group, amide group, carbonyl group and N- it is preferable to use a? -unsaturated compound (m-1) (hereinafter also simply referred to as (m-1)). When the crosslinking agent (C) to be described later has a functional group capable of chemically reacting with the functional group in (m-1), the functional group contained in the (m-1) and the functional group contained in the crosslinking agent (C) Thereby effectively causing a curing reaction due to crosslinking. As a result, the cohesive force of the cured coating film can be improved by the resin composition for sheet bonding. In addition, the effect of improving inter-resin interaction is great, and the cohesive force of the cured coating film is remarkably improved.

The effect of the functional group contained in the compound (m-1) includes not only the curing reaction according to this general crosslinking but also the functional group contained in the compound (m-1), and the addition of hydroxyl group, mercapto group, amino group, sulfonyl group, , The promotion of the reaction between the functional group having an active hydrogen group such as a phosphonyl group, a phosphinyl group and a silanol group and the functional group contained in the crosslinking agent (C) can promote a considerable catalytic effect. As a catalyst for promoting the curing reaction caused by the crosslinking between the functional group contained in the?,? - unsaturated compound (m-2) used in the copolymer (B) described later and the functional group contained in the crosslinking agent It is possible to remarkably improve the cohesive force of the cured coating film.

Especially, the functional group contained in (m-1) has a high catalytic effect such as a carboxyl group and an amide group, and an α, β-unsaturated compound having this functional group is more preferable.

Here, it is assumed that the catalytic effect of the functional group contained in (m-1) is caused by the following mechanism. Is capable of changing the nucleophilic and electrophilic properties of the resin composition for sheet bonding by copolymerizing an?,? - unsaturated compound having a functional group such as a carboxyl group and an amide group. The functional group contained in the crosslinking agent (C) The following effects are expected.

The isocyanate group is known to exhibit a resonance structure as represented by the general formula (1).

Among them, a carboxyl group is the resonance of the isocyanate group, C = N ⁺ -O ^- by moving the balance to promote the reaction of the active hydrogen, and an amino group and an amide group is N ^- active hydrogens by moving the balance to a -C = O ⁺ It is thought to promote the reaction.

It is preferable that 0.01 to 10 parts by weight of the?,? - unsaturated compound (m-1) is contained in 100 parts by weight of the?,? - unsaturated compound used for copolymerization of the copolymer (A) Still more preferably 0.2 to 2 parts by weight. When the amount is less than 0.01 part by weight, not only the cohesion of the cured coating film due to the curing reaction due to crosslinking with the crosslinking agent (C) can be improved but the catalytic effect due to the reaction promotion can not be obtained. On the other hand, when the amount of the crosslinking agent (C) is more than 10 parts by weight, the curing shrinkage due to the curing reaction due to crosslinking becomes prominent, and not only the adhesion force can not be obtained but the catalytic effect upon reaction promotion is too high. There is a fear that the progress of the operation is too fast and the port life (housework time) becomes short. The range of 0.2 to 2 parts by weight is effective in improving the cohesion of the cured coating film and of exhibiting the catalytic effect of the curing reaction and keeping the port life in balance and balance.

Examples of the carboxyl group-containing?,? - unsaturated compound in the?,? - unsaturated compound (m-1) having at least one functional group selected from the group consisting of a carboxyl group, an amide group, a carbonyl group and an N-alkoxyalkyl group include, (2-methyl) propenoic acid (also referred to as "(2-methyl) propenoic acid" hereinafter), 2-methylenesuccinic acid, propylene-1,2-dicarboxylic acid 2-butenyldicarboxylic acid, 2-butenoic acid, 4-ethenylbenzoic acid, phthalic acid-2-hydroxyethyl-2- (2- Hydroxy-ethyl-2- (2-propenyloxy) ethyl ester and phthalic acid-2-hydroxyethyl-2- (2-methyl) 2-propenyloxy) ethyl ester ". (The same applies hereinafter), tetrahydrophthalic acid-2-hydroxyethyl-2- (2-methyl) 2-propenyloxy) ethyl ester, hexahydrophthalic acid- (2-methylphenyloxy) ethyl ester, and succinic acid-2-hydroxyethyl-2- (2-methyl) 2-propenyloxy) ethyl ester.

Examples of the amide group-containing?,? - unsaturated compounds include (2-methyl) 2-propenamide, 2-methylpropene-2-enoylamide, N, , N, N-diethyl-2-propenamide, N- [3- (N ', N'-dimethylamino) propyl] -2- Aldehyde group-containing ethers such as ethynyl acetamide, N-ethenyl- alpha -methylthioacetamide, N-ethenylformamide and N-hydroxymethyl-2-propenamide;

Examples of the?,? - unsaturated compound having a carbonyl group include 2- (1,3-dioxobutoxy) ethyl (2-methyl) (2-methyl) propenoic acid 2- (1,3-dioxobutoxy) propyl, (2-methyl) propenoic acid 3- (2-methyl) propenoic acid 3- (1,3-dioxobutoxy) butyl and (2-methyl) propenoic acid 4- (1,3-dioxobutoxy) Methyl) propenoic acid esters;

For example, N- (1,1-dimethyl-3-oxobutyl) -2-propenamide, N- (1,1-dimethyl- Of ethanols containing a ketone structure.

Examples of the?,? - unsaturated compound having an N-alkoxyalkyl group include N-methoxymethyl-2-propenamide, N- ethoxymethyl (2- Ethoxyethyl (2-methyl) propenamide, N- (n- iso) butoxyethyl (2-methyl) propenamide, N- (2-methyl) propenamide, and the like.

(2-methyl) propenoic acid, 2-methylenesuccinic acid (2-methylene) succinic acid (2-methylpentanoic acid) and the like are preferable from the viewpoint of completion of the curing reaction and cross- -Methyl) 2-propenamide is preferred.

The copolymerization of the?,? - unsaturated compounds other than (m-1) used in the copolymer (A) will be described later. (m-1) may be used singly or in combination of two or more.

≪ Copolymer (B) >

The copolymer (B) of the present invention is a copolymer obtained by copolymerizing an?,? - unsaturated compound and having a glass transition point (Tg) of not less than 10 ° C. and less than 110 ° C. by adjusting a composition ratio of an α, β-

By using the copolymer (B), there is an effect of enhancing the cohesive force depending on the entropy elasticity of the resin composition for sheet bonding. It is preferable to adjust the Tg of the copolymer (B) from 10 占 폚 to less than 110 占 폚 in view of the balance between the adhesion to the film at the time of laminating and the cohesive force according to the entropy elasticity of the resin composition for sheet bonding, More preferably from 25 DEG C to less than 60 DEG C, and still more preferably from 25 DEG C to less than 60 DEG C. When the Tg is less than 10 ° C, the effect of increasing the cohesive strength of the resin composition for sheet bonding is low, and the internal cohesive force is lowered to lower the adhesive strength. When the Tg is 110 ° C or more, compatibility with the copolymer (A) The wettability of the resin composition for sheet bonding may decrease, and the initial adhesion to the film during lamination may be lowered. A balance of the cohesive force and the balance of the internal cohesive force due to the viscosity, the compatibility and the entropy elasticity are easily within a range of Tg 25 ° C or higher and lower than 60 ° C.

If the Tg of the homopolymer that can be formed of each monomer as the constituent component of the copolymer (B) is already known, the copolymer (B) can be obtained by FOX based on the Tg of each homopolymer and the composition ratio of each monomer, ) Can be theoretically obtained.

The weight average molecular weight of the copolymer (B) is preferably from 2,000 to 80,000, more preferably from 5,000 to 50,000, even more preferably from 10,000 to 30,000, in order to secure the coating suitability of the resin composition for sheet bonding and the cohesive strength of the resin desirable. If the weight average molecular weight is less than 2,000, the internal cohesive force is insufficient due to the entropy elasticity of the resin, and the cohesive failure may occur due to the cohesive failure. If the weight average molecular weight is more than 80,000, the viscosity of the copolymer (B) And the compatibility with the copolymer (A) is deteriorated, so that the resin composition for sheet bonding sometimes becomes cloudy. The weight average molecular weight of 10,000 to 30,000 is suitable for the balance of the coatability, cohesion and compatibility This is easy.

The α, β-unsaturated compound used in the copolymer (B) is not particularly limited as long as it is a known one. Among them, an α, β-unsaturated compound (m-2) (Hereinafter simply referred to as (m-2)). Specific examples of the active hydrogen group used in the?,? - unsaturated compound (m-2) include a hydroxyl group, a sulfonyl group, and a phosphonyl group, and among them, a hydroxyl group is preferable.

As the monomer containing a hydroxyl group in the?,? - unsaturated compound (m-2) having an active hydrogen group, for example,

(2-methyl) propenoic acid, 2-hydroxypropyl (2-methyl) propenoic acid, 2-hydroxypropyl (2-methyl) propenoate, 2-hydroxybutyl (2-methyl) propenoate, 4-hydroxybutyl (2-methyl) propenoic acid esters having a hydroxyl group such as tin oxide, (2-methyl) propenoic acid polypropene oxide;

Examples thereof include polyalkylene glycol-containing (2-methyl) propenoic acid derivatives such as (2-methyl) propenoic acid polyethene oxide and (2-methyl) propenoic acid polypropene oxide;

For example, there can be mentioned 2-hydroxy-4- [2- (2-methyl) propane-2-enoyloxy] ethoxydiphenylmethanone, 2- 2-enoyloxy] butoxydiphenylmethanone, 2,2'-dihydroxy-4- [2- (2-methyl) (2-methyl) diphenylmethanone-based hydroxyl group-containing (2-methyl) diphenylmethanone such as 4- [2- (2-methyl) propane-2-enoyloxy] ethoxy- Propene acid derivatives;

, And hydroxyl group-containing?,? - unsaturated compounds.

Examples of the sulfonyl group-containing?,? - unsaturated compounds in the?,? - unsaturated compound (m-2) include eptenylbenzenesulfonic acid, ethenylsulfonic acid, arylsulfonic acid, allyloxybenzenesulfonic acid, methacrylosulfonic acid, methacryloxy And alkenyl group-containing sulfonic acid compounds such as benzenesulfonic acid and vinylsulfuric acid, and the like.

(2-methyl) propenoic acid phosphohydroxyethyl, (2-methyl) propenoic acid phosphooxypropyl, (2-methyl) propenoic acid phospho Chloro-2-acid phosphoxypropyl, (2-methyl) propenoic acid, 3-chloro-2-acid phosphohydroxyethyl, (2-methyl) propenoic acid phosphorophosphate oxide (the number of mols of addition of ethenoxide: 4 to 10), (2-methyl) propenoic acid phosphorophosphate And (2-methyl) propenoic acid esters having a phosphonyl group such as oxypropene oxide (number of moles of propene oxide added: 4 to 10), and the like.

(2-methyl) propenoic acid 4-hydroxybutyl (2-methyl) propenoic acid is preferable.

The amount of the?,? - unsaturated compound (m-2) having an active hydrogen group in the 100 parts by weight of the?,? - unsaturated compound used for copolymerization of the copolymer (B) is preferably 0.01 to 20 parts by weight, By weight, more preferably from 0.2 to 5 parts by weight. When the amount is less than 0.01 part by weight, it is difficult to obtain an effect of improving the cohesion by the effect of improving the molecular weight by the curing reaction caused by the crosslinking with the functional group contained in the cross-linking agent (C) described later. If the amount is more than 20 parts by weight, the curing shrinkage due to the curing reaction becomes prominent, and a sufficient adhesive force may not be obtained in some cases. The range of 0.2 to 5 parts by weight improves the molecular weight due to crosslinking of the cured coating film and secures an internal cohesive force capable of exhibiting entropy elasticity and is more preferable because it hardly causes curing shrinkage.

As described above, by giving the entropy elasticity to the cured coating film, it is possible to follow the gentle expansion and contraction movement of the substrate due to the environmental change, and the decrease in the adhesion force can be prevented.

(m-2) may be used singly or in combination of two or more.

As the other copolymerizable alpha, beta -unsaturated compound (m-3) used in the copolymer (A) and the copolymer (B), an alpha, beta -unsaturated compound copolymerizable with (m- do.

For example, N-alkoxyl group-containing acrylamides such as N-methyl-N-methoxyacrylamide and N-methyl-N-methoxy methacrylamide;

Propyl (2-methyl) propenoate, 2-propyl (2-methyl) propenoate, Butyl (2-methyl) propanoate, tert-butyl (2-methyl) propane, n-amyl 2-ethylhexyl (2-methyl) propenoate, n-octyl (2-methyl) propene, Propenyl dodecyl, (2-methyl) propenoic acid dodecyl, (2-methyl) propenoic acid dodecyl, (2-methyl) (2-methyl) propenoic acid alkyl esters such as lauryl (2-methyl) propenoate and stearyl (2-methyl) propenoate;

For example, there can be mentioned (2-methyl) propenoic acid cyclohexyl, (2-methyl) propenoic acid benzyl, (2-methyl) (2-methyl) propenoic acid-1, 4-dioxaspiro [4,5] -decarboxylic acid dicyclopentenyl, (2-methyl) (2-methyl) propenoic acid tricyclopentenyl (2-methyl) propenate-1-adamantyl, (2-methyl) propenoic acid tricyclopentanyloxyethyl, (2-methyl) propenoic acid cyclic esters such as (2-methyl) propenoic acid-2-ethyl-2-adamantyl;

Examples thereof include (2-methyl) propenoic acid polyethenoxide, methyl (2-methyl) propenoate, poly (2-methyl) propenoate, poly (2-methyl) propenoate, poly (2-methyl) propenoate, (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, Phenylnonyl, (2-methyl) propenoic acid polypropene oxide, phenyl paracoolyl, and other alkoxypoly Alkyl glycol-containing (2-methyl) propene acid derivatives;

For example, ethynylbenzenes such as ethenylnaphthalene and ethenylanthracene;

(2-methyl) propenoic acid allyl, (2-methyl) propenoic acid 1-methylallyl, (2-methyl) (2-methyl) propenoic acid 2-butenyl, (2-methyl) propenoic acid 3-butenyl, (2-methyl) propenoic acid, 2- (allyloxy) ethyl, (2-methyl) propenoic acid, (2-methyl) propenic acid cinnamyl, (2-methyl) propenesulfonyl, (2-methyl) (2-methyl) propenoic acid esters further containing an unsaturated group such as pentanoyl, heptyl, and pentanoyl;

(2-methyl) propenoic acid perfluoroethyl, (2-methyl) propenoic acid perfluoroethyl, (2-methyl) (2-methyl) propane acid perfluorooctyl, (2-methyl) propenoic acid trifluoromethyl methyl, (2-methyl) propenoic acid 2-trifluoromethyl ethyl, Perfluoroethylmethyl, (2-methyl) propenoic acid, 2-perfluoroethylmethyl (2-methyl) (2-methyl) propenoic acid, 2-perfluorohexylethyl (2-methyl) propenoate, 2-perfluorohexylethyl (2-methyl) propenyl-2,6-dibromo-4-butylphenyl, 2-methylpiperidylethyl, Propane-2,4,6-tribromophenoxyethyl, (2-methyl) propen-2, 4, Bromophenol ethene oxide adduct (ethene oxide addition molar number: 4-12), a halogen-containing (2-methyl) prop pensan alkyl esters and the like;

(3-methyl-3-oxetanyl) propenoic acid (3-methyl-3-oxacyclohexyl) (2-methyl) propenoic acid esters having an oxygen atom and containing heterocyclic rings such as methyl, (2-methyl) propenoate tetrahydrofurfuryl;

For example, 3- (2-methylpropane-2-enoyloxypropyl) trimethoxysilane, 3- (2-methylpropane-2-enoyloxypropyl) triethoxysilane, 3- 3- (2-methylpropan-2-enoyloxypropyl) triisopropoxysilane, 3- (2-methylpropan-2-enoyloxypropyl) methyldimethoxysilane, 3- Alkoxysilyl group-containing (2-methyl) propenoic esters such as diethoxysilane and 3- (propane-2-enoyloxypropyl) trimethoxysilane;

As the amino group-containing?,? - unsaturated compound

(2-methyl) propenoic acid N, N-dimethylaminoethyl, (2-methyl) propenoic acid, N- (2-methyl) propenoic acid esters having an amino group having a chain amino group such as N, N-diethylaminoethyl propenoate;

For example, a ring having one nitrogen atom such as (2-methyl) propenoic acid morpholinoethyl, (2-methyl) propenoic acid pentamethylpiperidinyl, (2-methyl) (2-methyl) propenoic acid ester having a formylamino group;

For example, there can be mentioned 2-ethynylpyridine, 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, Pyrrole, 1-benzyl-2-ethenyl-1H-pyrrole, 2- (1-pyrroyl) ethyl vinyl ether, 1- 3-bromo-4- (1-iodo-2-perfluorobutyl-ethenyl) thiophene, 2- Phenyl] -ethenyl] - thiophene, 5- [4- [2- [4-diphenyl-phenyl- (4-diphenylamino-phenyl) -ethenyl] -benzaldehyde, diethenyl ethylurea, and the like A cyclic amino group having a nitrogen atom Heterocyclic Ethereal nilryu that;

Pyrrol-2,5-dione, 1-ethyl-lH-pyrrole-2,5-dione, 1-propyl-lH-pyrrole- Pyrrole-2,5-dione, 1-butyl-1H-pyrrole-2,5-dione, 1-octyl- Containing nitrogen atoms such as stearyl-1H-pyrrole-2,5-dione, 1-phenyl-1H-pyrrole-2,5-dione and 1-cyclohexyl- Lt; / RTI >derivative;

(2-methyl) propene acid ethenoxide, di (2-methyl) propene triene oxide, di (2-methyl) propenoate tetraenetoxide, di (2-methyl) propene acid dipropene oxide, di (2-methyl) propene acid tripropene oxide, di (2-methyl (2-methyl) propene pentenoic acid, di (2-methyl) propenoic acid, 2,2-dimethylpropyl, di (2-methyl) propenoic acid hydroxypivalate monohydroxypivalate dicaprolactonate, di (2-methyl) propenoic acid 1,6-hexane Di (2-methyl) propenoic acid 1,2-hexanediol, di (2-methyl) propenoic acid 1,5-hexanediol, di -methyl (2-methyl) propenoic acid 1, di (2-methyl) propenoic acid 1,1-octanediol, di Decanediol, di (2-methyl) propenoic acid, 1,2-decanediol, di (2-methyl) Dodecanediol di (2-methyl) propenoate, 1,12-dodecanediol di (2-methyl) Hexadecanediol di (2-methyl) propenoic acid, 1,2-tetradecanediol di (2-methyl) Methyl-2, 5-pentanediol di (2-methyl) propenoic acid 2-methyl- 1,3-propanediol, di (2-methyl) propenoic acid 2,4-dimethyl-2,4-pentanediol, di (2- Di (2-methyl) propenoic acid 2,2,4-trimethyl-1,3-pentanediol, di (2-methyl) Dimethyl-2,5-hexanediol, di (2-methyl) propenoic acid 2-ethyl-1,3-hexanediol, 2-ethyl-1,3-propanediol di (2-methyl) propenoate, 2,4-diethyl 1,2-hexanediol di (2-methyl) propenate, 1,5-hexanediol di (2-methyl) Hexanediol, di (2-methyl) propenoic acid 1,7-heptanediol, di (2-methyl) propenoic acid 1,8-octanediol, di (2- (2-methyl) propenoic acid 1,10-dione diol, di (2-methyl) propane 1,1- (2-methyl) propenoic acid, di (2-methyl) propenoic acid, 1,2-dodecanediol di Di (2-methyl) propenoic acid, 1,2-tetradecanediol, di (2-methyl) Di (2-methyl) propene-2-hexadecanediol, di (2-methyl) Propane-1,3-propanediol, di (2-methyl) propene 2,4-dimethyl-2,4-pentanediol, di (2- Propane diol, di (2-methyl) propenoic acid, 2,2,4-trimethyl-1,3-pentanediol, di (2- Butyl-2-ethyl-1, 2-ethyl-1,3-hexanediol, di (2-methyl) propenoic acid 2,5- Propane diol, di (2-methyl) propenoic acid 2,4-diethyl-1,5-pentanediol, di (2-methyl) propenoic acid 1,1,1- Methyl) propene-based bifunctional derivative;

Di (2-methyl) propenic acid tricyclodecane dimethylol, di (2-methyl) propenoic tricyclodecane dimethylol dicaprolactonate, di ) Propane tetraethylene oxide adduct, di (2-methyl) propene-2,2-bis (hydroxyphenyl) methane tetraethyleneoxide adduct, di (2-methyl) '-Tetraene oxide adduct of sulfonyldiphenol, a tetraethylene oxide adduct of 2,2-bis (hydroxyphenyl) propane with di (2-methyl) Bis (hydroxyphenyl) methane added with di (2-methyl) propenic acid-water, 2,2-bis (hydroxyphenyl) Bis (hydroxyphenyl) methane and di (2-methyl) propenic acid-2,2-bis (hydroxyphenyl) propane added with 2,2-bis (hydroxyphenyl) Prolactonate, di (2- ) Pro pensan-2,2-bis (hydroxyphenyl) Ten oxide adduct to a solution of methane-dicarboxylic Pro Lactobacillus carbonate (2-methyl) propene-based bifunctional derivatives;

Trifunctional monomers such as tri (2-methyl) propane glycerin, tri (2-methyl) propene trimethylol propane, tri (2-methyl) propene trimethylol propane triethylene oxide, tri Tri (2-methyl) propane trimethylol ethane, tri (2-methyl) propenoate trimethylol hexane, tri (2-methyl) Trifunctional (meth) acrylates such as propane pentaerythritol, tri (2-methyl) propenoate 1,1,1-trishydroxymethylethane and 1,1,1-tris (hydroxymethyl) 2-methyl) propenoic acid esters;

(4-methyl) propane pentaerythritol, tetra (2-methyl) propane pentaerythritol tetracaprolactonate, tetra (2-methyl) propenoic acid, glycerin, tetra ) Propene ditrimethylol propane, tetra (2-methyl) propenoic acid ditrimethylolpropane tetracaprolactonate, tetra (2-methyl) propenoate ditrimethylolethane, tetra (2-methyl) , Dipentaerythritol tetra (2-methyl) propenoate, dipentaerythritol hexa (2-methyl) propane, dipentaerythritol hexa Hepta (2-methyl) propene acid tripentaerythritol, octa (2-methyl) propene acid tripentaerythritol, hepta (2-methyl) Dipentaerythritol polyalkene graphite and other polyfunctional (2- Naphthyl) prop pensan esters;

Examples of the organic peroxide include organic peroxides such as 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 Lauryl 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, Decylphenylmethylhexyl ether, ethenylphenylmethylhexyl ether, ethenylphenylmethylhexyl ether, ethenylphenylmethylhexyl ether, ethenylphenylmethylhexyl ether, ethenylphenylmethylhexyl ether, ethenylphenylmethylhexyl ether, ethenylphenylmethylhexyl ether, Heptyl ether, ethenyl phenyl methyl octyl ether, ethenyl phenyl methyl nonyl ether, ethenyl phenyl methyl decyl ether, ethenyl phenyl methyl Decyl ether, decyl ether, decyl ether, ethenyl phenyl methyl lauryl 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 , Aromatic ethenyls having long-chain alkyl groups such as ethenyl phenyl methyl octadecyl ether, ethenyl phenyl methyl nonadecyl ether, ethenyl phenyl methyl eicosyl ether, ethenyl phenyl methyl hexoxyl ether, ethenyl phenyl methyl docosyl ether Ethers;

For example, isopropenylphenylmethylbutyl ether, isopropenylphenylmethylpentylether, isopropenylphenylmethylhexylether, isopropenylphenylmethylheptylether, isopropenylphenylmethyloctylether, isopropenylphenylmethylnonyl Isopropenylphenylmethyldecyldecyl ether, isopropenylphenylmethyldecyldecyl ether, isopropenylphenylmethyldecyldecyl ether, isopropenylphenylmethyltridecyl ether, isopropenylphenylmethyltetradecyl ether, isopropenylphenylmethyldecyldecyl ether, isopropenylphenylmethyldecyldecyl ether, Isopropenylphenylmethyloctadecyl ether, isopropenylphenylmethylnonadecyl ether, isopropenylphenylmethyl octadecyl ether, isopropenylphenylmethyl octadecyl ether, isopropenylphenylmethyl nonadecyl ether, isopropenylphenylmethyl octadecyl ether, Isopropenylphenylmethylhexecyl ether, isopropenylphenylmethyldodeco Isopropenylphenyls having a long-chain alkyl group such as a silyl ether;

For example, hexyl 4-ethenylbenzenecarboxylate, octyl 4-ethenylbenzenecarbonate, nonyl 4-ethenylbenzenecarbonate, decyl 4-ethenylbenzenecarboxylate, dodecyl 4-ethenylbenzenecarboxylate, 4-ethenylbenzenecarboxylic acid tetradecyl, 4-ethenylbenzenecarboxylic acid hexadecyl, 4-ethenylbenzenecarboxylic acid octadecyl, 4-ethenylbenzenecarboxylic acid eicosyl, 4-ethenylbenzenecarboxylic acid docosyl, 4-isopropenylbenzenecarboxylic acid decyl, 4-isopropenylbenzenecarboxylic acid decyl, 4-isopropenylbenzenecarboxylic acid dodecyl, , Tetradecyl 4-isopropenylbenzenecarboxylate, hexadecyl 4-isopropenylbenzenecarboxylate, octadecyl 4-isopropenylbenzenecarboxylate, eicosyl 4-isopropenylbenzenecarboxylate, 4-isopropenyl Benzenecarboxylic acid docosyl and other long-chain alkyl groups. Reuryu or isopropenyl benzene carboxylic acid esters;

For example, it is possible to use an organic peroxide such as ethenylbenzene,? -Isopropenylbenzene,? -Isopropenylbenzene, 1-methylethenylbenzene, 2-methylethenylbenzene, 3-methylethenylbenzene, Aromatic ethers such as 1-chloro-4-isopropenylbenzene;

(Ethene oxide) ethenyl phenyl ether, propyl tetra (ethene oxide) ethenyl phenyl ether, n-butyl (ethene oxide) ethenyl phenyl ether, methyl tetra Tetraphenyl ethers such as tetra (ethene oxide) ethenyl phenyl ether, n-pentyl tetra (ethenoxide) ethenyl phenyl ether, tetra (propene oxide) ethenyl phenyl ether, methyl tetra (propene oxide) ethenyl phenyl ether, ethyl tetra (Pentenoic) ethenyl phenyl ether, propoxytetra (propene oxide) ethenyl phenyl ether, n-butyl tetra (propene oxide) ethenyl phenyl ether, n-pentoxy cetetra (Ethene oxide) ethenyl phenyl ether, methyl poly (ethene oxide) ethenyl phenyl ether, ethyl poly (ethene oxide) ethenyl phenyl ether, poly (propene oxide) ethenyl (Ethene oxide) ethenylbenzyl ether, ethylpoly (ethylene oxide) ethenylphenyl ether, ethyl poly (propene oxide) ethenyl phenyl ether, poly (ethene oxide) ethenyl benzyl ether, (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) (Phenylphenyl) ethyl ether, methylpoly (ethylene oxide) ethenyl phenyl ethyl ether, ethyl poly (ethene oxide) ethenyl phenyl ethyl ether, poly (oxypropylene) Ether, ethynylbenzenes having a long chain polyalkenoic oxide moiety such as ethylpoly (propene oxide) ethenyl phenylethyl ether;

For example, there may be mentioned poly (ethylene oxide) isopropenylphenyl ether, poly (ethylene oxide) isopropenylphenyl ether, methylpoly (ethylene oxide) isopropenylphenyl ether, (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, Isopropenyl having polyalkene oxide moieties such as ethylpoly (ethylene oxide) isopropenyl benzyl ether, poly (propene oxide) isopropenyl benzyl ether, methyl poly (propene oxide) isopropenyl benzyl ether;

For example, fluorine-containing ethers such as perfluoroethane, perfluoropropene, perfluoro (propylenetereether), and fluorinated ethenylidene;

For example, trienyloxysilyl group-containing ethers such as ethenyltrimethoxysilane and ethenyltriethoxysilane;

For example, there may be mentioned ethynylenevinylenes such as octenyl ethanoate, octenyl propanoate, octenyl pivalate, ethenyl benzenecarboxylate, 3-phenyl-2-propenoate, diallyl cis- (Z) -octadec-9-ene ethenyl, (9Z, 12Z, 15Z) -octadeca-9,12,15-trienoate ethenyl Ethynyl esters such as ethyleneglycol;

Nitrile group-containing ethers such as 2-propenenitrile, 2-methyl-2-propenenitrile and (2-methyl) propenoic acid 2-cyanoethyl;

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

Butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 1-tetracosene, 1-hexacosene, 1-octacosene, 1-toriacotene, 1 -dryriacontene, 1-tetratriacotene, 1- Hexatriacotene, 1-octatriacotene, 1-tetracotene, etc., and mixtures thereof;

Examples thereof include dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene and 2-chloro-1,3-butadiene;

For example, chloroethene, 1,1-dichloroethene, allyl chloride, allyl alcohol, and the like, but the present invention is not limited thereto.

For example, a copolymer of an?,? - unsaturated compound having at least one propane-2-enoyl group and 2-methylpropane-2-enoyl group in the molecule and having?,? - unsaturated double Polymeric copolymers of the high molecular weight type with bonds, so-called macromonomers.

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

Next, the polymerization initiator used in producing the copolymer (A) and the copolymer (B) will be described. The copolymer (A) and the copolymer (B) of the present invention contain 0.001 to 20 parts by weight of a polymerization initiator per 100 parts by weight of the total of the various?,? - unsaturated compounds (m-1) to (m-3) Is synthesized by methods such as bulk polymerization solution polymerization, emulsion polymerization, suspension polymerization and the like. Preferably synthesized in solution polymerization.

Examples of the polymerization initiator include 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutanenitrile), 1,1'-azobis (cyclohexane 1-carbonitrile Azo compounds such as 2,2'-azobis (2,4-dimethylpentanonitrile), 2,2'-azobis (2,4-dimethyl-4-methoxypentaronitrile) Azo compounds such as bis (2-methylpropionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2-hydroxymethylpropionitrile) And [2- (2-imidazolin-2-yl) propane].

Also, examples of the organic peroxides include dibenzoyl dioxides, tert-butyl perbenzoate, tert-butyl peroxypivalate, tert-hexyl peroxy pivalate, octanoyl peroxide, lauroyl peroxide, cumene hydroperoxide, Butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-butyl (2-ethoxyethyl) peroxydicarbonate, Organic peroxides such as peroxy pivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide.

In the synthesis, it is also preferable to use chain transfer agents such as mercaptans such as lauryl mercaptan and n-dodecyl mercaptan,? -Methylstyrene dimer and limonene.

Among them, 2,2'-azobisisobutyronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and dibenzoyl dioxidane, tert-butyl azodicarboxylate and the like are preferable from the viewpoints of molecular weight control and molecular weight distribution control. Butyl perbenzoate, tert-butyl peroxypivalate, tert-hexyl peroxy pivalate, octanoyl peroxide, lauroyl peroxide, and tert-butyl peroxy-2-ethylhexanoate are preferable.

When the copolymer (A) and the copolymer (B) are prepared by a solution polymerization method, examples of the solvent include aromatic solvents such as methylbenzene and 1,2-dimethylbenzene; Alcohol-based solvents such as ethanol, propan-2-ol and 1-butanol; Ether-based solvents such as 1-methoxy-2-propanol, (2-methoxymethylethoxy) -propanol, 2-ethoxyethanol and 2-butoxyethanol; Ester solvents such as ethyl acetate, butyl acetate, and 2-ethoxyethanol acetate; Ketone solvents such as 2-propanone, 2-butanone, 4-methyl-2-pentanone and 2,4-pentanedione; And organic solvents such as an amide solvent such as dimethylformamide. However, the present invention is not limited to these 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?,? - unsaturated compounds (m-1) to (m-3) components and the viscosity and concentration of the copolymer (A) and the copolymer do.

The polymerization conditions for producing the copolymer (A) and the copolymer (B) may be suitably set according to the polymerization method, and are not particularly limited. The polymerization temperature is preferably room temperature to 150 ° C, more preferably 40 to 120 ° C. The reaction time may be suitably set so that the polymerization reaction of the components of the?,? - unsaturated compounds (m-1) to (m-3) is completed.

≪ Crosslinking agent (C) >

Next, the crosslinking agent (C) will be described. The crosslinking agent (C) can be used without limitation as long as it can cure with the copolymer (A) and the copolymer (B). When (m-1) is used as the?,? -Unsaturated compound for the copolymer (A), the functional group contained in the compound (m-1) (at least one kind selected from the group consisting of a carboxyl group, an amide group, a carbonyl group and an N-alkoxyalkyl group Functional group) is preferably used. When (m-2) is used as the?,? - unsaturated compound for the copolymer (B), a crosslinking agent which reacts with a functional group having an active hydrogen group contained in the compound (m-2) is preferable. The crosslinking agent (C) may be used alone or in combination. A crosslinking agent capable of reacting with both the copolymer (A) and the copolymer (B) can be used, or a crosslinking agent (C) capable of reacting with the copolymer (A) (C) may be used in combination.

The cross-linking agent (C) improves the molecular weight of the cured coating film of the resin composition for sheet bonding and improves the internal cohesive force for manifesting energy elasticity, and can also be expected to have an effect of improving the interaction with the substrate surface described later. (A) and the copolymer (B) and the substrate (B) by chemically reacting the reactive functional group in the cross-linking agent (C) with the substrate, for the substrate subjected to the chemical treatment modified with physical treatment such as corona discharge treatment or acid treatment Can exhibit a strong interaction with the substrate. By using the crosslinking agent (C) in this way, it is possible to form a hardened coating film, so that the expansion and contraction movement of the substrate due to a sudden change in the environment can be suppressed by the crosslinking agent (C) exhibiting energy elasticity.

As the crosslinking agent (C), a polyisocyanate compound (c-1), a polyfunctional epoxy compound (c-2), a metal chelate compound (c-3) and a polycarbodiimide compound (c- Polycarbodiimide compounds), N-methylol group-containing compounds, and aziridine compounds (c-5) (more preferably polyfunctional aziridine compounds).

Among them, the curing reaction by crosslinking of the crosslinking agent (C) effectively works, and it is possible to react with the carboxyl group, the amide group, the carbonyl group and the N-alkoxyalkyl group in the copolymer (A) A compound having two or more functional groups in the molecule is preferable. Particularly, the polyisocyanate compound is preferably used because it is excellent in adhesion of the resin composition for sheet bonding after the curing reaction.

The polyisocyanate compound (c-1) in the crosslinking agent (C) may be any compound having a plurality of isocyanate groups in the molecule and is not particularly limited. Examples of polyisocyanate compounds include, but are not limited to, triethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl xylene Polyisocyanate compounds such as diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate and polymethylene polyphenyl isocyanate, and polyisocyanate compounds such as polyol compounds such as 2- (hydroxymethyl) -2-ethylpropane-1,3-diol An isocyanate compound of these polyisocyanate compounds, or a mixture of these polyisocyanate compounds with known polyether polyols or polyester polyols, polypropene acid alkyl polyols, polybutadiene polyisocyanates, Diene may be a polyol, such as the air duct member as polyisoprene polyol.

Of these, from the viewpoints of the pot life immediately after the addition of the resin composition for sheet bonding, the control of the reaction rate after the coating, and the improvement of the transparency of the coating film, a buret of hexamethylene diisocyanate (c-1-1), which is an aliphatic polyisocyanate (C-2) isocyanurate, adducts of hexamethylene diisocyanate with known polyether polyols, polyester polyols, polypropene acid alkyl polyols, polybutadiene polyols, polyisoprene polyols and the like, alicyclic polyisocyanate compounds 1-2) phosphorus, isophorone diisocyanate, hydrogenated xylylene diisocyanate, buretecene isocyanurate of hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate and Known polyether polyols or poly Thermal polyols, polypropylene is preferred pensan body alkyl-based polyol, polybutadiene polyol, polyisoprene polyol as air ducts.

From the viewpoints of adhesion of the resin composition for sheet bonding, resistance to heat and humidity after the curing reaction, and transparency, it is particularly preferable to use an adduct of hexamethylene diisocyanate and 2- (hydroxymethyl) -2-ethylpropane- Hexamethylene diisocyanate isocyanurate, hexamethylene diisocyanate burette (c-1-1), isophorone diisocyanate and 2- (hydroxymethyl) -2-ethylpropane-1,3-diol A duct body, and an isophorone diisocyanate isocyanurate trimer (c-1-2) are preferable.

The polyfunctional epoxy compound (c-2) is preferably a compound having a plurality of epoxy groups in the molecule and is not particularly limited. Examples of the polyfunctional epoxy compound include ethylene glycol diglycidyl ether, polyethyleneglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A epichlorohydrin type epoxy resin, N, N, (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N'-tetraglycidyl-m-xylenediamine, Diglycidyltoluidine, and the like.

As a high molecular weight polycarbodiimide compound, Carbodite series of Nisshin Sekisui is listed. Of these, carboditlite V-01, 03, 05, 07 and 09 are preferable because they have good compatibility with organic solvents.

Examples of the polyfunctional aziridine compound include 2,2'-bis hydroxymethyl butanol tris [3- (1-aziridinyl) propionate], 4,4'-bis (ethyleneiminocarbonylamino) diphenyl methane And the like.

Examples of the metal chelate compound (c-3) include polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium, Butanoate and the like.

The crosslinking agent (C) can be used alone or in combination.

The crosslinking agent (C) is preferably added in an amount of 0.1 to 30 parts by weight, more preferably 1 to 25 parts by weight, and still more preferably 2 to 15 parts by weight per 100 parts by weight of the total of the copolymer (A) and the copolymer (B) Parts by weight. If the amount of the crosslinking agent (C) is less than 0.1 parts by weight, the effect of improving the molecular weight of the cured coating film due to the curing reaction can not be obtained, and the energy elasticity is not sufficiently exhibited. If the amount exceeds 30 parts by weight, excess crosslinking agent (C) may remain unreacted in the resin composition for sheet bonding to deteriorate the adhesive strength. When the resin composition for sheet bonding is used for bonding two films, The cross-linking agent (C) undergoes a curing reaction due to crosslinking, resulting in deterioration such as excessively high energy elasticity of the resin composition for sheet bonding or deterioration of wettability to the substrate. The range of 2 to 15 parts by weight is more preferable in terms of the effect of improving the cohesive force and the effect of reducing the residual crosslinking agent.

<Resin composition for sheet bonding>

Next, the resin composition for sheet bonding will be described.

The resin composition for sheet bonding of the present invention is characterized by containing a copolymer (A), a copolymer (B) and a crosslinking agent (C), wherein the copolymer (A), the copolymer (B) and the crosslinking agent Called 3-liquid mixed type resin composition for sheet bonding is also preferable, and a copolymer mixture in which a copolymer (A) and a copolymer (B) are mixed in advance and a crosslinking agent (C) , And a resin composition for sheet bonding of a one-liquid type in which a main resin and a cross-linking agent (C) are preliminarily mixed may be used depending on the conditions of use.

The copolymer (A), the copolymer (B) and the cross-linking agent (C) may be independently used in various types. (B), an organic solvent and other additives, and the second liquid contains a cross-linking agent (C), an organic solvent, and other additives .

The copolymer (A) is preferably contained in an amount of 30 to 95 parts by weight, preferably 40 to 80 parts by weight, more preferably 50 to 70 parts by weight, based on 100 parts by weight of the total of the copolymer (A) and the copolymer (B) It is good to include weight parts. When the amount is less than 30 parts by weight, the cohesive force of the copolymer (B) is remarkably increased, the wettability of the resin composition for sheet bonding is lost, and the adhesiveness to the film during lamination is lowered. , The cohesive force of the cured coating film of the resin composition for sheet bonding is insufficient and the adhesive force is deteriorated due to the tendency of cohesive failure at the time of peeling. A balance between the wettability and the cohesive force of the 50 to 70 part cured coating film is good and high adhesion is often obtained.

The resin composition for sheet bonding of the present invention can provide a cured coating film that does not affect various environmental changes by the curing reaction caused by crosslinking of the copolymer (A), the copolymer (B) and the crosslinking agent (C). Since the function of the copolymer (A) is relatively low Tg and a high molecular weight form, it exhibits effective wettability to various substrates and exhibits stress relaxation property in accordance with the curing reaction by the crosslinking agent. Since the function of the copolymer (B) is high Tg and a low molecular weight type, it exhibits entropy elasticity that follows the expansion and contraction movement of the base material in accordance with gentle environmental change. The crosslinking agent (C) exhibits energy elasticity for suppressing the rapid expansion and contraction movement of the base material because it exhibits a hard constitution due to the magnetic reaction in addition to the curing reaction caused by the crosslinking with both copolymers. The cured coating film resulting from the crosslinking forms an interpenetrating polymer network (IPN) independently expressing the respective characteristics and microscopically forms a multi-layer structure. Thus, the copolymer (A), the copolymer (B ) And the cross-linking agent (C), it is possible to control each viscoelastic behavior, and the present invention can be applied to a wide variety of applications such as change of use environment and applicability of various substrates.

Other additives may be added to the resin composition for sheet bonding of the present invention without departing from the gist of the present invention by adding a silane coupling agent, a tackifier, a leveling agent, a phosphorus-based or phenolic antioxidant, a UV stabilizer, , A fire retardant, a plasticizer, an organic or inorganic pigment, and the like.

When a metal layer (metal foil, metal plate, or the like) is used as the film constituting the solar cell protection sheet, in order to improve the metal adhesiveness of the resin composition for sheet bonding of the present invention, a phosphate compound such as phosphoric acid, Pyrophosphoric acid, phosphorous acid or its ester, etc. may be added.

The resin composition for sheet bonding of the present invention is preferably used as an adhesive for producing a solar cell protective sheet and can also be used as an anchor coat for a solar cell laminate sheet in which thermocompression is performed at a high temperature of 100 DEG C or more for 30 minutes or longer after coating . In this case, it is preferable to add mineral silica such as talc, diatomaceous earth, calcium carbonate, feldspar, quartz and the like and an antiflocculating agent of PMMA (2-methyl-2-propenoate methyl) in order to eliminate stickiness after coating.

In addition, known additives for the resin composition for sheet bonding can be blended without limitation without departing from the gist of the present invention. For example, a known leveling agent or an extinguishing agent may be blended in the resin composition for sheet bonding for the purpose of improving the appearance of the laminate.

Examples of the leveling agent include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified polydimethylsiloxane, polyetherester-modified hydroxyl-containing polydimethylsiloxane, poly Ether-modified polymethylalkylsiloxane, (2-methyl) propenoate alkyl ester copolymer, lecithin, or a mixture thereof.

Examples of the antifoaming agent include known resins such as a silicone resin, an alkylether ethyl ether and a (2-methyl) propenoate alkyl ester copolymer, or a mixture thereof. When a leveling agent and an extinguishing agent are added, one compound may be used independently or two or more compounds may be arbitrarily used in combination.

As known additives to be used in the present invention, known additives such as phosphorus-based and phenol-based antioxidants, ultraviolet stabilizers, antioxidants, antioxidants, antioxidants, antioxidants, A metal deactivating agent can be incorporated into the resin composition for sheet bonding. These may be used alone or in combination of two or more. The phosphorus-based and phenol-based antioxidants, ultraviolet stabilizers and metal deactivators used in the present invention are preferably used in an amount of 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the solid content of the copolymer (A) to be. If the addition amount is less than 0.05 part by weight, a sufficient deterioration yellowing suppressing effect may not be obtained, and if it is more than 20 parts by weight, the adhesive force of the resin composition for sheet bonding can be significantly deteriorated.

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

Examples of the solvent for use in the resin composition for sheet bonding include ester solvents such as ethyl ethanoate, butyl ethane and 2-ethoxyethanol acetate; Ketone solvents such as 2-propanone, 2-butanone, 4-methyl-2-pentanone and 2,4-pentanedione; Aromatic solvents such as methylbenzene and 1,2-dimethylbenzene; Halogenated hydrocarbons such as methylene chloride and ethylene chloride; and amide solvents such as dimethylformamide. As the solvent to be used, one type of solvent may be used, or two or more solvents may be arbitrarily used.

Next, a laminate comprising the resin composition for sheet bonding will be described.

A commonly used method can be used to produce a multilayer film as a typical laminate using the resin composition for sheet bonding according to the present invention. For example, a resin composition for sheet bonding may be coated on one side of one side of a film by a comma coater or a dry laminator, the solvent may be volatilized if necessary, the other side of the film to be laminated may be cured, You. The resin composition for sheet bonding to be applied to the film is preferably about 1 to 50 g / m 2. When constituting a multilayer of three or more layers, it is possible to use the resin composition for sheet bonding according to the present invention in all or a part when the films of the respective layers are bonded together.

The resin composition for sheet bonding of the present invention is produced by applying a resin composition for sheet bonding to a film, drying and laminating the films, and curing the laminate at 20 to 60 DEG C for several days. The curing reaction of the copolymer (A) and the copolymer (B) and the crosslinking agent (C) is promoted by the curing process (dark reaction process), and the viscoelastic behavior can be controlled while improving the interaction with the laminated film.

Next, the laminate of the present invention will be described. The laminate of the present invention can be formed by laminating a layer made of the resin composition for sheet bonding of the present invention on one side or both sides of a substrate (G). Examples of the substrate G include a plastic film (including a plastic sheet), a metal foil, and the like, and appropriately selected according to the properties required for the laminate.

For example, waterproofing properties can be imparted by using a plastic film or a metal foil on which a polyolefin film and a metal oxide or a non-metal inorganic oxide are deposited, by using a polyester film to be described later and by using a fluorine film And the like.

Examples of the plastic film include polyester-based resin films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN); Polyvinylidene fluoride, polychlorotrifluoroethylene, polyethylene tetrafluoroethylene, Teflon, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, etc. Based resin film; Polyolefin films such as polyethylene resin films such as low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) and polypropylene type resin films; A polyvinyl chloride resin film, a polycarbonate resin film, a polysulfone resin film, and a poly (2-methyl) propenoic acid resin film.

The above plastic film can be used as a plastic film in which the surface is subjected to physical treatments such as corona discharge, plasma treatment and frame treatment and chemical treatment for improving the film surface by acid or alkali, a film having fine irregularities on the film surface, With respect to the composition, those which have been subjected to easy adhesion treatment can be preferably used.

As the plastic film on which the metal oxide or the non-metal inorganic oxide is deposited, an oxide such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium or yttrium is deposited on the plastic film . Polyethylene terephthalate (PET) is suitably used as the plastic film used for deposition.

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

With respect to the laminated film, those colored with black or white can also be used for the purpose of improving the designability or improving the light reflectance and improving the conversion efficiency of the solar cell.

When the laminate is formed into a composite structure, as a method for developing an excellent adhesive force of the resin composition for sheet bonding according to the present invention, for example, a polyester resin film or a fluorine resin film, It is possible to increase the interaction with the substrate in the heating and solvent removal process, and it is more preferably used because it is coated on the film surface which is very difficult to adhere to an olefin substrate such as polypropylene.

Next, a solar cell protective sheet using a laminate obtained by laminating a layer made of the resin composition for sheet bonding of the present invention on one side or both sides of a substrate (G) and a method for producing the same will be described. As described in the background art, various manufacturing methods and configurations can be employed in accordance with the purposes and requirements of heat resistance, weather resistance, water vapor permeability, electrical insulation, and the like, as well as the manufacturing method and construction of the solar cell protection sheet.

Among these films, polyethylene terephthalate (PET) having resistance to the temperature among the above-mentioned films is used in order to meet the performance of weather resistance, water vapor permeability, electrical insulation, mechanical characteristics, , Polyethylene naphthalate (PEN), a polycarbonate-based resin film, and a polyolefin-based film for preventing the power output of the solar cell due to the influence of water, or a metal oxide or non- A metal foil such as a plastic film or an aluminum foil on which an oxide is deposited, and a solar cell protection sheet in which a weather resistant polyolefin film or a fluorine resin film is laminated is preferable in order to prevent appearance defect due to light deterioration.

The resin composition for sheet bonding of the present invention is characterized by having excellent weatherability and high transparency. The solar cell protective sheet of the present invention can not deteriorate the light transmittance even when used as a protective sheet on the light receiving surface side, and can exhibit excellent power generation efficiency. Therefore, it is possible to use it as a surface protective sheet and a back protective sheet.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. In the Examples, parts by weight in solid conversion and% is by weight.

Production Example 1 (Synthesis Example A-1)

&Lt; Preparation of Copolymer (A) >

A?,? - unsaturated (meth) acrylate having a functional group selected from the group consisting of the following monomers, carboxyl groups, amino groups and amide groups in a polymerization tank and a dropping apparatus of a polymerization apparatus equipped with a polymerization apparatus, a stirrer thermometer, a reflux condenser, a dropping apparatus, The compound (m-1), the?,? -Unsaturated compound (m-3), the polymerization initiator and the solvent were respectively introduced in the following proportions.

[Polymerization tank]

 Ethyl acetate: 100 parts

[Loading device]

 2-methyl-2-propenoic acid (m-1-2): 9 parts

 2-ethylhexyl propenoate (m-3-4): 86 parts

 Methyl 2-methyl-2-propenoate (m-3-6): 5 parts

 Ethyl acetate: 51.8 parts

 2,2'-azobisisobutyronitrile: 1.2 parts

The air in the polymerization vessel was replaced with nitrogen gas, and the mixture was dropped in a dropping apparatus at a reflux temperature of 78 ° C of ethyl ethane under a nitrogen atmosphere while mixing. The mixture was dripped for 2 hours, aged for 6 hours while stirring further, and then cooled to obtain a resin solution containing the copolymer (A-1). This solution was colorless transparent and had a nonvolatile content of 40.3% by weight. The copolymer (A-1) had a weight-average molecular weight of 82,000 and a molecular weight distribution of 2.3 according to the method described below. The calculated Tg was -35.2 占 폚.

Production Examples 2 to 11 (Synthesis Examples A-2 to 11)

A resin solution of Copolymers (A-2) to (A-11) was obtained in the same manner as in Synthesis Example 1 except that the raw materials and amounts shown in Table 1 were used.

Name of sample Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Production Example 6 Production Example 7 Production Example 8 Production Example 9 Production Example 10 Production Example 11 Copolymer
(A) Resin No A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 (M-1) (m-1-1) 1.2 1.2 1.2 4.0 7.0 (m-1-2) 9.0 (m-1-3) 4.0 2.0 (m-1-4) 4.0 (m-1-5) 8.0 (m-1-6) 5.0 (M-3)
(m-3-2) 71.0 80.0 (m-3-3) 25.0 72.0 73.0 52.0 48.0 80.0 72.8 68.0 70.0 (m-3-4) 86.0 (m-3-6) 5.0 26.8 18.0 23.0 42.0 18.8 26.0 28.0 23.0 (m-3-7) 40.0 (m-3-11) 5.0 polymerization
Initiator polymerization
Initiator 1 1.2 0.05 0.7 2 polymerization
Initiator 2 2 3 2.5 1.8 4 1.9 2 solvent Solvent 1 151.8 233.5 153.0 154.5 153.8 151.1 153.0 152.7 156.0 152.9 153.0 Synthesis result Non-volatile matter 40.3 30.5 40.4 40.6 40.2 40.1 40.6 40.4 40.4 40.0 39.9 Weight average
Molecular Weight 82000 810000 213000 180000 205000 63000 86000 280000 96000 210000 234000 Molecular Weight
Distribution 2.3 3.2 4.6 5.2 4.54 2.8 3.4 4.8 2.8 4.1 4.9 Calculation Tg -35.2 -25.1 -19.5 -4.5 -19.6 8.4 7.9 -28.5 4.8 -15.6 -18.7

The abbreviations in Table 1 are as follows.

An?,? - unsaturated compound (m-1) having at least one functional group selected from the group consisting of a carboxyl group, an amide group, a carbonyl group and an N-alkoxyalkyl group "

(m-1-1) propenoic acid,

(m-1-2) 2-methyl-2-propenoic acid,

(m-1-3) 2-methylene succinic acid,

(m-1-4) 2-propenamide,

(m-1-5) 2-methyl-2-propenoic acid 2- (1,3-dioxobutoxy) ethyl,

(m-1-6) N-methoxymethyl-2-propenamide;

Other copolymerizable?,? - unsaturated compounds (m-3) except for (m-1) and (m-2)

(m-3-2) ethyl propionate,

(m-3-3) n-butyl propionate,

(m-3-4) propenyl 2-ethylhexyl,

(m-3-5) iso-propenoate,

(m-3-6) Methyl 2-methyl-2-

(m-3-7) Ethyl 2-methyl-2-propenoate,

(m-3-11) 2-propenenitrile,

(m-3-12) 2-methyl-2-propenic acid N, N-dimethylaminoethyl.

(Polymerization Initiator 1) 2,2'-azobis (2-methylpropionitrile)

(Polymerization initiator 2) tert-Butyl peroxy-2-ethylhexanoate

(Solvent 1) ethyl ethanoate.

Production Examples 12 to 20 (Synthesis Examples B-1 to 9)

(B-1) to (B-9) resin solutions were obtained in the same manner as in Production Example 1 except that the raw materials and amounts shown in Table 2 were used.

Name of sample Manufacturing example
12 Production Example 13 Production Example 14 Production Example 15 Production Example 16 Production Example 17 Production Example 18 Production Example 19 Production example 20 Copolymer (B) Resin No B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 (M-2)


(m-2-1) 10.0 2.0 3.0 0.1 2.0 2.0 (m-2-2) 0.4 0.1 (m-2-3) 8.0 (M-3)





(m-3-1) 10.0 (m-3-2) 34.0 (m-3-3) 38.0 30.0 24.0 11.0 (m-3-4) 35.0 (m-3-6) 75.0 60.0 64.6 64.9 63.0 100.0 74.0 87.0 (m-3-8) 80.0 17.0 (m-3-11) 5.0 polymerization
Initiator polymerization
Initiator 1 1.4 20 10 4 3.5 10 10 10 10 solvent Solvent 1 101.4 120 110 104 103.5 110 110 110 110 Synthesis result


Non-volatile matter 50.3% 49.9% 49.8% 50.1% 50.2% 50.4% 50.5% 49.8% 50.3% Weight average molecular weight 74000 4800 10900 21000 28000 9800 9300 10800 10300 Molecular Weight
Distribution 2.5 2.1 2.3 2.5 2.1 2.0 1.8 2.3 1.9 Calculation Tg 14.7 67.2 25.2 40.8 31 44.6 104.9 49.4 75.7

The abbreviations in Table 2 are as follows. Other copolymerizable alpha, beta -unsaturated compounds (m-3), the polymerization initiator and the solvent which are the same as those in Table 1 are not shown.

?,? -Unsaturated compound (m-2) having an active hydrogen group (except for (m-1)):

(m-2-1) propenoic acid 2-hydroxyethyl,

(m-2-2) 2-methyl-2-propenoic acid 2-hydroxyethyl,

(m-2-3) propene 4-hydroxybutyl,

Other copolymerizable alpha, beta -unsaturated compounds (except for (m-1), (m-2)):

(m-3-1) methyl propionate,

(m-3-8) 2-Methyl-2-propane butyl.

Production Examples 21 to 30

The resin solutions of the copolymers (H-1) to (H-10) were obtained in the same manner as in Production Example 1 except that the raw materials and amounts shown in Table 3 were used.

Name of sample Production Example 21 Production Example 22 Production Example 23 Production Example 24 Production example 25 Production Example 26 Production Example 27 Production Example 28 Production Example 29 Production Example 30
Resin Outline compare
A-1 compare
A-2 Comparison A-3 compare
A-4 compare
B-1 compare
B-2 compare
B-3 compare
B-4 compare
H-1 compare
H-2 Resin No H-1 H-2 H-3 H-4 H-5 H-6 H-7 H-8 H-9 H-10 (M-1) (m-1-1) 7.0 5.0 (m-1-2) 2.0 (M-2) (m-2-1) 1.5 (m-2-2) 4.0 10.0 4.0 (M-3)







(m-3-3) 98.0 75.0 20.0 10.0 5.0 (m-3-4) 33.0 81.0 (m-3-5) 93.0 (m-3-6) 25.0 70.0 70.0 3.0 (m-3-7) 62.0 25.0 (m-3-8) 76.0 20.0 (m-3-9) 85.0 12.0 (m-3-10) 98.5 (m-3-12) 5.0 polymerization
Initiator
polymerization
Initiator 1 0.13 0.1 0.02 0.3 10 2.6 10 0.1 One polymerization
Initiator 2 One solvent Solvent 1 150.2 150.2 151.5 233.4 150.5 110.0 102.6 110.0 100.1 101.0 synthesis
result


Non-volatile matter 39.9% 40.2% 40.3% 29.8% 40.2% 50.2% 50.0% 50.1% 50.3% 50.4% Weight average molecular weight 450000 480000 240000 830000 210000 12000 45000 11000 119000 48000 Molecular Weight
Distribution 3.2 3 4.6 3.6 2.4 2.6 2.1 2.3 2.5 2.1 Calculation Tg
(° C) -48.7 -45.9 15.6 -22.7 74.6 116.9 4.4 24.4 56.6 -34.2

The abbreviations in Table 3 are as follows. The abbreviations shown in Tables 1 and 2 are not shown.

Other copolymerizable alpha, beta -unsaturated compounds (except for (m-1), (m-2)):

(m-3-9) 2-methyl-2-propenecyclohexyl,

(m-3-10) dicyclopentenyl 2-propenate.

<Measurement of number average molecular weight, weight average molecular weight, molecular weight distribution>

The molecular weight and the molecular weight distribution of each of the copolymers obtained in each of Production Examples and Comparative Production Examples were measured by GPC (gel permeation chromatography) using GPC-8020 made by Tosoh Corporation. The sample was dissolved in tetrahydrofuran and tetrahydrofuran was measured with a developing solvent at a rate of 0.6 ml / min and a column temperature of 40 ° C. The polystyrene reduced number average molecular weight and the weight average molecular weight of the copolymer (A) and the copolymer (B) were measured, and the molecular weight distribution was a weight average molecular weight / number average Was calculated from the molecular weight.

Example 1 75 parts by weight of the copolymer (B-1) obtained in Synthesis Example 10 was added to and mixed with 25 parts by weight of the copolymer (A-1) obtained in Synthesis Example 1, 1 (1) Prepolymer of polymethylene polyphenyl isocyanate 13.7 parts by weight of Sumiera Bayer Urethane Sumiju E21-1 (NCO%: 16.0% solids 100%), epoxy compound (c-2): N, N, N ', N '-Tetraglycidyl-m-xylenediamine was added to the flask. To make the nonvolatile content to about 30%, ethyl acetate was added to obtain a frequently-stirred sheet resin composition (S-1).

<Evaluation method of pot life> The viscosity of the obtained resin composition for sheet bonding was measured at 25 ° C for 1 hour, 4 hours, 8 hours, and 24 hours using a B-type viscometer (manufactured by Tokyo Kagaku KK) , And the pot life (pot life) was evaluated in four stages.

aa: No viscosity change. Viscosity increase less than 2 times until 24 hours. Very good.

a: A slight increase in viscosity is recognized, less than 4 hours is recognized, and viscosity increase rate is less than 2 times up to 8 hours. Good.

b: Rapid increase in viscosity is recognized, viscosity increase rate is more than 2 times. There is a problem in practical use.

c: Viscosity increase more than 2 times at 1 hour of addition. There is a problem in practical use.

In Example 1, the viscosity increase rate was 1.3 times at 8 hours, and the viscosity increase rate at 24 hours was 2.4 times.

&Lt; Method of forming laminate > The corona-treated side (hereinafter referred to as &quot; corona treated side &quot;) of a polyester film (Lumirra-X-10S manufactured by Torayi Co., ) Was coated with the resin composition for sheet bonding (S-1) by a dry laminator in such an amount as to give a dry coating amount of 5 to 7 g / m 2. Then, the solvent was volatilized in a drying oven, laminated to a corona-treated polyester film, and then cured at 50 DEG C for 96 hours to obtain a laminated body 1. [

In the same manner, the laminate 2 (corona-treated polyester film / sheet resin composition layer / JIS1N30 soft aluminum foil), laminate 3 [corona-treated polyester film / resin composition layer for sheet adhesion, (Lumirra-X-10S, untreated surface with a thickness of 50 占 퐉) / resin composition layer for sheet adhesion / ETFE (manufactured by Mitsui Chemicals, Inc., trade name: (Resin film for corona-treated polyester film / sheet bonding / corona-treated LLDPE series film (manufactured by Asahi Glass Co., Ltd .: FluonetFE film, thickness 25 탆) ETF (ethylene-tetrafluoroethylene copolymer) film (product of Asahi Glass Co., Ltd.: FluonETFE film, thickness 25 占 퐉) / sheet bonding resin (LL-XUM N # 30 manufactured by Futamura Chemical Co., A composition layer, silicon dioxide (Manufactured by Mitsubishi Plastics, trade name: Tech Barrier)] was formed and evaluated as follows.

&Lt; Coating property evaluation method > The cured state of the obtained laminate 1 was visually observed and evaluated in three steps.

a: A smooth coated surface was obtained. Very good.

b: Some protrusion and foaming are recognized at the end of the coating surface, but it is good.

c: There is a problem in practice because it is recognized that protrusion, foaming, cloudiness or streaking occurs on the coating surface.

In Example 1, a smooth coated surface was obtained, which was very good.

&Lt; Peel strength test before curing > The laminate 1 before curing was cut into a size of 200 mm x 15 mm and allowed to stand for 6 hours under the environment of 25 deg. C and a humidity of 65%, and then subjected to a tensile test using a tensile tester in accordance with the test method of ASTM D1876-61 Deg.] C, and a humidity of 65%, and subjected to a 180 DEG peeling test at a load speed of 100 mm / min.

aa: Peel strength is 2N / 15mm or more. Very good adhesion.

a: peel strength 1N / 15mm or more and less than 2N / 15mm. Excellent adhesion.

b: Peel strength of 0.1 N / 15 mm or more and less than 1 N / 15 mm. There is a problem in practical use.

c: Peel strength is less than 0.1 N / 15 mm. Peeling occurs when winding, and there is a problem in practical use.

In Example 1, the peel strength was 1.5 N / 15 mm and the adhesion was excellent.

<Cracking strength test after curing> After curing, the laminate 1 to 5 were each cut into a size of 200 mm x 15 mm and allowed to stand for 6 hours under an environment of 25 ° C and a humidity of 65%, and then subjected to a tensile tester At 180 DEG C under a load of 100 mm / min under an environment of 25 DEG C and a humidity of 65%.

aa: Peel strength is 8N / 15mm or more. Very good adhesion.

a: peel strength 5N / 15mm or more and less than 8N / 15mm. Excellent adhesion.

b: peel strength 3N / 15mm or more and less than 5N / 15mm. Adhesion is somewhat insufficient and there is a problem in practical use.

c: peel strength less than 3N / 15mm. There is a practical problem due to poor adhesive property.

Example 1 was as shown in Table 3, but the result was that the adhesive property was excellent.

&Lt; Peel strength test after humidity and heat resistance test > After curing, the stacked layers 1, 4 and 5 were each cut into a size of 200 mm x 15 mm and allowed to stand for 1000 hours and 3000 hours in an environment of 85 캜 and 85% humidity. Thereafter, the resultant was allowed to stand at 25 ° C and 65% humidity for 6 hours, and then subjected to 180 ° peeling at a load speed of 100 mm / min under an environment of 25 ° C and a humidity of 65% using a tensile tester in accordance with the test method of ASTM-D1876-61 Test was conducted.

aa: peel strength of 8 N / 15 mm or more, or substrate breakage. Excellent adhesion.

a: peel strength 5N / 15mm or more and less than 8N / 15mm. Excellent adhesion.

b: peel strength 3N / 15mm or more and less than 5N / 15mm. There is a problem in practical use due to lack of adhesiveness. However, because the 3000-hour heat test was overestimated, it was judged to be practicable in evaluation b.

c: peel strength less than 3N / 15mm. There is a practical problem due to poor adhesive property.

Example 1 is as shown in Table 4, but in the case of the layered product 5, the peel strength was 5.6 N / 15 mm and the adhesive property was good, and the result was excellent in moisture resistance test.

&Lt; Inner Thickness Denaturation Test > Evaluation of yellowing by UV irradiation

The film side of the LLDPE film side of the film laminate 5 was set as an irradiated surface on a UV irradiation tester (i-Super UV measuring device W13 (trade name) manufactured by Iwasaki Electric Works Co., Ltd.) and irradiated under conditions of an illuminance of 100 W / . The color difference (Δ b value) before and after irradiation was measured in the color difference meter and the yellowing degree was evaluated. The evaluation criteria are as follows.

aa: Δ b value is less than 3. Very good weathering resistance.

a: Δ b value is more than 3 and less than 6;

b: Δ b value is more than 6 and less than 10.

c: Δ b value is 10 or more. Clear yellowing. There is a problem in practical use.

Example 1 was as shown in Table 3, but Δ b value was 5.1, indicating that the inner sulfur denaturation was excellent.

&Lt; Appearance after Weathering Test > The appearance of the laminate 5 after the UV irradiation test of the above-described inner weathering test was visually observed and evaluated in three stages.

a: The phenomenon of peeling off between the film and the resin composition for sheet bonding does not occur, and the transparency of the laminate is also maintained.

b: No peeling phenomenon occurred between the resin composition for film and sheet bonding, but the transparency of the laminate deteriorated. There is a problem in practical use.

c: Slipping occurs between the resin composition for film and sheet bonding. There is a problem in practical use.

In Example 1, no phenomenon was observed and transparency was maintained, which is good.

(Examples 2 to 19) Sheet-bonding resin compositions (S-2) to (S-19) were obtained in the same manner as in Example 1 except that the raw materials and amounts shown in Tables 4 and 5 were used. The same evaluation as in Example 1 is shown.

Name of sample Example One 2 3 4 5 6 7 8 9 S-1 S-2 S-3 S-4 S-5 S-6 S-7 S-8 S-9 Resin (A)
Resin No AA-1 AA-2 AA-3 AA-4 AA-5 AA-6 AA-7 AA-8 AA-9 adding
Weight portion 25 40 50 85 60 65 96 35 75 Resin (B)
Resin No B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 adding
Weight portion 75 60 50 15 40 35 4 65 25 The crosslinking agent (C)




c-1 &lt; / RTI &gt; (1) 13.7 7.0 c-1 (2) 21.0 0.8 c-1-1-1 10.9 c-1-1-2 6.4 13.1 3.2 c-1-2-1 14.0 c-2 13.2 Portlife a a aa a aa aa aa aa aa Coating Evaluation revelation b a aa a a b a a b Curing before
Peel strength The laminate 1 a a aa a aa aa a a aa After curing
Peel strength






The laminate 1 a aa aa aa a aa a aa aa Actual value (N) 5 12 13 15 7 10 7 12 12 The laminate 2 a a a a aa aa a a a The laminate 3 a a aa a a a a a a The laminate 4 a a aa aa a aa a aa aa Actual value (N) 6 7 9 9 7 8 7 8 8 The laminate 5 a a aa a aa aa a aa aa The laminate 6 a a aa a a aa a aa aa Wet heat test
After 1000h
Peel strength


The laminate 1 a aa aa aa aa aa a aa aa The laminate 4 a a aa a a aa a a a Actual value (N) 5 7 8 7 6 8 6 7 7 The laminate 5 a a aa a a aa a aa a Wet heat test
After 3000h
Peel strength

The laminate 1 aa aa aa aa aa aa aa aa a The laminate 4 a a aa a a a a a a The laminate 5 a a aa a a aa a a a Myelin degeneration
exam The laminate 4 a a aa a a aa aa aa aa Weatherability test
After appearance The laminate 4 a a a a a a a a a

Name of sample Example 10 11 12 13 14 15 16 17 18 19 S-10 S-11 S-12 S-13 S-14 S-15 S-16 S-17 S-18 S-19 Resin (A)
Resin No A-8 A-3 A-9 A-3 A-3 A-3 A-3 A-3 A-10 A-11 adding
Weight portion 50 50 50 50 50 90 75 60 50 50 Resin (B)
Resin No B-3 B-3 B-3 B-8 B-9 B-8 B-8 B-8 B-8 B-8 adding
Weight portion 50 50 50 50 50 10 25 40 50 50 The crosslinking agent (C)
c-1-1-1 8.0 6.1 4.3 c-1-1-2 4.9 4.9 4.9 4.9 4.9 4.9 4.9 Portlife aa aa aa aa aa aa aa aa aa a Coating Evaluation revelation a a a a a a a a a a Curing before
Peel force The laminate 1 aa aa aa aa aa aa aa aa aa aa After curing
Peel force






The laminate 1 aa aa aa aa aa aa aa aa aa aa Actual value (N) 8 15 15 Exfoliation
Impossible 16 7 11 Exfoliation
Impossible Exfoliation
Impossible Exfoliation
Impossible The laminate 2 aa aa aa aa aa a aa aa aa aa The laminate 3 aa aa aa aa aa a aa aa aa aa The laminate 4 aa aa a aa aa a aa aa aa aa Actual value (N) 8 9 7 10 10 7 8 10 10 8 The laminate 5 aa aa aa aa aa a a aa aa aa The laminate 6 a aa a aa aa a a aa aa aa Wet heat test
After 1000h
Peel force


The laminate 1 aa aa aa aa aa a a aa aa aa The laminate 4 a aa a aa aa a a aa aa aa Actual value (N) 7 9 6 10 10 6 6 10 10 9 The laminate 5 aa aa aa aa aa a a aa aa aa Wet heat test
After 3000h
Peel force

The laminate 1 aa aa aa aa aa a a aa a a The laminate 4 a a a aa aa a a aa a a The laminate 5 aa aa aa aa aa a a aa a b Weatherability
exam The laminate 4 aa aa aa aa aa aa aa aa aa aa Weatherability test
After appearance The laminate 4 a a a a a a a a a a

The abbreviations in Tables 4 and 5 are as follows.

[Crosslinking Agent (C)] Polyisocyanate (c-1):

(c-1 (1)) Prepolymer of polymethylene polyphenyl isocyanate Sumiju E21-1 (NCO%: 16.0% solids 100%) manufactured by Sumika Bayer Urethane Co.,

(c-1 (2)) Adduct of styrene diisocyanate and 2- (hydroxymethyl) -2-ethylpropane-1,3-diol DeSmodule L-75 (NCO%: 13.0 % Solids 75%),

Aliphatic polyisocyanate (c-1-1):

(c-1-1-1) Adducts of hexamethylene diisocyanate and 2- (hydroxymethyl) -2-ethylpropane-1,3-diol Sumijuh HT (NCO%: 13.0% Solid content 75%),

(c-1-1-2) Isocyanurate 3-combination of hexamethylene diisocyanate Sumija Bayer Urethane Co., Ltd. Sumiju N3300 (NCO%: 21.8% solids 100%)

Alicyclic polyisocyanate compound (c-1-2):

(c-1-2-1) Isocyanurate trifunctional isomer of isophorone diisocyanate TOLONATE® IDT 70 B (NCO%: 12.3%, solid content: 70%) manufactured by Perstorp Co.,

Epoxy compound (c-2): N, N, N ', N'-tetraglycidyl-m-xylenediamine, bisamide crosslinking agent (c- Trifluoromethyl-lebonyl) -bis- (2-methyl aziridine)

(Comparative Example 1) - (Comparative Example 12) Resin compositions (Comparative Example 1) to (Comparative Example 12) for sheet bonding were obtained in the same manner as in Example 1 except that the raw materials and amounts shown in Table 6 were used. The same evaluation as in Example 1 is shown. Comparative Example 4 is disclosed in Patent Document 4, Patent Reference 4, Comparative Example 11 is disclosed in Japanese Patent Application Laid-Open No. 2010-263193, Patent Reference 7, Comparative Example 12 is disclosed in Japanese Patent Application Publication No. 2012-142349 .

Name of sample


Comparative Example
One 2 3 4 5 6 7 8 9 10 11 12 Comparison-1 Comparison-2 Comparison-3 Comparison-4 Comparison-5 Comparison-6 Comparison-7 Comparison-8 Comparison-9 Comparison-10 Comparison-11 Comparison-12 Resin (A)
Resin No A-1 A-3 none H-1 H-2 H-2 H-3 A-3 A-3 H-4 H-9
100 H-10
100 adding
Weight portion 100 100 85 40 60 50 70 80 80 Resin (B)
Resin No none none B-1 H-5 H-6 B-2 H-8 H-7 H-6 H-8 adding
Weight portion 100 15 60 40 50 30 20 20 Cross-linking agent
(C)



c-1 (1) 22.6 c-1-1-1 25.3 16.2 c-1-1-2 6.4 6.6 9.2 4.6 15.0 10.3 c-1-2-1 12.3 c-3 0.1 additive
Compound 1 0.6 Compound 2 0.2 Portlife c b a b a a a a a aa aa a Coating Evaluation revelation c a a a c a b a c aa a a Curing before
Peel strength The laminate 1 potter
Impossible
















b c b a b c a b a c a After curing
Peel strength






The laminate 1 b Pasting
Impossible















a b a c b a c b a Found
(N) 4 5 3 6 2 5 6 2 3 7 The laminate 2 b c c b c b b c c a The laminate 3 b b b b c b b c c a The laminate 4 b b c a c b b c b b Found
(N) 4 4 One 7 2 3 5 2 3 4 The laminate 5 b a c a c b a c b b The laminate 6 b b c b c c b c b b Wet heat test
After 1000h
Peel strength


The laminate 1 b b c c c b b c c c The laminate 4 b b c b c c b c c b Found
(N) 3 3 2 3 One 2 4 2 One 3 The laminate 5 b b c a c c b c c c Wet heat test
After 3000h
Peel strength

The laminate 1 b c c c c c b c c c The laminate 4 b c c c c c b c c c The laminate 5 b c c c c c b c c c Weather
Sulfur modification
exam The laminate 4 a a b a a b c b aa aa Weatherability
After the test
Exterior The laminate 4 a b b a a b b b a a

The abbreviations in Table 6 are the same as in Tables 3 and 4, and the additives are as follows.

Compound 1: 2 [4- (octyl-2-methylethanoate) oxy-2-hydroxyphenyl] -4,6- [bis (2,4-dimethylphenyl)] - 1,3,5-

Compound 2: 1,3,5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)

As shown in Table 3, the resin composition for sheet bonding of the examples exhibited excellent peel strength before curing, peel strength after curing, peel strength after the heat and humidity resistance test, and maintained the bonding strength over a long period of time. This is because, by mixing other resins with resin Tg, it is possible to improve the wettability of the substrate at the time of curing before curing and the substrate at the time of curing by the copolymer (A) having a low glass transition point, (B) and the cross-linking agent (C) by curing reaction by crosslinking the copolymer (A) and the cross-linking agent (C) to form wettability and agglomeration by the formation of the IPN structure It is presumed that it is done to heighten and balance. In the wet heat test, in comparison with the comparative example, the adhesiveness was severely deteriorated after curing. In the Examples, the glass transition temperature distribution in the entire coating film was maintained while maintaining a high adhesive strength, It is considered that the resin composition for bonding is excellent in long-term moisture resistance qualities for outdoor use only.

In addition, the moisture resistance test B-2 stipulates that the test is based on JIS C 8917 (environment test method and durability test method for crystal solar cell module) that it is capable of withstanding 1,000 hours at 85 ° C and humidity 85%. In the present embodiment, it has been shown that the adhesive strength can be maintained over a long period of time of more than 1000 hours and 3000 hours, and the resin composition for sheet bonding of the present invention has sufficient long-term moisture resistance.

The resin composition for sheet bonding according to the present invention can be used for various purposes such as a multi-layer laminated material for use in an outdoor industry such as a building material (barrier wall material, exterior wall material, roofing material, solar panel material (solar cell protection sheet), window material, outdoor flooring material, Etc.) can be provided with a strong adhesive strength. In addition, it is possible to prevent a decrease in adhesive strength over time due to hydrolysis and the like during outdoor exposure, and to maintain a strong adhesive strength for a long period of time.

In Comparative Example 1 and Comparative Example 2, the copolymer (B) was not added to the copolymer (A). In Comparative Example 1, the effect of accelerating the curing reaction of the isocyanate group by the acid was strong and the pot life was poor. There was no result. In Comparative Example 2, it was possible to coat, but because of the low Tg of the resin, the cohesive force was insufficient and sufficient peeling strength could not be obtained.

In Comparative Example 3, only the copolymer (B) was attempted to be coated, and when the resin Tg was too high, the film peeled off and adhesion became impossible.

From the results of Comparative Examples 1, 2 and 3, it is difficult to ensure high adhesive strength when the copolymer (A) and the copolymer (B) are coated alone.

Comparative Examples 4 to 6 are examples in which the glass transition point of the copolymer (A) is lower than this right range. If the glass transition temperature of the copolymer (A) is too low, the cohesive force becomes insufficient and the adhesive strength can not be obtained. In addition, Comparative Example 4 is an example of Patent Document 4. In the copolymer (B), since no active hydrogen is contained, the curing reaction due to crosslinking does not proceed and the cohesive force of the coating film is lowered.

Comparative Example 7 is an example in which the copolymer (A) has a high glass transition point. If the glass transition point of the copolymer (A) is high, the wettability at the time of sticking is insufficient and a gap is formed in the film and the coating film. Therefore, it is difficult to increase the interaction between the coating film and the film at the time of curing, so that the adhesive strength after curing can not be obtained.

Comparative Example 8 is an example in which the copolymer (B) has a low glass transition point. When the glass transition point of the copolymer (B) was low, the adhesive strength was not problematic at the time of adhering, but the cohesive force of the entire coating film after curing was insufficient and the adhesive strength could not be obtained.

Comparative Example 9 is an example in which the copolymer (B) has a high glass transition point. When the glass transition point of the copolymer (B) is too high, compatibility with the copolymer (A) tends to deteriorate and the coated film becomes rough. As a result, the oxidation is promoted in the oxidation resistance test, and yellowing occurs. In addition, since the wettability after coating is lowered and the bonding strength before curing is insufficient, the bonding strength after curing can not be obtained.

It was estimated from the above Comparative Examples 4 to 9 that the glass transition point of the copolymer (A) and the copolymer (B) had optimum values.

Comparative Example 10 is an example in which the crosslinking agent (C) was not added. The effect of improving the energy elasticity of the coating film due to the curing reaction of the crosslinking agent (C) can not be obtained since the crosslinking agent (C) is not used and the bonding strength is insufficient.

In Comparative Example 11 and Comparative Example 12, the copolymer (A) and the copolymer (B) were not mixed and designed as a single resin. Comparative Example 11 is an example of Patent Document 7, and Comparative Example 12 is an embodiment of Patent Document 8. In Comparative Example 11, the glass transition point of the resin was too high, so that the wettability was poor, and the adhesive strength could not be obtained as in Comparative Example 3. In Comparative Example 12, since the design Tg of the resin was low, the adhesive strength was low and the heat resistance was low.

[Industrial Availability]

The resin composition for sheet bonding according to the present invention can be suitably used for bonding the same or different materials. For example, it is suitable for joining a multilayer laminate of a plastic-based material and a metal-related material, plastic-based films, and metal-based films. In addition, since it has an excellent adhesive strength, it is possible to secure the bonding strength with a thin film, thereby making it possible to reduce the weight of the solar cell protection sheet. In addition, it is possible to maintain a high adhesive strength even when exposed to a high temperature and high humidity environment, so that a multi-layer laminated material (for example, a barrier material, an outer wall material, a roof material, a solar panel material Floor coverings, light protection materials, automobile parts, etc.). Among these, it is particularly preferable to form a solar cell protection sheet, for example, in which an adhesive strength over a long period of time can be maintained and environmental resistance is strongly demanded.

The resin composition for sheet bonding according to the present invention exhibits a high bonding strength particularly in a laminate including a surface treatment layer of a plastic film, but it can be applied to a surface treatment film (including a surface treatment plastic film).

This application claims priority based on Japanese patent application No. 2013-037894 filed on February 27, 2013, including all disclosures therein.

Claims (12)

1. A solar cell protection sheet comprising a laminate,
The laminate includes a base material (G) and a layer made of a resin composition for sheet bonding, which is laminated on one side or both sides of the base material (G)
In the resin composition for sheet bonding,
And a cross-linking agent (C) for the main resin,
Wherein the main resin comprises a copolymer (A) and a copolymer (B) containing an active hydrogen group, and satisfies the following (1) to (3):
(1) The copolymer (A) is a copolymer of an?,? - unsaturated compound and has a glass transition point (Tg) of -40 ° C. or more and less than 10 ° C.,
(2) The copolymer (B) is a copolymer of an?,? - unsaturated compound and has a glass transition point (Tg) of 10 ° C or more and less than 110 ° C,
(3) The copolymer (B) is a copolymer of an alpha, beta -unsaturated compound excluding an alpha, beta -unsaturated compound having at least one functional group selected from the group consisting of a carboxyl group, an amide group, a carbonyl group and an N-alkoxyalkyl group Solar cell protection sheet. The method according to claim 1,
Wherein the copolymer (A) is an α, β-unsaturated compound (m-1) having at least one functional group selected from the group consisting of a carboxyl group, an amide group, a carbonyl group and an N-alkoxyalkyl group, Is a copolymer of the compound (m-3) except that (m-1) and (m-2) below,
The copolymer (B) is obtained by reacting an α, β-unsaturated compound (m-2) (excluding m-1) having an active hydrogen group and other copolymerizable α, , Except that (m-1) and (m-2) are excluded). 3. The method of claim 2,
Wherein the copolymer (A) contains 0.01 to 10 parts by weight of an?,? - unsaturated compound (m-1) in 100 parts by weight of an?,? - unsaturated compound used in copolymerization and a copolymerizable?,? m-3) of 90 to 99.99 parts by weight. 3. The method of claim 2,
Wherein 0.01 to 20 parts by weight of the?,? - unsaturated compound (m-2) (excluding (m-1)) in 100 parts by weight of the?,? - unsaturated compound used in the copolymerization, , And other copolymerizable?,? - unsaturated compounds (m-3) except for (m-1) and (m-2). The method according to claim 1,
Wherein the copolymer (A) is contained in an amount of 30 to 95 parts by weight, based on 100 parts by weight of the total of the copolymer (A) and the copolymer (B). The method according to claim 1,
Wherein the weight average molecular weight of the copolymer (A) is 50,000 to 1,000,000, and the weight average molecular weight of the copolymer (B) is 2,000 to 80,000. The method according to claim 1,
When the crosslinking agent (C) is a polyisocyanate compound (c-1), a polyfunctional epoxy compound (c-2), a metal chelate compound (c-3), a carbodiimide compound ). &Lt; / RTI &gt; The solar cell protection sheet of claim &lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; The method according to claim 1,
Wherein the crosslinking agent (C) is a polyisocyanate (c-1). 9. The method of claim 8,
Wherein the polyisocyanate (c-1) is an aliphatic polyisocyanate (c-1-1) and / or an alicyclic polyisocyanate compound (c-1-2). A solar cell module comprising the solar cell protection sheet according to any one of claims 1 to 9. delete delete