KR20140123947A - Easy-adhesion agent for solar cell protection sheet, solar cell protection sheet, and solar cell module - Google Patents

Abstract

An easy adhesive for a solar cell protection sheet excellent in adhesiveness and adhesion durability, a solar cell protection sheet, and a solar cell module using the solar cell protection sheet. The easy adhesive for a solar cell protective sheet of the present invention comprises a resin (R) other than the (meth) acrylic copolymer (A), and a resin (R) derived from a (meth) acryloyl group having an iodine value of 0.01 to 50 Carbon-carbon double bond. The solar cell protection sheet of the present invention comprises a plastic film which is formed on the outermost surface and has a facilitating adhesive layer formed by an easy adhesive for a solar cell protective sheet of the above form and one main surface supporting the easy adhesive layer .

Description

TECHNICAL FIELD [0001] The present invention relates to an easy adhesive for a solar cell protection sheet, a solar cell protection sheet, and a solar cell module,

The present invention relates to an easy adhesive for a solar cell protection sheet. Further, the present invention relates to a solar cell protection sheet using an easy adhesive for the solar cell protection sheet and a solar cell module using the solar cell protection sheet.

As the awareness of environmental problems has recently been improved, solar cells have attracted attention as a clean energy source free of environmental pollution, and have been put to practical use in terms of practical research in terms of utilization of useful energy resources.

There are various types of solar cell elements, and typical examples thereof include a crystalline silicon solar cell device, a polycrystalline silicon solar cell device, an amorphous silicon solar cell device, a copper indium-selenide solar cell device, and a compound semiconductor solar cell device. Among these, polycrystalline silicon solar cell devices, amorphous silicon solar cell devices and compound semiconductor solar cell devices are being actively researched and developed in various fields because they are comparatively low cost and can be made large-sized. Among these solar cell elements, a thin film solar cell element represented by an amorphous silicon solar cell element in which silicon is laminated on a semiconductor metal substrate and a transparent conductive layer is formed thereon is lightweight, has excellent impact resistance and flexibility, Which is a promising form.

Among the solar cell modules, the simple structure is a constitution in which sealing material protecting materials are sequentially stacked on both sides of the solar cell element. Representative examples of the protective material include a glass plate, a solar cell protective sheet (hereinafter referred to as a "protective sheet "), and the like. The glass plate is very excellent in transparency, weather resistance and scratch resistance, but has problems in cost, sheet property and processability. On the other hand, a protective sheet has been proposed (for example, Patent Document 1) in various kinds of protective sheets excellent in cost, sheet property and workability. In addition, an ethylene-vinyl acetate copolymer (hereinafter referred to as "EVA") having high transparency and excellent moisture resistance is generally used as the sealing material.

Examples of the protective sheet include (i) a single-layer film such as a polyester film, (ii) a polyester film and the like, and (iii) a film of a metal oxide and a non- Film, a multilayer film obtained by laminating films such as an aluminum foil, and the like.

The protective sheet of the multi-layer structure can impart various performances according to the multi-layer structure. For example, by using a polyester film, it is possible to impart water vapor barrier properties by using an aluminum foil (see Patent Documents 2 to 4).

Adhesion and adhesion durability to the sealant are basic and important performance requirements for various performance requirements of the protective sheet. If the adhesiveness to the sealing material is insufficient, the protective sheet is peeled off and the solar cell can not be protected from moisture and external factors, resulting in deterioration of the output of the solar cell.

(1) a method of performing an easy adhesion treatment on the surface of the protective sheet in contact with the sealing material, (2) a method of using a highly adhesive film with the sealing material on the surface of the protective sheet in contact with the sealing material .

The method (1) includes surface treatment such as corona treatment and easy adhesive coating treatment for applying an easy adhesive.

However, in the surface treatment such as the corona treatment of the electron, the initial adhesion is ensured, but the problem of poor adhesion durability is a problem. The latter easy adhesive used in the case of the adhesive coating treatment is disclosed in Patent Documents 1, 5 and 6.

Patent Document 5 discloses that a crosslinking agent selected from the group consisting of an oxazoline group-containing polymer, a urea resin, a melamine resin, and an epoxy resin and a resin component other than a crosslinking agent selected from a polyester resin or an acrylic resin having a glass transition point of 20 to 100 캜 (See claims 2 and 3 of this document). More specifically, an example using a coating liquid containing an epoxy resin and an acrylic resin is described (see Example 5 of this document). However, in this case, the adhesive strength to the EVA sheet is about 10 to 20 N (that is, 7.5 to 15 N for a 15 mm width) at a width of 20 mm (see Table 2 of this document). The adhesion between the sealing material and the protective sheet greatly affects the power output of the solar cell. Therefore, in the market, higher adhesion is required and reliability of the adhesive performance under more severe conditions is required. I can not meet the market demand. Although the adhesive strength is improved in Patent Document 1, a higher performance adhesive is demanded in the market.

Patent Document 6 discloses a method for producing a laminated film comprising a polyester film and a protective sheet in which at least one kind of resin selected from the group consisting of a polyester resin and a polyester polyurethane resin is crosslinked with an alkylated melamine or polyisocyanate crosslinking agent, The configuration that is installed on the surface is posted.

As the method (2) (a method of using a film having high adhesiveness with a sealing material on the surface of the protective sheet in contact with the sealing material), for example, a method using polybutylene terephthalate (PBT) .

However, such a film generally has a thickness of several tens of 탆, which causes a problem in that the cost is higher than the above-mentioned adhesion treatment.

Patent Document 8 discloses an adhesive layer made of an acrylic adhesive containing an acryl-based polymer obtained by polymerizing a monomer component containing a monomer represented by the following general formula (I) on a surface to be bonded to a filler (sealing material) constituting a solar cell module A back sheet for a solar cell module is disclosed.

???????? CH ₂ = C (R ¹ ) -CO-OZ ????? (1)

R ¹ in the formula (1) represents a hydrogen atom or a methyl group, and Z represents a hydrocarbon group having 4 to 25 carbon atoms.

Patent Document 9 discloses a fluorine-based copolymer, an acrylic copolymer or a polyurethane-based copolymer (polymer a), a polymerizable monomer having at least one ethylenic unsaturated group for photo-curing and / or an oligomer (monomer b) and / A protective sheet for a solar cell element having a primer layer composed of a compound (polyisocyanate c) containing at least one ethylenic unsaturated group and at least two isocyanate groups in the molecule is disclosed.

Japanese Patent Application Laid-Open No. 2009-246360 Japanese Patent Application Laid-Open No. 2004-200322 Japanese Patent Application Laid-Open No. 2004-223925 Japanese Patent Application Laid-Open No. 2001-119051 Japanese Patent Application Laid-Open No. 2006-152013 Japanese Patent Application Laid-Open No. 2007-136911 Japanese Patent Application Laid-Open No. 2010-114154 Japanese Patent Application Laid-Open No. 2010-263193 Japanese Patent Application Laid-Open No. 11-17272

An object of the present invention is to provide an easy adhesive for a solar cell protection sheet excellent in adhesiveness and adhesion durability, a solar cell protection sheet and a solar cell module using the solar cell protection sheet.

The easy adhesive for a solar cell protective sheet of the present invention is a resin composition containing a resin (R) other than the (meth) acrylic copolymer (A), wherein the amount of the carbon-carbon double bonds derived from the (meth) acryloyl group is an iodine value (G / 100 g).

An easy adhesive for a solar cell protective sheet of the present invention can be exemplified by the following preferred embodiments.

Preferable forms of the resin (R) include those having a number average molecular weight of 10,000 to 250,000 and a glass transition temperature of -40 to 100 ° C.

A preferable form of the resin (R) is at least one of a hydroxyl group and an amino group, and the sum of a hydroxyl value and an amine value is 2 to 100 (mgKOH / g).

Preferred examples of the resin (R) include a resin selected from the group consisting of a fluorine resin, an olefin resin, a polyester resin, a polyurethane resin, a polyurethaneurea resin and a polyamide resin.

Preferred examples of the carbon-carbon double bond derived from the (meth) acryloyl group include (i) those contained in the resin (R), and (ii) those contained in the resin (R) (B) having a (meth) acryloyl group, and the resin (R) of (i) has a carbon-carbon double bond derived from a (meth) acryloyl group, (R) other than the (meth) acrylic copolymer (A), and the resin (R) in the above (ii) is a resin other than the (meth) acryl- Rb).

The preferable form of the resin (R) is a polyisocyanate compound (C) containing at least one of a hydroxyl group and an amino group and having an isocyanate group in an amount of 0.1 to 10 moles relative to the molar amount of the hydroxyl group and the amino group There is.

(Ra-1) to (Ra-2) described in at least one of the following (1-1) to (1-5) ).

(1-1) The resin (Rb) has at least one of a hydroxyl group and an amino group, and the resin (Rb) is a resin obtained by adding a (meth) acrylic monomer having an isocyanate group to at least one of the hydroxyl group and the amino group (Ra-1).

(1-2) A resin (Ra-2) obtained by adding the (meth) acrylic monomer having a glycidyl group to the carboxyl group in the resin (Rb), wherein the resin (Rb) has a carboxyl group.

(1-3) A resin (Ra-3) obtained by adding the (meth) acrylic monomer having a carboxyl group to the glycidyl group in the resin (Rb), wherein the resin (Rb) has a glycidyl group.

(1-4) A resin (Ra-4) obtained by adding the (meth) acrylic monomer having a hydroxyl group to the acid anhydride group in the resin (Rb), wherein the resin (Rb) has an acid anhydride group.

(1-5) A resin composition comprising (meth) acrylate (meth) acrylate having a functional group capable of polymerizing with each other and having a (meth) acryloyl group in the side chain and a component having no (meth) acryloyl group in the side chain, A resin (Ra-5) containing a carbon-carbon double bond derived from diarrhea.

The preferred form of the adhesive for a solar cell protective sheet of the present invention includes 0.1 to 20 parts by weight of the compound (B) having the (meth) acryloyl group per 100 parts by weight of the resin (Rb) .

The preferred form of the compound (B) having a (meth) acryloyl group is one having two or more (meth) acryloyl groups in the molecule.

The solar cell protection sheet (Z ') of the present invention comprises the easy adhesive layer (D') formed on the outermost surface and the plastic film (E) supporting one side of the easy adhesive layer (D ' The adhesive layer (D ') is formed by the easy adhesive for the solar cell protective sheet described above.

The solar cell module of the present invention comprises a solar cell III, a solar cell surface protection material I positioned on the light receiving surface side of the solar cell, a sealing material II located on the light receiving surface side of the solar cell III, And a solar cell back protection material (V) located on a non-light receiving surface side of the solar cell (III) and a sealing material (IV) located on a non- light receiving surface side of the solar cell (III) The solar cell surface protection material I is obtained by arranging the easy adhesive layer D 'provided on the solar cell protective sheet Z' of the above-described type in contact with the sealing material II to cure the easy adhesive layer D ' And the solar cell back protection material (V) is obtained by disposing the easy adhesive layer (D ') provided on the solar cell protection sheet (Z') of the above form in contact with the sealing material (IV) D ').

In a preferred embodiment of the solar cell module of the present invention, at least one of the sealing material (II) and the sealing material (IV) contains an organic peroxide.

In a preferred embodiment of the solar cell module of the present invention, at least one of the sealing material (II) and the sealing material (IV) is composed mainly of an ethylene-vinyl acetate copolymer (EVA).

By using the easy adhesive for solar cell protective sheet of the present invention, it is possible to provide an easy adhesive for a solar cell protective sheet excellent in adhesion and durability, and a solar cell protective sheet and a solar cell module using the solar cell protective sheet Effect. Provided is a solar cell module using the solar cell protective sheet of the present invention and having a small output drop even when exposed to a high temperature and high humidity environment for a long time.

1 is a diagram schematically showing a cross section of a solar cell module of the present invention.

Hereinafter, the present invention will be described in detail. It is needless to say that other embodiments are included in the scope of the present invention as long as they are consistent with the purpose of the present invention. The numerical range specified by using "~ " in the present specification includes numerical values before and after" ~ "as a range of lower limit and upper limit. In the present specification, the term "film" or "sheet" In other words, the term "sheet" in this specification includes thin film, and the term "film"

The term "(meth) acryl-based copolymer" used herein means to include "acrylic copolymer", "methacrylic copolymer" and "acrylic-methacrylic copolymer" Acrylate "means " acryloyl "," methacryloyl ", and "(meth) acrylic"

1 is a schematic cross-sectional view of a solar cell module according to the present invention. The solar cell module has at least a solar cell surface protection material (I), a sealing material (II) on the light receiving surface side, a solar cell (III), a sealing material (IV) . The light receiving surface side of the solar cell III is protected by the solar cell surface protecting material I through the sealing material II on the light receiving surface side. On the other hand, the non-light receiving surface side of the solar cell (III) is protected by the protection material (V) on the solar cell through the sealing material (IV) on the non-light receiving side.

At least one of the solar cell surface protection material (I) and the solar cell backing protection material (V) is obtained by the following process. That is, the solar cell surface protection material I is obtained by curing the adhesive layer D 'by disposing the easy adhesive layer D' provided on the solar cell protective sheet Z 'to be described later in contact with the sealing material II , And / or the solar cell backing material (V), the easy adhesive layer (D ') provided on the solar cell protection sheet (Z') to be described later is placed in contact with the sealing material (IV) .

The solar cell protection sheet Z 'is not limited to being capable of taking various known aspects, but it is preferable that the solar cell protection sheet Z' has a structure in which the easy adhesive layer D 'formed on the surface layer and the easy adhesive layer D And a plastic film (E) for supporting the plastic film (E). The easy adhesive layer (D ') is formed by an easy adhesive for a solar cell protective sheet of the present invention (hereinafter simply referred to as "easy adhesive").

The easy adhesive for a solar cell protective sheet of the present invention is a resin composition containing a resin (R) other than the (meth) acrylic copolymer (A), wherein the amount of the carbon-carbon double bond derived from the (meth) acryloyl group is an iodine value Is 0.01 to 50 (g / 100 g).

In addition, the easy adhesive layer (D ') formed by the easy adhesive for the solar cell protective sheet of the present invention undergoes a crosslinking reaction by a heat pressing process in forming the solar cell module. In the present invention, the easy adhesive layer before the hot pressing process is distinguished as the easy adhesive layer (D '), and the crosslinked easy adhesive layer after the hot pressing process as the easy adhesive layer (D). Similarly, the solar cell protection sheet (Z ') before the heat pressing step and the solar cell protection sheet (Z) after the hot pressing step are distinguished.

(R) (hereinafter also simply referred to as resin (R)) other than the (meth) acrylic copolymer (A) of the present invention will be described.

The (meth) acrylic copolymer (A) referred to here is obtained by polymerizing the following various monomers to form a main chain.

Examples of the monomer include (meth) acrylic monomers having an alkyl group, (meth) acrylic monomers having a hydroxyl group, (meth) acrylic monomers having a carboxyl group, and (meth) acrylic monomers having a glycidyl group. And copolymers thereof with vinyl acetate, maleic anhydride, vinyl ether, vinyl propionate, and styrene.

Examples of the (meth) acrylic monomer having an alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) And the like.

Examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

Examples of the (meth) acrylic monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid and citraconic acid.

Examples of the (meth) acrylic monomer having a glycidyl group include glycidyl acrylate, glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether.

As the resin (R) other than the (meth) acrylic copolymer (A), an olefin resin (r1), a fluorine resin (r2), a polyester resin (r3), a polyurethane resin (r4), a polyurethaneurea resin r5), a polyamide-series resin (r6), and the like. These may be used alone or in combination.

The olefinic resin (r1) can be obtained by polymerizing an ethylenic monomer capable of polymerization by a conventional radical polymerization method. The olefin resin (r1) may be either a homopolymer or a copolymer, preferably a copolymer.

Examples of the polymerizable ethylenic monomer include olefins such as ethylene, propylene, n-butene, isobutylene, 2-butene, cyclopentene and cyclohexene, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, n Vinyl ethers such as hexyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether and hydroxybutyl vinyl ether, vinyl acetate, vinyl caprate, lauric acid Vinyl esters such as vinyl, vinyl palmitate, vinyl stearate, vinyl benzoate, vinyl cyclohexylcarboxylate and the like.

These ethylenic monomers may be used alone or in combination of several kinds. However, in the present invention, when the monomer used for the olefin resin (r1) contains a fluoroolefin monomer, the resin belongs to the fluorine resin (r2).

Examples of the olefin resin (r1) include "Unistall" (Mitsui Gagaku Co., Ltd.) and "Auroren" (manufactured by Nippon Seishi Chemical Co., Ltd.).

The fluorine-containing resin (r2) can be obtained by subjecting a polymerizable fluoroolefin to a monomer by a conventional radical polymerization method. The fluororesin (r2) may be either a homopolymer or a copolymer, preferably a copolymer. The copolymer may be a copolymer of fluorine monomers or a copolymer of a fluorine monomer and a monomer not containing fluorine.

Examples of polymerizable fluoroolefin monomers include vinyl fluoride, trifluoroethylene, tetrafluoroethylene, perfluoroalkyl vinyl ether, hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, and the like.

These fluoroolefins may be used singly or in a mixture of various types. If necessary, the above-mentioned ethylenic monomers and the like may be mixed and used.

Examples of the fluororesin (r2) include "Lumipuron" (product of Asahi Garas Co., Ltd.), "Fluoronate" (product of DIC Co.), "Jetflu" (product of Daikin Corporation) have.

The polyester resin (r3) is a resin obtained by reacting a carboxylic acid component and a hydroxyl group component (esterification reaction, transesterification reaction).

The carboxylic acid component constituting the polyester resin (r3) is preferably at least one selected from the group consisting of benzoic acid, p-tert-butylbenzoic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid, tetrahydrophthalic anhydride, , Maleic anhydride, fumaric acid, itaconic acid, tetrachlorophthalic anhydride, 1,4-cyclohexane dicarboxylic acid, anhydrous trimellitic acid, methylcyclohexene tricarboxylic anhydride, anhydrous pyromellitic acid, epsilon -caprolactone, Fatty acids can be exemplified.

Examples of the hydroxyl group component constituting the polyester resin (r3) include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol , 3-methylpentanediol, 1,4-cyclohexanedimethanol, and other diol components such as glycerin, trimethylolethane, trimethylolpropane, trishydroxymethylaminomethane, pentaerythritol, dipentaerythritol, Alcohol can be exemplified.

The polyester resin (r3) can be used as a polyester resin by polymerizing such a carboxylic acid component and a hydroxyl group component according to a general method.

The polyurethane resin (r4) is a resin which is obtained by reacting an isocyanate compound with a hydroxyl group component.

Examples of the isocyanate compound constituting the polyurethane resin (r4) include the same polyisocyanate compound (C) described later. Trimethylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), methylenebis (4,1-phenylene) = diisocyanate (MDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate ), And xylene diisocyanate (XDI). Examples of the diisocyanate include trimethylolpropane adducts of these diisocyanates, isocyanurate isomers of triplets, and bidet conjugates. Polymer diisocyanates And the like.

The hydroxyl group component constituting the polyurethane resin (r4) includes a polyester polyol, a polyether polyol and a polycarbonate polyol. A polyurethane polyol, which is a reaction product of such a polyol and a diisocyanate, can also be used.

As the polyester polyol, a polyester resin (r3) having a terminal hydroxyl group can be used.

As the polyether polyol, a known polyether polyol may be used. For example, by polymerizing an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran using a compound having two or more hydroxyl groups such as ethylene glycol and propylene glycol as an initiator or water as an initiator May be used. Specifically, polypropylene glycol, polyethylene glycol, polytetramethylene glycol and the like having two or more functional groups can be used.

Examples of the polycarbonate polyol include (1) a reaction of a compound having two or more hydroxyl groups such as ethylene glycol and propylene glycol with a carbonic ester, (2) reaction of a compound having two or more hydroxyl groups as described above in the presence of an alkali And a reaction in which phosgene is activated.

Specific examples of the carbonic ester used in the production method of the above (1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate and the like.

The polyester polyol, the polyether polyol, and the polyurethane polyol, which is a reaction product of the polycarbonate polyol and the diisocyanate, can be obtained by subjecting such a polyol and a diisocyanate to a urethane reaction so that the two terminals are hydroxyl groups. (TDI), hexamethylene diisocyanate (HDI), methylene bis (4,1-phenylene) = diisocyanate (MDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl Isocyanate (IPDI), and xylene diisocyanate (XDI).

As the polyurethane-urea-series resin (r5), urethane prepolymers are synthesized by making hydroxyl groups and diisocyanate compounds such as polyester polyols, polyether polyols and polycarbonate polyols at the two ends to be isocyanate groups, A resin obtained by reacting a compound (Am) having two or more amine groups may be used. The reaction can also be controlled using a reaction terminator (S), if necessary.

As the compound (Am) having two or more amino groups, known compounds can be used. Examples of the diamine compound include ethylene diamine, propylene diamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine , Aliphatic polyamines such as trilylene diamine, hydrazine, and piperazine; Aliphatic polyamines including aliphatic cyclic polyamines such as isophoronediamine, dicyclohexylmethane-4,4'-diamine and the like; Aromatic polyamines such as phenylenediamine and xylenediamine; Diamino-2-butanol, 1-amino-3- (aminomethyl) -3,5,5-trimethylcyclohexan-1-ol, 4- (2-aminoethyl) -4,7,10-triazadecan-2-ol, 3- (2-hydroxypropyl) -o-xylene- ?,? '- diamine, 1,11-diamino- 2-propanol, 2- [bis (2-aminoethyl) amino] -2-propanol, Propylenediamine, (2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethyl) Diamino alcohols such as (hydroxyethyl) propylenediamine, (2-hydroxypropyl) ethylenediamine and (di-2-hydroxypropyl) ethylenediamine.

Compounds usable as the reaction terminator (S) include monofunctional alcohols, secondary amines, hydroxyl groups and compounds having one secondary amino group.

The monofunctional alcohols include alcohols such as methyl alcohol, ethanol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decanyl alcohol, undecanoyl alcohol, lauryl alcohol, But are not limited to, alcohol, pentadecyl alcohol, isobutyl alcohol, isopentyl alcohol, isohexyl alcohol, isoheptyl alcohol, isooctyl alcohol, isononyl alcohol, isodecanyl alcohol, isodecanyl alcohol, Monofunctional aliphatic alcohols such as tetradecyl alcohol and isopentadecyl alcohol; Benzyl alcohol, methylphenyl methanol, methoxyphenyl methanol, ethylphenyl methanol, ethoxyphenyl methanol, butyl phenyl methanol, butoxyphenyl methanol, phenyl ethanol, methylphenyl ethanol, Butanol, methylphenylbutanol, methoxyphenylbutanol, ethylphenylmethylphenylether, methoxyphenylpropanol, ethoxyphenylpropanol, butylphenylpropanol, butoxyphenylpropanol, phenylbutanol, methylphenylbutanol, methoxyphenylbutanol, ethylphenyl Monofunctional aromatic alcohols such as butanol, ethoxyphenyl butanol, butylphenyl butanol, and butoxyphenyl butanol are mentioned.

Examples of secondary amines include dibutylamine, dipentylamine, dihexylamine, di- (2-ethylhexyl) amine, diheptylamine, dioctylamine, dinonylamine, dideckanylamine, But are not limited to, amines such as diethylamine, diethylamine, diethanolamine, diarylamine, ditridecylamine, ditetradecylamine, dipentadecylamine, diisobutylamine, diisopentylamine, diisobutylamine, diisoohexylamine, diisooctylamine, diisononylamine, di There may be mentioned, for example, aliphatic amines such as isodecanylamine, diisodecanylamine, diisowurylamine, diisotridecylamine, diisotetradecylamine, diisopentadecylamine, butylpentylamine, butylhexylamine, hexylpentylamine, Aliphatic secondary amines such as nonyl octyl amine; (Ethoxybenzyl) amine, di- (methylbenzyl) amine, di- (methoxybenzyl) amine, di- (Methoxyphenyl) amine, di- (ethylphenethyl) amine, di- (ethoxyphenyl) amine, di- (methoxyphenyl) (Methoxycinnamyl) amine, di- (ethylcinnamyl) amine, di- (ethylcinnamethyl) amine, di- Aromatic secondary amines such as - (ethoxycinnamyl) amine, di- (butylcinnamyl) amine, and di- (butoxycinnamyl) amine.

Examples of the compound having a hydroxyl group and one secondary amino group include monoethanolamine, ethanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) Propanediol, 2-aminopropanol, and 3-aminopropanol.

Among the above-mentioned reaction terminators (S), a compound having a hydroxyl group and one secondary amino group is more preferable in that a polyurethaneurea resin (r5) having a hydroxyl group at the terminal can be obtained. The hydroxyl group present at the terminal may also serve as a bridge site when the polyisocyanate compound (C) is added to the polyurethaneurea resin (r5) and crossed. 2-Amino-2-methyl-propanol is also particularly good because it is easy to control the reaction.

The polyamide-series resin (r6) is obtained, for example, by reacting the aforementioned carboxylic acid component with a compound (Am) having two or more amine groups.

The reaction for obtaining the polyamide-series resin (r6) can be obtained by, for example, collecting a compound (Am) having two or more carboxylic acid component and amine group under the absence of solvent and dehydrating condensation reaction. This reaction may be carried out under a normal atmospheric pressure or under a reduced pressure.

It is important for the easy adhesive of the present invention to contain a carbon-carbon double bond derived from a (meth) acryloyl group in an amount defined in the range of 0.01 to 50 (g / 100 g) of iodine value. The iodine value is preferably in the range of 0.1 to 30 g / 100 g, more preferably 0.5 to 20 g / 100 g. By setting the iodine value to 50 (g / 100 g) or less, the crosslinking reaction of the adhesive can be made easy and the adhesive force can be drawn more effectively. 0.01 (g / 100 g) or more, sufficient crosslinking reaction is carried out and excellent adhesion can be obtained.

Here, the iodine value can be obtained by the following measuring method.

0.3 to 1 g of the sample is measured in an Erlenmeyer flask to the number of digits of 0.1 mg, 50 cm 3 of chloroform is added, and the mixture is allowed to stand in a constant temperature water bath at 25 캜 for 30 minutes. Remove the Erlenmeyer flask from the thermostatic water bath and add 25 cm3 of the solution of the whiskey solution using a pipette. The flask is gently shaken until it becomes uniform, and the solution is allowed to stand in a constant temperature water bath at 25 ° C for 120 minutes. Remove the Erlenmeyer flask from the constant-temperature water bath, add 10 cm3 of an aqueous solution of potassium iodide at a concentration of 100 g / L, shake vigorously with a stopper. Next, titration is carried out using 0.1 mol / L sodium thiosulfate aqueous solution. When the water tank of the upper layer becomes a little yellow, 1 cm 3 of starch solution is added, and the titration is continued until the purple color of the solution disappears.

The iodine value is obtained by the following formula. The iodine value should be converted into the solid content of the easy adhesive (unit: g / 100 g).

Iodine value (g / 100 g) = [{(V0 - V1) x c 12.69} / m] / (solid content concentration / 100)

Where m is a weight (g) of the sample,

V0: Appropriate amount of blank test (cm3)

V1: Appropriate amount of sample (cm3)

c: concentration of sodium thiosulfate solution (mol / L)

The iodine value of the present invention is the value measured by the above method.

The wise solution used for titration of the iodine value is prepared in the following procedure.

4.8 to 5.2 g of iodine trichloride are weighed to the extent of 0.1 g and placed in a 1 L brown bottle with a stopper cap coated with Teflon. In an Erlenmeyer flask equipped with a stopper, a quantity of 5.5 g of iodine is measured up to 0.1 g, and 640 cm 3 of acetic acid is added to dissolve. This solution is put in a brown bottle with iodine trichloride, mixed and made into a wise solution. In the present invention, after preparation of the solution, the solution was stored in a cool dark place and used within 30 days after the solution preparation.

The sealing material (II) and the sealing material (IV) of the solar cell (III) are not particularly limited, and known materials can be suitably applied. Suitable materials include EVA (ethylene-vinyl acetate copolymer), polyvinyl butyral, polyurethane, and polyolefin. Among them, EVA is mainly used in terms of cost. The sealing material (II) and the sealing material (IV) are preferably sheets (including a film), but they may be paste-like.

At least one of the sealing material (II) and the sealing material (IV) may contain an organic peroxide. It is possible to crosslink the sealing material II by the radical reaction when the solar cell III is sandwiched and heated by the sealing material II and the sealing material IV ) And the sealing material (IV) can be crosslinked, or the sealing material (IV) can be efficiently crosslinked. That is, the crosslinking reaction can be promoted.

By containing an organic peroxide in the sealing material (II) and / or the sealing material (IV), the organic peroxide easily acts on the carbon-carbon double bond in the adhesive layer (D ') during heat sealing, '), Or facilitate crosslinking in the adhesive layer (D'). From the viewpoint of better promoting the adhesion of the solar cell protection sheet, it is preferable to include an organic peroxide in the sealing material on the side in contact with the solar cell protection sheet.

Therefore, the carbon-carbon double bond of the easy adhesive forming the easy adhesive layer (D ') of the present invention means a carbon-carbon double bond moiety (C = C) capable of being polymerized with each other due to radical reaction activity, Reactive inactive carbon-carbon double bonds such as the pyridine ring do not apply. Among them, it is important that the carbon-carbon double bond is highly reactive, such as a (meth) acryloyl group, and the carbon-carbon double bond such as a vinyl group is remarkably less reactive. The "hardening treatment" in this specification refers to a treatment for joining the sealing materials (II, IV) and the solar cell protection sheet (Z ') after joining them.

Various methods may be considered as methods for containing a carbon-carbon double bond derived from a meta) acryloyl group in an amount of 0.01 to 50 (g / 100 g) of iodine in the easy adhesive layer of the present invention. As an example, the following can be exemplified. (B) contained in (i) the resin (R), or (ii) not contained in the resin (R) and having a (meth) acryloyl group. At this time, the resin (R) of (i) is a resin (Ra) other than the (meth) acrylic copolymer (A) having a carbon-carbon double bond derived from a (meth) acryloyl group , And the resin (R) of (ii) is a resin (Rb) other than the (meth) acryl-based copolymer (A) which has no (meth) acryloyl group )to be. (i) and (ii) may be used singly or in a mixed system of (i) and (ii).

First, a case in which a carbon-carbon double bond derived from a (meth) acryloyl group corresponds to a form embedded in a resin (R) of (i) will be described. As the resin (Ra), resins (Ra-1) to (Ra-5) described in at least one of the following (1-1) to (1-5) can be cited as an appropriate example.

(1-1) The resin (Rb) has at least one of a hydroxyl group and an amino group, and the resin (Ra-1) obtained by adding a (meth) acrylic monomer having an isocyanate group to at least one of the hydroxyl group and the amino group of the resin One). (Ra-1) can be obtained by introducing a (meth) acryloyl group starting from the hydroxyl group and / or amino group of the resin (Rb).

Examples of the (meth) acrylic monomer having an isocyanate group to be used herein include 2-isocyanate ethyl acrylate and 2-isocyanate ethyl methacrylate. These products include car lenses AOI, Ka Lens MOI and so on.

(1-2) A resin (Ra-2) obtained by adding a (meth) acrylic monomer having a carboxyl group and a glycidyl group in a carboxyl group in the resin (Rb). The resin (Ra-2) can be obtained by introducing a (meth) acryloyl group starting from the carboxyl group of the resin (Rb).

(1-3) A resin (Ra-3) obtained by adding a (meth) acrylic monomer having a carboxyl group to a glycidyl group in the resin (Rb), wherein the resin (Rb) has a glycidyl group. (Ra-3) can be obtained by introducing a (meth) acryloyl group starting from the glycidyl group of the resin (Rb) as a starting point.

(1-4) A resin (Ra-4) obtained by adding a (meth) acrylic monomer having a hydroxyl group to an acid anhydride group in the resin (Rb), wherein the resin (Rb) has an acid anhydride group. (Ra-4) can be obtained by introducing a (meth) acryloyl group starting from the acid anhydride group of the resin (Rb).

(1-5) A polymer having a functional group capable of polymerizing with each other and having a (meth) acryloyl group in a side chain and a component having no (meth) acryloyl group in a side chain, A resin (Ra-5) containing a carbon-carbon double bond derived from diarrhea. (1-5) can be particularly utilized when a polyurethane-based resin (r4) and a polyurethane-urea-based resin (r5) are obtained.

For example, in the case of the polyurethane-based resin (r4) and the polyurethane-urea-based resin (r5), by using the (meth) acryloyl group and the hydroxyl group component (T) having two or more hydroxyl groups as one of the hydroxyl groups, A polyurethane resin (r4) having a (meth) acryloyl group, and the like can be synthesized.

For the addition reaction of (1-1) to (1-4), a known catalyst may be used. For example, a tertiary amine compound, an organometallic compound, and the like.

Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- (5,4,0) ).

Examples of the organometallic compounds include tin compounds and non-tin compounds. Examples of the tin compound include dibutyltin chloride, dibutyltin oxide, dibutyltin bromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin Tributyl tin oxide, tributyl tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, tributyl tin chloride, tributyl tin trichloroacetate, 2-ethylhexanoic acid tin and the like .

Examples of the non-tin compound include titanium-based compounds such as dibutyltitanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate , Iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate, zirconium naphthenate .

Examples of the hydroxyl group (T) ((meth) acryloyl group and hydroxyl group having two or more hydroxyl groups) used in the method (1-5) include a compound having two or more epoxy groups, The added compound (U), glycerin mono (meth) acrylate, trimethylol ethane mono (meth) acrylate, trimethylol propane mono (meth) acrylate, pentaerythritol mono (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, and the like. The hydroxyl group component (T) may be used alone or in combination of two or more.

Examples of the compound (U) (compound in which (meth) acrylic acid is added to the epoxy group of the compound having two or more epoxy groups) include (meth) acrylic acid adduct of propylene glycol diglycidyl ether, 1,6- (Meth) acrylic acid adducts of ethylene glycol diglycidyl ether, (meth) acrylic acid adducts of sebacic acid ether, (meth) acrylic acid adducts of sebacic acid ester, (meth) acrylic acid adducts of ethylene glycol diglycidyl ether, (meth) acrylic acid adducts of 1,4-butanediol diglycidyl ether, (Meth) acrylic acid adduct of diglycidyl ether, a (meth) acrylic acid adduct of 1,6-hexanediol diglycidyl ether, a (meth) acrylic acid adduct of 1,9-nonanediol diglycidyl ether (Meth) acrylic acid adduct of neopentyl glycol diglycidyl ether, (meth) acrylic acid adduct of bisphenol A diglycidyl ether, (meth) acrylic acid adduct of hydrogenated bisphenol A diglycidyl ether, glycerin The (meth) acrylic acid addition of diglycidyl ether And the like.

Next, the addition of the carbon-carbon double bond derived from the (meth) acryloyl group in the compound (B) having the (meth) acryloyl group (hereinafter also referred to simply as "compound (B)") · We explain case corresponding to formulation type. That is, the resin (R) contained in the easy adhesive is a resin (Rb) other than the (meth) acryl-based copolymer (A) having no (meth) acryloyl group, and the carbon derived from the (meth) acryloyl group - An example in which a compound (B) having a (meth) acryloyl group as a carbon double bond is contained will be described.

The compound (B) having a (meth) acryloyl group of the present invention may be any compound having at least one (meth) acryloyl group in the molecule. Examples thereof include trimethylolpropane tri (meth) acrylate, (Meth) acrylates of polyhydric alcohols such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate, bisphenol A diglycidyl ether (Meth) acrylates such as di (meth) acrylate of polyethylene glycol diglycidyl ether and di (meth) acrylate of polyethylene glycol diglycidyl ether.

Among them, from the viewpoint of the reactivity, the compound (B) preferably has two or more (meth) acryloyl groups in the molecule, more preferably three or more in the molecule.

The compound (B) may contain a hydroxyl group or other functional groups to the extent that the crosslinking between the resin (Rb) and the polyisocyanate compound (C) is not inhibited.

The organic peroxide contained in the sealing material (II) and / or the sealing material (IV) is preferably used in an amount of 0.05 to 3.0 parts by weight based on 100 parts by weight of the resin of the sealing material. Specific examples of the organic peroxide include tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy-2-ethylhexyl isopropyl carbonate, tert-butyl peroxyacetate, tert-butyl cumyl peroxide, , 5-2 (tert-butylperoxy) hexane di-tert-butyl peroxide, 2,5-dimethyl-2,5-2 (tert-butylperoxy) (Tert-butylperoxy) hexane, 1,1-2 (tert-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-2 1,1-2 (tert-hexylperoxy) cyclohexane, 1,1-2 (tert-amylperoxy) cyclohexane, 2,2-2 (tert-butylperoxy) butane, methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5-diperoxybenzoate, tert-butyl hydroperoxide, dibenzoyl peroxide, p-chlorobenzoyl peroxide, tert-butyl peroxyisobutyrate, n- -2 (tert-butylperoxy) valerate, ethyl-3,3-di (tert-butylperoxy) ) Butyrate, hydroxyheptyl peroxide, dichlorohexanone peroxide, 1,1-2 (tert-butylperoxy) 3,3,5-trimethylcyclohexane, n-butyl- Peroxy) valerate, and 2,2-2 (tert-butylperoxy) butane. Such an organic peroxide can be contained in the sealing material by, for example, adding the resin of the sealing material to the sheet during processing and melting and kneading.

(B) having a (meth) acryloyl group is contained preferably in a proportion of 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, and more preferably 1 to 10 parts by weight, based on 100 parts by weight of the resin (Rb) Particularly desirable. (B) having a (meth) acryloyl group can be appropriately crosslinked by setting the ratio to 0.1 parts by weight or more so that the adhesive strength can be more effectively improved and by setting it to 20 parts by weight or less, Can be effectively improved.

In the present invention, the resin (R) preferably has a number average molecular weight of 10,000 to 250,000 and a glass transition temperature of -40 to 100 ° C. When the number average molecular weight of the resin (R) is 250,000 or less, the adhesive force to the sealing material is effectively brought to 10,000 or more. Thus, the humidity resistance of the coating film of the easy adhesive is improved and the adhesion to the sealing material . The number average molecular weight of the resin (R) is preferably 10,000 to 150,000, more preferably 10,000 to 100,000, even more preferably 15,000 to 75,000, and particularly preferably 20,000 to 60,000. The number average molecular weight (Mn) is a value of the resin (R) in terms of polystyrene by gel permeation chromatography (GPC). For example, when the temperature of the column (KF-805L, KF-803L and KF-802 manufactured by Showa Denko K.K.) is 40 ° C, THF is used as the eluent and the flow rate is 0.2 mL / RI, sample concentration of 0.02%, and polystyrene as a standard sample. The number average molecular weight of the present invention is a value measured by the above method.

By setting the glass transition temperature of the resin (R) to 100 占 폚 or less, it is possible to easily maintain the hardness of the coating film of the adhesive and to improve the adhesion to the sealing material. By setting the temperature at or above -40 ° C, it is possible to maintain the moisture resistance and heat resistance of the coating film of the adhesive easily, maintain the adhesion to the sealing material well after the heat test, effectively prevent wrinkles from occurring on the surface of the coating film, If the sheet is rolled after the production, it may be difficult to cause blocking. The glass transition temperature of the resin (R) is more preferably -10 to 80 占 폚, particularly preferably 10 to 70 占 폚.

The glass transition temperature refers to a value measured by differential scanning calorimetry (DSC) on a resin having a solid content of 100% by drying the resin (R). For example, an aluminum pan with a sample weighed about 10 mg and an aluminum pan without sample are set in the DSC apparatus and quenched to -100 ° C using liquid nitrogen in a stream of nitrogen, then at 20 ° C / min , The temperature was raised to 200 DEG C, and the DSC curve was plotted. The straight line extending from the low temperature side of the DSC curve to the high temperature side (the DSC curve portion in the temperature region that does not cause the transition and reaction in the specimen) of the DSC curve and the point where the slope of the curve of the step- The extrapolated glass transition start temperature (Tig) can be obtained from the intersection of the tangent line and the tangent line, and this can be obtained as the glass transition temperature. The glass transition temperature of the present invention is a value measured by the above method.

It is preferable that the resin (R) has at least one of a hydroxyl group and an amino group for the purpose of improving adhesion between the plastic film (E) and the sealing material by crosslinking, or imparting moisture resistance and heat resistance to the adhesive layer. The sum of the hydroxyl value and the amine value of the resin (R) is preferably 2 to 100 (mgKOH / g), more preferably 2 to 50 (mgKOH / g) Is particularly preferable. By setting the sum of the hydroxyl value and the amine value of the resin (R) to 100 (mgKOH / g) or less, it is possible to appropriately crosslink the coating film of the adhesive agent and improve the adhesive force to the plastic film (E) It is possible to effectively prevent the crosslinking reaction from progressing and the adhesive strength from decreasing after the heat and humidity test. In addition, by setting the sum of the hydroxyl value and the amine value to 2 (mgKOH / g) or more, crosslinking of the coating film of the easy adhesive can be appropriately performed to improve the heat and humidity resistance of the coating film and to prevent the adhesive force of the sealing material from deteriorating after the heat and heat test.

The amine value (mgKOH / g) of the present invention can be obtained by the following measurement method. Measure 0.1 to 3 g of the sample in a beaker to 0.1 mg of the supernatant, add 10 mL of acetic acid and stir gently until the sample is completely dissolved. The test solution is titrated potentiometrically from 0.10 mol / L perchloric acid acetic acid solution to the end point near 600mV using an automatic titrator. The amine value of the sample is calculated by the following formula.

Amine value (mg KOH / g) = {(V x F x 5.61) / m} / (Solid content concentration / 100)

Where m is a weight (g) of the sample,

V: Capacity of 0.10 mol / L perchloric acid acetic acid solution (mL)

F: concentration factor of 0.10 mol / L perchloric acid acetic acid solution

c: concentration of sodium thiosulfate solution (mol / L)

The amine value of the present invention is the value measured by the above method.

Next, the polyisocyanate compound (C) will be described.

The polyisocyanate compound (C) reacts with the hydroxyl group and / or the amino group in the resin (R) to crosslink the resins (R), thereby easily imparting moisture resistance and heat resistance to the adhesive layer, E) and the sealing material (II) and / or the sealing material (IV). Therefore, it is preferable that the polyisocyanate compound (C) has two or more isocyanate groups in one molecule. Examples thereof include aromatic polyisocyanates, chain aliphatic polyisocyanates, and cyclic aliphatic polyisocyanates. The polyisocyanate compound (C) may be used alone or in combination of two or more.

The aromatic polyisocyanate may be 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- Isocyanate, isocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, Diphenyl ether diisocyanate, 4,4 ', 4 "-triphenyl methane triisocyanate, and the like.

The chain aliphatic polyisocyanate is selected from the group consisting of trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, Dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

The cyclic aliphatic polyisocyanate may be selected from the group consisting of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate , Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), 1,4-2 (isocyanate methyl) cyclohexane, .

In addition to the polyisocyanate, an adduct of the polyisocyanate with a polyol compound such as trimethylolpropane, a buret chain isocyanurate of the polyisocyanate, and a polyether polyol or a polyester polyol , Acryl polyol, polybutadiene polyol, and polyisoprene polyol.

Of the polyisocyanate compounds (C), aliphatic or alicyclic ring polyisocyanates of low sulfur modification are preferable from the viewpoint of formability, and isocyanurate compounds are preferable from the viewpoint of resistance to humid heat. More specifically, an isocyanurate of hexamethylene diisocyanate (HDI) and an isocyanurate of 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (IPDI) are preferred.

The blocked polyisocyanate compound (C1) can be obtained by reacting almost all of the isocyanate groups of these polyisocyanate compounds (C) with a blocking agent. It is preferable that the easy adhesive layer (D ') obtained by applying the easy adhesive for the solar cell protective sheet of the present invention before curing is in an uncrosslinked state until the solar cell module is manufactured by sticking to the sealing material. Thus, the polyisocyanate compound C) is preferably a blocked polyisocyanate compound (C1).

Examples of the blocking agent include phenols such as phenol, thiophenol, methylthiophenol, xylenol, cresol, resorcinol, nitrophenol and chlorophenol, oximes such as acetone oxime, methyl ethyl ketone oxime and cyclohexanone oxime, Butanol, t-pentanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, Alcohols such as methanol, ethanol, propanol, isopropanol, butanol and the like; alcohols such as methanol, ethanol, isopropanol, , 3-dichloro-2-propanol and the like, lactams such as? -Caprolactam,? -Valero-lactam,? -Butyrolactam and? -Propyllactam, Ethyl acetoacetate, acetic acid It may include an active methylene compounds such as acetone, methyl malonic acid, ethyl malonic acid. In addition, amines, imides, mercaptans, imines, ureas and diaryls can be mentioned. One block or two or more blocking agents may be used together.

Among these blocking agents, the dissociation temperature of the blocking agent is preferably 80 to 150 ° C. When the dissociation temperature is less than 80 캜, it is easy to apply an adhesive, and when the solvent is volatilized, the curing reaction progresses, which may lower the adhesion with the filler. When the dissociation temperature is higher than 150 캜, the curing reaction does not progress sufficiently in the vacuum heating and pressing process for constituting the solar cell module, and the adhesion with the filler is lowered.

The blocking agent having an evaporation temperature of 80 deg. C to 150 deg. C is methyl ethyl ketone oxime (evaporation temperature: 140 deg. C, the same applies), 3,5-dimethylpyrazole (120 deg. C), diisopropylamine For example.

The amount of the polyisocyanate compound (C) in the easy adhesive of the present invention is preferably such that the amount of the isocyanate group is in the range of 0.1 to 10 moles relative to 1 mole of the sum of the hydroxyl group and amine group in the resin (R) More preferably 5 moles. By setting the content to 0.1 mole or more, crosslinking density can be made appropriate and humidity and heat resistance can be made satisfactory. By setting the content to 10 moles or less, excess isocyanate reacts with water in the air during the heat and humidity test to cure the coating film, It is possible to effectively prevent the plastic film (E) and the sealing material constituting the battery protection sheet from causing a decrease in the adhesive strength.

The easy adhesive of the present invention may contain 0.01 to 30 parts by weight of organic particles or inorganic particles to be described later with respect to 100 parts by weight of solids. By adding these particles, wrinkles on the surface of the easy adhesive layer (D ') before the curing treatment can be reduced. Particularly, when 5 to 30 parts by weight of the inorganic particles are added, talc, hydrotalcite, mica and kaolin are more preferable among the inorganic particles because anticorrosion properties can be expected to be improved. If the content is less than 0.01 part by weight, the wrinkles on the surface of the easy adhesive layer (D ') before the hardening treatment can not be sufficiently reduced, and if it is less than 30 parts by weight, adhesion between the easy adhesive layer (D') and the sealing material And the adhesive force can be effectively increased.

As the organic particles, those having a melting point or a softening point of 150 DEG C or higher can be preferably used. When the melting point or the softening point of the organic particles is lower than 150 캜, the particles are softened in the step of vacuum heating and pressing at the time of constituting the solar cell module, and adhesion with the sealing material can be hindered.

Specific examples of the organic particles include polymers such as polymethylmethacrylate resin, polystyrene resin, nylon (registered trademark) resin, melamine resin, guanamine resin, phenol resin, urea resin, silicone resin, methacrylate resin, Particles, or cellulose powder, nitrocellulose powder, sawdust, waste paper powder, chaff powder, starch powder, and the like. The organic particles may be used either singly or in combination.

The polymer particles can be obtained by a polymerization method such as an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a soap pre-polymerization method, a seed polymerization method and a micro suspension polymerization method. The organic particles may contain impurities to such an extent that their properties are not impaired. The shape of the particles may be any shape such as powder, granular, granular, flat, or fiber.

Specific examples of the inorganic particles include inorganic particles containing oxides, hydroxides, sulfates, carbonates and silicates of metals such as magnesium, potassium, barium, zinc, zirconium, molybdenum, silicon, antimony and titanium. Specific examples thereof include silica gel, aluminum oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, zinc oxide, lead oxide, diatomaceous earth, zeolite, aluminosilicic acid, talc, white carbon, Inorganic particles containing glass powder, glass beads, clay, warasnite, iron oxide, antimony oxide, titanium oxide, lithopone, pumice powder, aluminum sulfate, zirconium silicate, barium carbonate, dolomite, molybdenum disulfide, . Some particles may be used alone or two or more may be used together.

The above-mentioned inorganic particles may contain impurities to such an extent that their properties are not impaired. The shape of the particles may be any shape such as powder, granular, granular, flat, or fiber.

If necessary, the easy adhesive of the present invention may be added with a crosslinking accelerator within a range not hindering the effect of the present invention. The crosslinking promoter serves as a catalyst for promoting the crosslinking reaction between the hydroxyl group and the amino group of the resin (R) other than the (meth) acrylic copolymer (A) and the isocyanate group of the polyisocyanate compound (C). Examples of the crosslinking accelerator include tin compounds, metal salts and bases, and specific examples thereof include tin octylate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, tin chloride, iron octylate, cobalt octylate , Zinc naphthenate, triethylamine, triethylenediamine, and the like. These may be used alone or in combination.

The easy adhesive of the present invention may contain additives such as fillers, thixotropic agents, antioxidants, antioxidants, antistatic agents, fire retardants, thermal conductivity improvers, plasticizers, flow-down agents Various additives such as an antioxidant, an antifouling agent, a preservative, a bactericide, an extinguishing agent, a leveling agent, a hardener, a thickener, a pigment dispersant and a silane coupling agent may be added.

Further, by adding an epoxy resin (Ep) to the easy adhesive of the present invention, the effect of improving wet heat resistance can be expected. The addition amount of the epoxy resin (Ep) is preferably 0.1 to 70 parts by weight, more preferably 0.5 to 60 parts by weight, especially 1 to 50 parts by weight, relative to 100 parts of the resin (R). Examples of the epoxy resin (Ep) include a glycidyl ether compound and a glycidyl ester compound.

Examples of the glycidyl ether compound include bisphenol-type epoxy resins, novolac epoxy resins, biphenol-type epoxy resins, beacilene-type epoxy resins, trihydroxyphenylmethane-type epoxy resins, and tetraphenylolethane-type epoxy resins. Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin and hydrogenated bisphenol A type epoxy resin.

Examples of the novolac epoxy resin include phenol novolak type epoxy resin, cresol novolak type epoxy resin, brominated phenol novolak type epoxy resin, naphthalene skeleton containing phenol novolak type epoxy resin, dicyclopentadiene skeleton containing phenol novolac epoxy resin And the like.

Examples of the glycidyl ester compound include diglycidyl ester of terephthalic acid and the like. These epoxy resins may be used alone or in combination of two or more.

The easy adhesive used in the present invention includes a solvent. Examples of the solvent include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether and diethylene glycol methyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane , Ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene, xylene and cumene; esters such as ethyl acetate and butyl acetate; Depending on the composition of the composition, a suitable one may be used, and a boiling point of 50 占 폚 to 200 占 폚 may be preferably used. If the boiling point is lower than 50 캜, the solvent tends to volatilize when the easy adhesive is applied, the solids content becomes high and it becomes difficult to coat the film with a uniform film thickness, and when the boiling point is higher than 200 캜, the solvent becomes difficult to dry. Two or more kinds of solvents may be used.

The easy adhesive of the present invention is coated on the plastic film E to form the easy adhesive layer D 'to produce a solar cell protection sheet Z' having good adhesion to the sealing material II and / or the sealing material IV .

As a method for coating the plastic film (E) with the easy adhesive of the present invention, a conventionally known method can be used. Specifically, comma coating, gravure coating, reverse coating, roll coating, lip coating, spray coating and the like can be mentioned. The easy adhesive layer (D ') before the curing treatment can be formed by applying the easy adhesive in this way and by volatilizing the solvent by heating and drying. The thickness of the easy adhesive layer (D ') before the curing treatment to be formed is preferably 0.01 to 30 탆, more preferably 0.1 to 10 탆.

Examples of the plastic film (E) include polyester resin films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, olefin films such as polyethylene, polypropylene and polycyclopentadiene, polyvinyl fluoride, polyvinylidene fluoride Film, a Teflon film, an ethylene-tetrafluoroethylene copolymer film, a fluorine-based film, an acrylic film, and a triacetylcellulose film. From the viewpoints of film stiffness and cost, a polyester-based resin film is preferable, and among these, a polyethylene terephthalate film is preferable. The plastic film (E) may be a single layer or a multilayer structure of two or more layers. The plastic film (E) may be laminated with a vapor deposition film obtained by vapor-depositing a metal oxide or a non-metal inorganic oxide.

When a polyester-based resin film is used as the plastic film (E), the film is a polyester-based resin film formed of a polyester resin having an intrinsic viscosity of 0.6 (dL / g) or more and a cyclic trimer content of 1 wt% It is good. It is more preferable that the intrinsic viscosity is 0.6 to 1.2 (dL / g). The lower the content of the cyclic trimer is, the better the lower the content is, but the lower the content of the cyclic trimer is, the more preferable the content is 0.5 wt% or less. By using such a film, degradation of strength due to hydrolysis in long-term exposure such as outdoor can be suppressed.

The content of the cyclic trimer of the polyester resin forming the polyester-based resin film is obtained by dissolving 100 mg of the polyester resin in 2 mL of orthochlorophenol and measuring the weight percentage by liquid chromatography.

The intrinsic viscosity of the polyester resin forming the polyester-based resin film is determined by the following formula.

That is, the intrinsic viscosity η sp = (η / η 0) -1 is obtained by extrapolating η sp / c, which is the amount obtained by dividing by the concentration c, to zero.

Η0 is the viscosity of the solvent, c (g / mL) is the concentration of the resin in the solvent, η is the viscosity of the resin solution in c (g / mL), and η sp is the viscosity ratio of the resin solution and solvent.

As the metal oxide or non-metal inorganic oxide deposited on the plastic film (E), oxides such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium and yttrium can be used. , An alkaline earth metal fluoride, and the like, and they may be used alone or in combination. These metal oxides and non-metal inorganic oxides can be deposited by a known CVD method such as PVD method such as vacuum deposition, ion plating, sputtering, plasma CVD, microwave CVD or the like.

When the solar cell protection sheet Z 'is used on the non-light receiving surface side, the plastic film E constituting the solar cell protection sheet Z' may be colorless or may contain coloring components such as pigments or dyes good. When the solar cell protection sheet Z 'is used on the light receiving surface side, it is preferable that the plastic film E constituting the solar cell protection sheet Z' is colorless. The method of containing a coloring component includes, for example, a method of kneading a coloring component in advance when a film is formed, a method of printing a coloring component on a colorless transparent film substrate, and the like. In addition, a colored film and a colorless transparent film may be stuck together and used.

The solar cell protection sheet Z 'is formed by laminating a film layer such as a metal foil F or a weather-resistant resin layer G on the surface of the plastic film E on the side where the easy adhesive layer D' Or may be provided in multiple layers.

The metal foil (F) may be an aluminum foil, an iron foil, a zinc laminate, or the like. Among them, an aluminum foil is preferable from the viewpoint of corrosion resistance. The thickness is preferably 10 탆 to 100 탆, more preferably 20 탆 to 50 탆. Various known adhesives can be used for the lamination of the metal foil (F).

The weather-resistant resin layer (G) is formed by laminating a polyester resin film such as a polyvinylidene fluoride film, polyethylene terephthalate, polybutylene terephthalate, or poly naphthalene terephthalate with various known adhesives, A coating layer formed by coating a high-weather-resistant coating such as lumi- fur, or the like can be used.

The solar cell module of the present invention is characterized in that the solar cell surface protection material I positioned on the light receiving surface side of the solar cell with respect to the solar cell III is sealed with the sealing material II before the curing treatment, And stacking the protective material (V) on the non-light-receiving surface side of the solar cell through the sealing material (IV) before the curing treatment, and hot-pressing the material in a vacuum at a high temperature.

Examples of the solar cell surface protection material (I) and the solar cell protective material (V) include a glass plate, a polycarbonate or a plastic plate of polyacrylate, but at least one of them is formed of the solar cell protection sheet (Z ' . The solar cell module of the present invention is characterized in that a glass plate is used for the solar cell surface protection material (I) in view of practical durability and combustibility, and the protection material (V) is formed of the solar cell protection sheet .

The sealing material such as EVA used as the sealing materials (II) and (IV) may contain additives such as an ultraviolet absorber for improving weather resistance, a light stabilizer, and an organic peroxide for crosslinking EVA itself.

Examples of the solar cell (III) include electrodes provided on photoelectric conversion layers such as a compound semiconductor represented by crystalline silicon, amorphous silicon, and copper indium selenide, and those obtained by laminating them on a substrate such as glass .

≪ Embodiment >

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples. In the Examples, parts are by weight, and% is by weight. The iodine value, number average molecular weight (Mn) and amine value are values measured by the above-mentioned method. The glass transition temperature and hydroxyl value were measured by the methods described below.

≪ Measurement of Glass Transition Temperature (Tg) >

The glass transition temperature was measured according to the differential scanning calorimetry (DSC) method described above. The sample for Tg measurement was obtained by heating and drying the acrylic resin solution at 150 DEG C for about 15 minutes.

≪ Measurement of hydroxyl value (OHV) >

Approximately 1 g of the sample is precisely weighed in a stoppered Erlenmeyer flask and dissolved in 100 mL of a mixture of toluene / ethanol (volume ratio: toluene / ethanol = 2/1). Exactly 5 mL of an acetylating agent (a solution of 25 g of acetic anhydride dissolved in pyridine and having a volume of 100 mL) is added and mixed for about 1 hour. Here, the phenolphthalein reagent is added as an indicator and maintained for 30 seconds. The solution is then titrated with 0.1 N alcoholic potassium hydroxide solution until it becomes pale red. The hydroxyl value was obtained through the equation. The hydroxyl value was a numerical value of the dry state of the resin (unit: mgKOH / g).

(MgKOH / g) = {{(b-a) x F x 28.25} / S] / (nonvolatile concentration / 100) + D

S: amount of sample (g)

a: consumption of 0.1N alcoholic potassium hydroxide solution (mL)

b: Consumed amount of 0.1N alcoholic potassium hydroxide solution (mL)

F: Potency of 0.1N Alcoholic Potassium Hydroxide Solution

D: acid value (mgKOH / g)

≪ Solution of olefin resin R11 >

A pressure-resistant autoclave was charged with 2,000 g of butyl acetate, 420 g of vinyl 2,2-methylpropylpentanoate, 100 g of vinyl benzoate and 15 g of 4-hydroxybutyl vinyl ether, and the autoclave was evacuated under reduced pressure. Then, the pressure was reduced again, 70 g of ethylene was put therein, and after the temperature was raised to 60 캜, 20 g of t-butylene peroxypivalate was put in and polymerized. When the pressure in the reactor reached a specific pressure, the reaction was stopped to obtain an olefin resin R11 having a number average molecular weight of 16,000, a hydroxyl value of 11.1 (mgKOH / g) and a Tg of 25 占 폚. This was dissolved in toluene to make the solid content 20%, which was used as the olefin resin R11 solution.

≪ Olefin resin R12 to R14, R16 to R18 solution >

Resins of olefinic resins R12 to R14 and R16 to R18 were synthesized in the same manner as in the case of the olefinic resin R11 solution except that the monomers used in the synthesis of the olefinic resin R11 solution were changed as shown in Table 1. Table 1 shows the Tg, the number average molecular weight, and the hydroxyl value of the obtained olefin resin.

≪ Olefin-based resin R15 solution >

Unistol P801 (manufactured by Mitsui Gagaku Co., Ltd.) was used as the olefin resin R15 solution. Table 1 shows the Tg, number average molecular weight and hydroxyl value of the olefin resin R15.

The abbreviations in Table 1 indicate the following.

ET: Ethylene

nBVE: n-butyl vinyl ether

CHVE: cyclohexyl vinyl ether

MPPV: 2,2-methylpropylpentanecarbonate

VBz: vinyl benzoate

HBVE: 4-hydroxybutyl vinyl ether

Olefin resin Ethylenic monomer
Tg
(° C) Number average molecular weight OH value ET nBVE CHVE MPPV VBz HBVE mgKOH / g R11 70 0 0 420 100 15 25 16000 11.1 R12 270 0 0 70 50 15 -32 26000 19.5 R13 50 50 0 50 400 30 52 19000 28.1 R14 100 0 60 350 50 80 10 16000 81.2 R15 Unistol P801 (manufactured by Mitsui Chemicals, Inc.) 42 120000 40.3 R16 300 0 0 70 0 20 -45 18000 12.8 R17 70 50 0 370 80 15 31 12000 17 R18 70 0 100 300 50 140 22 15000 138.2

≪ Solution of olefin resin R11 &

Into a three-necked flask equipped with a condenser, a nitrogen inlet tube, a stirrer, and a thermometer, 500 parts of the olefin resin R11 solution was added, and the temperature was raised to 40 ° C while stirring. 0.03 parts of dibutyltin dilaurate was added, and 7.1 parts of 2-isocyanate ethyl methacrylate (hereinafter abbreviated as MOI) was dropped for 3 hours while stirring at 40 占 폚. IR, the disappearance of the isocyanate peak (2260 cm < -1 >) was confirmed. The Tg was 23 ° C, the number average molecular weight was 16,000, the hydroxyl value was 5.0 mgKOH / g, the iodine value was 2.3 g / % Of an olefin resin R11 'solution.

<Olefin-based resin R12 'to R19' solution>

The olefin resin R12 'to R19' solutions were synthesized in the same manner as in the olefin resin R11 'solution except that the amount of 2-isocyanate ethyl methacrylate (MOI) used in the synthesis of the olefin resin R11' solution was changed as shown in Table 2. Table 2 shows the Tg, number average molecular weight, hydroxyl value and iodine value of the obtained olefin resin.

Olefin resin Used in the reaction
Olefin resin MOI
Addition amount Tg
(° C) Number average molecular weight OH value Iodine value Suzy Quantity mgKOH / g g / 100g R11 ' R11 500 7.1 23 16000 5.0 2.3 R12 ' R12 500 13.8 -33 26000 9.8 4.5 R13 ' R13 500 27.6 52 20000 8.2 9 R14 ' R14 500 13.8 7 16000 72 4.4 R15 ' R15 500 27.6 42 120000 20 9.3 R16 ' R16 500 6.9 -46 18000 7.7 2.2 R17 ' R17 500 13.8 30 12000 7.2 4.5 R18 ' R18 500 27.6 22 17000 109 9.1 R19 ' R18 500 165.6 13 18000 17 54

&Lt; Fluorine-based resin R21 solution >

A pressure-resistant autoclave was charged with 2,000 g of butyl acetate, 350 g of vinyl 2,2-methylpropylpentanoate, 50 g of vinyl benzoate and 15 g of 4-hydroxybutyl vinyl ether, and the autoclave was evacuated under reduced pressure. Subsequently, the pressure was reduced again, 100 g of trifluoroethylene and 70 g of ethylene were put in, and the temperature was raised to 60 DEG C, and 20 g of t-butylene peroxypivalate was put therein and polymerized. When the pressure in the reactor reached a specific pressure, the reaction was stopped to obtain a fluororesin R21 having a number average molecular weight of 17,000, a hydroxyl value of 12.8 (mgKOH / g) and a Tg of 41 占 폚. This was dissolved in coal tar naphtha and a solid content of 20% was used as the fluororesin R21 solution.

&Lt; Fluorine-based resin R22 to R24 and R26 to R28 solution >

Resins of fluorine resins R22 to R24 and R26 to R28 were synthesized in the same manner as in the fluororesin R21 solution except that the composition of the monomers used in the synthesis of the fluororesin R21 solution was changed as shown in Table 3. [ Table 3 shows the Tg, the number average molecular weight and the hydroxyl value of the obtained fluororesin.

&Lt; Fluorine-based resin R25 solution >

Lumipuron LF-200 (manufactured by Asahi Kasei Chemicals Co., Ltd.) is used as the fluororesin R25 solution. Table 3 shows the Tg, number average molecular weight, hydroxyl value and amine value of the olefin resin R25.

The abbreviations in Table 3 indicate those already shown in the table or the following.

TFE: Trifluoroethylene

CTFE: chlorotrifluoroethylene

Fluorine resin Ethylenic monomer
Tg
(° C) Number average molecular weight OH value ET TFE CTFE MPPV VBz HBVE mgKOH / g R21 70 100 0 350 50 15 41 17000 12.8 R22 250 50 0 70 0 15 -27 24000 17 R23 60 0 60 50 400 15 61 20000 15.6 R24 50 0 60 370 50 80 15 19000 77.3 R25 LUMIFLON LF-200 (manufactured by Asahi Kasei Chemicals Co., Ltd.) 35 18000 51.1 R26 280 20 0 70 0 20 -41 21000 13.2 R27 100 70 0 350 50 15 35 11000 14.9 R28 50 0 120 250 40 140 16 17000 115.5

<Fluorine Resin R21 'Solution>

A three-necked flask equipped with a cooling tube, a nitrogen inlet tube, a stirrer, and a thermometer was charged with 500 parts of the fluororesin R21 solution, and the temperature was raised to 40 ° C with stirring. 0.03 parts of dibutyltin diurate was added, and 6.9 parts of 2-isocyanate ethyl methacrylate (MOI) was dropped over 3 hours while stirring at 40 占 폚. IR of the isocyanate peak (2260 cm &lt; -1 &gt;) was lost. The Tg was 40 DEG C, the number average molecular weight was 17,000, the hydroxyl value was 7.9 (mgKOH / g), the iodine value was 2.3 (g / To obtain a fluororesin R21 'solution.

<Fluorine-based resin R22 'to R28' solution>

Fluorine Resin R21 'A fluorine resin solution R22' to R28 'solution was synthesized similarly to the fluorine resin R21' solution except that the amount of 2-isocyanate ethyl methacrylate (MOI) used in the synthesis of the solution was changed as shown in Table 4. Table 4 shows the Tg, the number average molecular weight, the hydroxyl value and the iodine value of the obtained fluorine resin.

Fluorine resin Used in the reaction
Fluorine resin MOI
Addition amount Tg
(° C) Number average molecular weight OH value Iodine value Suzy Quantity mgKOH / g g / 100g R21 ' R21 500 6.9 40 17000 7.9 2.3 R22 ' R22 500 13.8 -27 24000 7 4.7 R23 ' R23 500 6.9 61 20000 10.6 2.4 R24 ' R24 500 13.8 14 19000 67.8 4.6 R25 ' R25 500 13.8 35 18000 41.2 4.8 R26 ' R26 500 6.9 -41 21000 8.2 2.2 R27 ' R27 500 6.9 35 11000 10 2.3 R28 ' R28 500 13.8 16 18000 106 4.7

&Lt; Polyester resin R31 solution >

8 parts of terephthalic acid, 8 parts of isophthalic acid, 5 parts of adipic acid, 40 parts of sebacic acid, 10 parts of ethylene glycol, 10 parts of neopentyl glycol , And 17 parts of 1,6-hexanediol were put in a flask and heated at 160 to 240 占 폚 under stirring in a nitrogen stream to carry out ester exchange. Subsequently, the polymerization vessel was gradually depressurized to 1 to 2 Torr, and the reaction at reduced pressure was stopped when the viscosity became a predetermined value, and the number average molecular weight was 18,000, the hydroxyl value was 6.5 (mgKOH / g) and the Tg was -37 deg. A polyester polyol was obtained and diluted with ethyl acetate to obtain a polyester resin R31 solution having a solid content of 50%.

&Lt; Polyester resin R32 to R35, R37, R38 solution >

Ribbons of R32 to R35, R37 and R38 were synthesized in the same manner as in the case of the polyester-based resin R31 solution, except that the composition of the monomers used in the synthesis of the polyester-based resin R31 solution was changed as shown in Table 5. Table 5 shows the Tg, the number average molecular weight and the hydroxyl value of the obtained polyester-based resin.

&Lt; Polyester resin R36, R39 solution >

By-run GK880 (manufactured by Toyobo Co., Ltd.) was dissolved in MEK and the solids content was made 50%, thereby obtaining a polyester resin R36 solution. Further, Elitel UE-9900 (manufactured by Unitika Co., Ltd.) was dissolved in toluene and the solid content was adjusted to 30% as a polyester resin R36 solution. Table 5 shows the Tg, the number average molecular weight and the hydroxyl value of the obtained polyester-based resin.

The abbreviations in Table 5 indicate the following.

TPA: terephthalic acid

IPA: isophthalic acid

AdA: adipic acid

SeA: sebacic acid

EG: ethylene glycol

NPG: neopentyl glycol

1,6-HD: 1,6-hexanediol

TMP: trimethylol propane

Polyester resin Carboxylic acid component
Hydroxyl component
Tg
(° C) Number average molecular weight OH value TPA IPA Ada SeA EG NPG 1,6-HD TMP mgKOH / g R31 8 8 5 40 10 11 17 0 -37 18000 6.5 R32 15 15 0 37 15 17 0 0 -10 26000 4.5 R33 36 0 31 0 23 10 0 0 35 16000 7.8 R34 32 32 0 0 13 13 10 0 60 23000 5.3 R35 21 21 25 0 23 9 0 One 10 22000 12 R36 Byron GK880 (manufactured by Toyo Boseki Co., Ltd.) 84 18000 6 R37 6 6 0 60 20 8 0 0 -44 24000 4.9 R38 18 18 0 15 10 8 19 0 One 12000 9.4 R39 Elitel UE-9900 (manufactured by Unitika) 101 15000 8

<Polyester resin R31 'to R39' solution>

Except that the amount of the resin solution used in the synthesis of the fluororesin R21 'solution and the amount of the 2-isocyanate ethyl methacrylate (MOI) were changed as shown in Table 6, the polyester resin R31' to R39 'solutions were synthesized similarly to the fluororesin R21' did. Table 6 shows the Tg, number average molecular weight, hydroxyl value and iodine value of the obtained polyester-based resin.

Polyester resin Used in the reaction
Polyester resin MOI
Addition amount Tg
(° C) Number average molecular weight OH value Iodine value Suzy Quantity mgKOH / g g / 100g R31 ' R31 500 3.5 -37 18000 4 1.2 R32 ' R32 500 3.5 -10 26000 2 1.3 R33 ' R33 500 3.6 35 16000 5.1 1.4 R34 ' R34 500 3.5 60 23000 2.8 1.2 R35 ' R35 500 6.9 10 22000 7.1 2.4 R36 ' R36 500 3.5 84 18000 3.5 1.5 R37 ' R37 500 3.5 -44 24000 2.4 1.1 R38 ' R38 500 6.9 One 12000 4.4 2.3 R39 ' R39 500 3.5 101 15000 5.2 1.2

&Lt; Polyurethane resin R41 solution >

368 parts of C-2090 (polycarbonate polyol, manufactured by Kuraray Co., Ltd.), 32 parts of xylene diisocyanate and 100 parts of toluene were placed in a four-necked flask equipped with a stirrer, a thermometer and a dropping funnel And 0.03 part of dibutyltin dilaurate as a catalyst were charged, and the temperature was gradually raised to 100 占 폚 and reacted for 3 hours. After confirming that there was no NCO peak due to IR measurement, 300 parts of ethyl acetate was added to obtain a polyurethane resin R41 solution having a number average molecular weight of 23,000, a hydroxyl value of 4.9 (mgKOH / g), a Tg of -5 캜 and a solid content of 50% .

<Polyurethane resin R42 to R47 solution>

A polyurethane resin R42 to R47 solution was synthesized in the same manner as the polyurethane resin R41 solution except that the composition of the hydroxyl group component and the isocyanate compound used in the synthesis of the polyurethane resin R41 solution was changed as shown in Table 7. [ The Tg, the number average molecular weight, and the hydroxyl value of the obtained polyurethane-based resin are shown in Table 7.

In addition, the abbreviations in Table 7 indicate those already shown in the table or the following.

C-2090: polycarbonate polyol, product of Kuraray Co., Ltd.

PTMG-3000: polytetramethylene ether glycol, manufactured by Mitsubishi Kagaku Co., Ltd.

CHDM: Cyclohexanedimethanol

XDI: xylene diisocyanate

HDI: hexamethylene diisocyanate

IPDI: isophorone diisocyanate

Polyurethane resin Hydroxyl component
Isocyanate
compound Tg
(° C) Number average
Molecular Weight OH value C-2090 PTMG
-3000 1,6-HD CHDM TMP XDI HDI IPDI mgKOH / g R41 368 0 0 0 0 32 0 0 -5 23000 4.9 R42 263 0 0 44 0 0 0 93 65 18000 6.3 R43 0 369 5 0 0 0 26 0 -33 20000 5.5 R44 0 311 7 17 One 0 0 64 2 81000 8.6 R45 0 335 15 0 5 45 0 0 -10 16000 83 R46 355 0 0 11 0 34 0 0 8 9000 13.8 R47 0 303 36 0 0 0 61 0 -44 18000 5.9

<Polyurethane resin R41 'to R47' solution>

A polyurethane resin R41 'to R47' solution was synthesized in the same manner as in the fluororesin R21 'solution except that the amounts of the resin solution and 2-isocyanate ethyl methacrylate (MOI) used in the synthesis of the fluororesin R21' solution were changed as shown in Table 8 . Table 8 shows the Tg, the number average molecular weight, the hydroxyl value and the iodine value of the obtained polyurethane resin.

Polyurethane resin Used in the reaction
Polyurethane resin MOI
Addition amount Tg
(° C) Number average
Molecular Weight OH value Iodine value Suzy Quantity mgKOH / g g / 100g R41 ' R41 500 3.5 -5 23000 2.3 1.2 R42 ' R42 500 3.5 62 18000 3.7 1.4 R43 ' R43 500 3.5 -33 20000 3 1.2 R44 ' R44 500 3.5 2 81000 8.6 1.4 R45 ' R45 500 27.6 -15 17000 62.8 9 R46 ' R46 500 6.9 8 9000 8.7 2.4 R47 ' R47 500 3.5 -44 18000 2.3 1.2

<Polyurethane-urea resin R51 solution>

310 parts of C-2090 (polycarbonate polyol manufactured by Kuraray Co., Ltd.), 64 parts of xylene diisocyanate and 100 parts of toluene were put in a four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel And 0.03 part of dibutyltin dilaurate as a catalyst were charged, and the temperature was gradually raised to 100 占 폚 and reacted for 3 hours. After cooling to 40 DEG C, 200 parts of ethyl acetate was added, and 26 parts of isophoronediamine was dropped over 1 hour, and stirring was further continued for 1 hour. Amino-2-methylpropanol was added to the mixture to confirm that there was no NCO peak due to IR measurement, and the mixture was diluted with ethyl acetate to obtain a copolymer having a number average molecular weight of 26,000, a hydroxyl value of 4.3 (mgKOH / g) 50% of a polyurethane-urea-based resin R51 solution was obtained.

<Polyurethane-urea resin R52 to R59 solution>

The polyurethaneurea resin R52 to R59 were prepared in the same manner as the polyurethaneurea resin R51 solution except that the composition of the compound having two or more hydroxyl groups, isocyanate compounds and amino groups used in the synthesis of the polyurethaneurea resin R51 solution was changed as shown in Table 9 Solution was synthesized. Table 9 shows the Tg, the number average molecular weight and the hydroxyl value of the obtained polyurethaneurea resin.

The abbreviations in Table 9 also indicate those already shown in the table or the following.

HDA: hexamethylenediamine

IPDA: isophorone diamine

XDA: Xylene diamine

DAB: 1,4-diamino-2-butanol

Polyurethane
Urea system
Suzy Hydroxyl component
Isocyanate
compound Two or more amino groups
Compound Tg
(° C) Number average
Molecular Weight OH value C-2090 PTMG
-3000 1,6-HD CHDM XDI HDI HDA IPDA XDA DAB mgKOH / g R51 310 0 0 0 64 0 0 26 0 0 32 26000 4.3 R52 250 0 0 18 99 0 0 0 34 0 75 33000 3.5 R53 0 330 3 0 52 0 0 0 30 6 -12 96000 7.5 R54 240 0 0 0 0 118 0 0 0 49 44 38000 72 R55 0 297 12 0 0 69 14 0 0 8 -33 45000 10.1 R56 251 0 10 0 103 0 0 36 0 0 25 12000 9.5 R57 0 329 10 0 0 51 10 0 0 0 -45 22000 5.9 R58 161 0 5 0 0 163 0 0 0 71 30 17000 104.2 R59 187 0 0 14 141 0 0 0 59 0 102 18000 7.5

<Polyurethane-urea resin R51 'to R59' solution>

As in the case of the fluororesin R21 'solution except that the amount of the resin solution used in the synthesis of the fluororesin R21' solution and the amount of the 2-isocyanate methacrylate (MOI) were changed as shown in Table 10, the polyurethaneurea resins R51 'to R59' . Table 10 shows the Tg, the number average molecular weight, the hydroxyl value and the iodine value of the obtained polyurethaneurea resin.

Polyurethane
Urea
Cause Used in the reaction
Polyurethane urea resin MOI
Addition amount Tg
(° C) Number average
Molecular Weight OH value Iodine value Suzy Quantity mgKOH / g g / 100g R51 ' R51 500 3.5 32 26000 1.8 1.3 R52 ' R52 500 3.5 75 33000 1.1 1.3 R53 ' R53 500 3.5 -12 96000 4.9 1.2 R54 ' R54 500 13.8 40 39000 62.1 4.5 R55 ' R55 500 6.9 -33 45000 5.3 2.4 R56 ' R56 500 6.9 25 12000 4.4 2.4 R57 ' R57 500 3.5 -45 22000 2.2 1.3 R58 ' R58 500 3.5 30 17000 101.7 1.2 R59 ' R59 500 3.5 101 18000 4.8 1.3

&Lt; Polyamide-based resin R61 solution >

A flask equipped with a stirrer thermometer, a nitrogen inlet tube, a reflux condenser and a distillation tube was charged with 180 parts of ion-exchanged water, 73 parts of adipic acid, 100 parts of sebacic acid and 127 parts of hexamethylenediamine. The mixture was stirred until the temperature of the exotherm was constant. When the temperature was stabilized, the temperature was elevated to 110 ° C. After confirming the outflow of water, the temperature was elevated to 120 캜 after 30 minutes, and then the temperature was elevated by 10 캜 every 30 minutes until the temperature became 220 캜. The reaction was terminated when the amine value was reached at 220 ° C for 3 hours, and the reaction was terminated. The reaction mixture was diluted with toluene to obtain a polyamide-based resin having a number average molecular weight of 21,000, an amine value of 4.4 (mgKOH / g), a Tg of 35 ° C and a solid content of 30% To obtain a resin R61 solution.

&Lt; Polyamide-based resin R62 to R66 solution >

A polyamide resin R62 to R67 solution was synthesized in the same manner as in the case of the polyamide resin R61 solution except that the composition of the carboxylic acid component used in the synthesis of the polyamide resin R61 solution and the compound having two or more amine groups were changed as shown in Table 11 . Table 11 shows the Tg, the number average molecular weight and the amine value of the obtained polyamide-based resin.

The abbreviations in Table 11 indicate those already shown in the table.

Polyamide resin Carboxylic acid component
Two or more amino groups
Compound Tg
(° C) Number average
Molecular Weight Amine value TPA IPA Ada SeA XDA HDA IPDA mgKOH / g R61 0 0 73 100 0 127 0 35 21000 4.4 R62 0 0 71 98 132 0 0 59 72000 1.2 R63 30 30 0 174 126 0 0 88 22000 4.9 R64 0 0 64 88 0 0 148 31 31000 3.6 R65 0 0 62 86 0 62 90 30 10000 9.4 R66 60 60 0 22 100 0 0 105 17000 6.4

<Polyamide resin R61 'to R66' solution>

Except that the amounts of the resin solution and 2-isocyanate ethyl methacrylate (MOI) used in the synthesis of the fluororesin R21 'solution were changed as shown in Table 12, the polyamide resin R61' to R66 'solutions were synthesized similarly to the fluororesin R21' did. Table 12 shows the Tg, the number average molecular weight, the amine value and the iodine value of the obtained polyamide-based resin.

Polyamide resin Used in the reaction
Polyamide resin MOI
Addition amount Tg
(° C) Number average
Molecular Weight Amine value Iodine value Suzy Quantity mgKOH / g g / 100g R61 ' R61 500 3.5 35 21000 1.9 1.2 R62 ' R62 500 0.7 59 72000 0.7 0.5 R63 ' R63 500 3.5 88 22000 2.4 1.3 R64 ' R64 500 3.5 31 31000 1.1 1.3 R65 ' R65 500 6.9 30 11000 4.3 2.5 R66 ' R66 500 3.5 104 17000 3.9 1.4

<Preparation of Easy Adhesive Solution 1 to 221>

(B) having a (meth) acryloyl group, a polyisocyanate compound (a compound having a (meth) acryloyl group), a polyisocyanate compound 13-2, 13-3, 13-4, 15-1A, 15-1B, 15-2, 15-3A (C), epoxy resin (Ep) , 15-3B, 17-1A, 17-1B, 17-2A, 17-2B, 17-3A, 17-3B, 19-1A, 19-1B, 19-2A, 19-2B, 19-3A, 19 3B, 21-1A, 21-1B, 21-2A, 21-2B, 21-3A, 21-3B, 23-1, 23-2 and 23-3, &Lt; / RTI &gt;

&Lt; Easy adhesive solution 1 'to 30'

(H), a solution of a polyisocyanate compound (C), a solution of a polyisocyanate compound (C), a solution of a polyisocyanate compound (C), a solution of a fluorine resin, a solution of a polyester resin, a solution of a polyurethane resin, Were mixed in the compositions shown in Tables 14, 16, 18, 20, 22 and 24 to obtain easy adhesive solutions 1 'to 30'.

&Lt; Production of polyester film 1 >

A polyester film 1 having a thickness of 125 m was produced at a temperature of 250 캜 using a polyester resin having an intrinsic viscosity of 0.67 (dL / g) and a cyclic trimer content of 0.5% by weight by means of a T-die extruder did.

<Fabrication of solar cell protection sheet>

One side of the polyester film 1 was subjected to corona treatment, the easy adhesive solution 1 was applied to the treated surface with a gravure coater, and the solvent was dried to prepare a easy adhesive layer having a coating amount of 1 g / m 2 to prepare a solar cell protection sheet 1.

As in the case of the solar cell protection sheet 1, the solar cell protection sheets 2 to 221 were produced using the easy adhesive solution 2 to 221. [

&Lt; Preparation of Sample for Evaluation of Adhesion Force &

A solar cell protective sheet 1, and a solar cell protective sheet 1 were bonded so that the easy adhesive layer of the solar cell protective sheet 1 was in contact with the EVA film. I got it. Thereafter, the laminate was placed in a vacuum laminator, evacuated to about 1 Torr, heated at 150 占 폚 for 30 minutes at a press pressure of 0.1 MPa, and further heated at 150 占 폚 for 30 minutes to prepare a sample 10 for square-

Samples 2 to 56 for evaluating adhesion strength were prepared using the solar cell protective sheets 2 to 56 in the same manner as the adhesion strength evaluation sample 1.

[Example 1]

Adhesiveness to the EVA film of the easy adhesive layer and evaluation of adhesiveness after the moisture resistance heat test (after 1000 hours and after 2000 hours) were evaluated by the method 1 for evaluating adhesion strength.

&Lt; Evaluation of adhesiveness >

One side of the solar cell protective sheet of Sample 1 for adhesion evaluation was cut into a 15 mm width with a knife to measure the adhesion between the easy adhesive layer formed on the solar cell protective sheet 1 and the EVA film as a sealing material. For the measurement, a 180 degree peel test was carried out at a load speed of 100 mm / min using a tensile tester. The obtained measurements were evaluated as follows.

◎: 50N / 15mm or more

O: 30 N / 15 mm or more to 50 N / 15 mm or less

?: 10 N / 15 mm or more to less than 30 N / 15 mm

×: less than 10 N / 15 mm

&Lt; Evaluation of adhesiveness after anti-wet heat test >

The adhesive strength evaluation sample 1 was allowed to stand at an ambient temperature of 85 DEG C and a relative humidity of 85% RH for 1000 hours and 2000 hours, and then the adhesiveness after the moisture resistance heat test was evaluated in the same manner as the adhesion strength measurement.

[Examples 2 to 221], [Comparative Examples 1 to 30]

As in Example 1, the adhesive strength evaluation samples 2 to 221 and 1 'to 30' were used to evaluate the adhesiveness of the easy adhesive layer to the EVA film and the adhesiveness after the heat resistance test. The above results are shown in Tables 13-1, 13-2, 13-3, 13-4, 14, 15-1A, 15-1B, 15-2, 15-3A, 15-3B, 16, 17-1A, 1B, 17-2A, 17-2B, 17-3A, 17-3B, 18,19-1A, 19-1B, 19-2A, 19-2B, 19-3A, 19-3B, 20,21-1A, 21-1B, 21-2A, 21-2B, 21-3A, 21-3B, 22, 23-1, 23-2, 23-3,

Abbreviations in Tables 13-1 to 24 indicate the following.

<Compounds B1 to B6 having a (meth) acryloyl group>

(B1) to (B6) having a (meth) acryloyl group were used as they were.

B1: Aronix M-215 (manufactured by Toagosei Co., Ltd., isocyanuric acid EO-modified diacrylate)

B2: Aronix M-315 (manufactured by Toagosei Co., Ltd., isocyanuric acid EO-modified diacrylate)

B3: Epoxy ester 70PA (Epolite 70P acrylic acid adduct, manufactured by Kyoeisha Chemical Co., Ltd.)

B4: KAYARAD PET-30 (pentaerythritol triacrylate manufactured by Nihon Kayaku Co., Ltd.)

B5: TMPTA (trimethylolpropane triacrylate)

B6: DPHA (dipentaerythritol hexaacrylate)

&Lt; Polyisocyanate compound solution C >

The isocyanurate of hexamethylene diisocyanate blocked with 3,5-dimethylpyrazole was diluted to 75% with ethyl acetate to obtain a polyisocyanate compound solution (C).

<Aryl group-containing compounds H1 to H4>

As the aryl group-containing compounds H1 to H4, the following compounds were used as they were.

H1: TAIC (product of Nihon Kasei Corporation, triarylisocyanurate)

H2: neoaryl E-10 (product of Iso Co., glycerin monoaryl ether)

H3: Neoaryl T-20 (trimethylolpropane diarylate, product of ISOO Co., Ltd.)

H4: Neoaryl P-30M (pentaerythritol triallyl ether, product of Iso Corporation)

<Epoxy resins Ep1 to Ep3>

For the epoxy resins Ep1 to Ep3, the following compounds were used as they were.

Ep1: jER1001 (manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin)

Ep2: YDCN-704 (cresol novolak epoxy resin, product of Dodogasei Co., Ltd.)

Ep3: Denacol EX-821 (polyethylene glycol diglycidyl ether, product of Nagase Chemtech Co., Ltd.)

&Lt; Inorganic particles M1 to M4 >

The following inorganic particles were directly used for the inorganic particles M1 to M4.

M1: Talc LMS-400 (manufactured by Fuji Talc Co., Ltd.)

M2: hydrotalcite DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.)

M3: kaolinite SATINTONE W (product of Mori Kasei Co., Ltd.)

M4: montmorillonite KNIFER F (manufactured by Kuniminego Kogyo Co., Ltd.)

[Table 13-1]

The compounding ratios in Tables 13-1 to 13-4 are as follows: the solid content of the easy adhesive solution

[Table 13-2]

[Table 13-3]

[Table 13-4]

[Table 14]

The compounding ratio in the table means that the solids content of the easy adhesive solution

[Table 15-1A]

The mixing ratios in Tables 15-1A to 15-3B are as follows: the solid content of the easy adhesive solution

[Table 15-1B]

[Table 15-2]

[Table 15-3A]

[Table 15-3B]

[Table 16]

The compounding ratio in the table means that the solids content of the easy adhesive solution

[Table 17-1A]

The mixing ratios in Tables 17-1A to 17-3B are as follows: the solid content of the easy adhesive solution

[Table 17-1B]

The mixing ratios in Tables 17-1A to 17-3B are as follows: the solid content of the easy adhesive solution

[Table 17-2A]

[Table 17-2B]

[Table 17-3A]

[Table 17-3B]

[Table 18]

The compounding ratio in the table means that the solids content of the easy adhesive solution

[Table 19-1A]

The mixing ratios in Table 19-1A to 3B are as follows: the solid content of the easy adhesive solution

[Table 19-1B]

[Table 19-2A]

[Table 19-2B]

[Table 19-3A]

[Table 19-3B]

[Table 20]

The compounding ratio in the table means that the solids content of the easy adhesive solution

[Table 21-1A]

The compounding ratios in Table 21-1A to 21-3B are as follows: the solid content of the easy adhesive solution

[Table 21-1B]

[Table 21-2A]

[Table 21-2B]

[Table 21-3A]

[Table 21-3B]

[Table 22]

The compounding ratio in the table means that the solids content of the easy adhesive solution

[Table 23-1]

The blending ratios in Tables 23-1 and 23-2 are as follows: the solid content of the easy adhesive solution

[Table 23-2]

[Table 23-3]

[Table 24]

The compounding ratio in the table means that the solids content of the easy adhesive solution

As shown in Tables 13-1 to 24, Examples 1 to 221 have sufficient adhesiveness to a sealing material (EVA film) and adhesiveness after a heat and moisture resistance test because an easy adhesive for a solar cell protective sheet of the present invention is used.

On the other hand, in Comparative Examples 1 to 30, since an easy adhesive having no (meth) acryloyl group was used, the adhesiveness after the initial and wet heat resistance test was inferior.

[Example 222]

&Lt; Fabrication of solar cell module >

White plate glass ... Solar cell surface protection material (I)

EVA film - Sealing material on the light receiving surface (II)

Polycrystalline silicon solar cell ... Solar cell (III)

EVA film - Sealing material (IV) on the non-light receiving surface side

(I) - (IV) and the solar cell protection sheet 1 were stacked in order such that the adhesive layer of the solar cell protection sheet 1 easily contacts the sealing material IV on the non-light receiving surface side, and then placed in a vacuum laminator, The solar cell module 1 for evaluating the square-shaped photoelectric conversion efficiency of 10 m × 10 cm was produced by heating at 150 ° C. for 30 minutes and then heating at 150 ° C. for 30 minutes under a pressure of atmospheric pressure with a press pressure.

&Lt; Measurement of photoelectric conversion efficiency &

The solar cell output of the obtained solar cell module 1 was measured and the photoelectric conversion efficiency was measured according to JIS C8912 using a solar shaker (SS-100XIL, product of Hidehiko Seiki).

The photoelectric conversion efficiency after the moisture resistance heat test after standing for 500 hours, 1000 hours, 1500 hours, and 2000 hours under an environmental condition of a temperature of 85 캜 and a relative humidity of 85% RH was also measured. The initial photovoltaic conversion efficiency was calculated as follows. The ratio of the photovoltaic conversion efficiency after the wet heat resistance test was calculated.

○: Output drop is less than 10%

△: Output degradation is 10% or more and less than 20%

×: Output degradation of 20% or more

[Examples 223 to 245], [Comparative Examples 31 to 36]

The solar cell protection sheets 11, 25, 34, 39, 49, 63, 71, 78, 87, 102, 110, 115, 125, 139, 146, 150, 160, 174, 183, 189, 198 , 21, 21, 5 ', 10', 15 ', 20', 25 ', and 30', and the photoelectric conversion efficiency (after the initial moisture resistance test) was measured. Table 25 shows the above results.

[Table 25]

As shown in Table 25, in Examples 222 to 245, no large power reduction was observed, but in Comparative Examples 31 to 36, since the adhesion between the EVA film and the solar cell protective sheet was insufficient, intrusion of moisture caused deterioration of the solar cell element , The photoelectric conversion efficiency decreases.

This application claims priority based on Japanese patent application No. 2012-002616 filed on January 10, 2012 and inserts all of the disclosure here.

I: Solar cell surface protection material located on the light receiving side of the solar cell
II: Sealing material located on the light receiving surface side of the solar battery cell
III: Solar cell
IV: Seal material located on the non-light receiving surface side of the solar cell
V: a solar cell located on the non-light receiving surface side of the solar cell

Claims (13)

(R) other than the (meth) acrylic copolymer (A)
Wherein the amount of carbon-carbon double bonds derived from (meth) acryloyl groups is 0.01 to 50 (g / 100 g) in terms of iodine value. The method according to claim 1,
The resin (R) has a number average molecular weight of 10,000 to 250,000 and a glass transition temperature of -40 to 100 캜. 3. The method according to claim 1 or 2,
Wherein the resin (R) has at least one of a hydroxyl group and an amino group, and the sum of a hydroxyl value and an amine value is 2 to 100 (mgKOH / g). 4. The method according to any one of claims 1 to 3,
Wherein the resin (R) is a resin selected from the group consisting of a fluorine resin, an olefin resin, a polyester resin, a polyurethane resin, a polyurethaneurea resin and a polyamide resin. 5. The method according to any one of claims 1 to 4,
The carbon-carbon double bond derived from the (meth) acryloyl group is,
(i) those contained in the resin (R) and
(ii) those not contained in the resin (R) but contained in the compound (B) having a (meth) acryloyl group
, &Lt; / RTI &gt;
The resin (R) in the above (i) is a resin (Ra) other than the (meth) acrylic copolymer (A) having a carbon-carbon double bond derived from a (meth) acryloyl group,
Wherein the resin (R) of the above (ii) is a resin (Rb) other than the (meth) acrylic copolymer (A) having no (meth) acryloyl group. 6. The method according to any one of claims 1 to 5,
Wherein the resin (R) has at least one of a hydroxyl group and an amino group, and the amount of the isocyanate group relative to the sum of the molar amount of the hydroxyl group and the amino group is from 0.1 to 10 mols, Easy adhesive for protective sheet. 6. The method of claim 5,
Wherein the resin (Ra) is a resin (Ra-1) to (Ra-5) described in at least one of the following (1-1)
(1-1) The resin (Rb) has at least one of a hydroxyl group and an amino group, and the resin (Rb) is obtained by adding a (meth) acrylic monomer having an isocyanate group to at least one of the hydroxyl group and the amino group of the resin (Ra-1);
(1-2) a resin (Ra-2) obtained by adding a (meth) acrylic monomer having a glycidyl group to the carboxyl group in the resin (Rb), wherein the resin (Rb) has a carboxyl group;
(1-3) a resin (Ra-3) obtained by adding the (meth) acrylic monomer having a carboxyl group to the glycidyl group in the resin (Rb), wherein the resin (Rb) has a glycidyl group;
(1-4) A resin (Ra-4) obtained by adding the (meth) acrylic monomer having a hydroxyl group to the acid anhydride group in the resin (Rb), wherein the resin (Rb) has an acid anhydride group;
(1-5) A resin composition comprising (meth) acrylate (meth) acrylate having a functional group capable of polymerizing with each other and having a (meth) acryloyl group in the side chain and a component having no (meth) acryloyl group in the side chain, A resin (Ra-5) containing a carbon-carbon double bond derived from diarrhea. 6. The method of claim 5,
And 0.1-20 parts by weight of the compound (B) having the (meth) acryloyl group with respect to 100 parts by weight of the resin (Rb). 9. The method according to claim 5 or 8,
The compound (B) having a (meth) acryloyl group has at least two (meth) acryloyl groups in the molecule. (D ') formed on the outermost surface and a plastic film (E) supporting one of the easy adhesive layers (D') on one main surface,
Wherein the easy adhesive layer (D ') is formed by the easy adhesive for a solar cell protective sheet according to any one of claims 1 to 9. (I) positioned on the light receiving surface side of the solar cell (III), a sealing material (II) positioned on the light receiving surface side of the solar cell (III), a solar cell Receiving surface of the solar cell III and a solar cell backing material V located on a non-light-receiving surface side of the solar cell III,
The solar cell surface protection material I is obtained by arranging the easy adhesive layer D 'provided on the solar cell protection sheet Z' according to the present invention so as to be in contact with the sealing material II, ), And / or
The solar cell back protection material (V) is obtained by disposing the easy adhesive layer (D ') provided on the solar cell protection sheet (Z') according to claim 10 so as to be in contact with the sealing material (IV) Of the solar cell module. 12. The method of claim 11,
Wherein at least one of the sealing material (II) and the sealing material (IV) contains an organic peroxide. 13. The method according to claim 11 or 12,
Wherein at least one of the sealing material (II) and the sealing material (IV) comprises an ethylene-vinyl acetate copolymer (EVA) as a main component.

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