TW201335315A - Easy bonding agent for solar cell protection sheet, solar cell protection sheet, and solar cell module - Google Patents

Abstract

An easy-to-bonding agent for a solar cell protective sheet, which is excellent in bonding property and bonding durability, and a solar cell protective sheet and a solar cell module using the solar cell protective sheet are provided. The easy-bonding agent for a solar cell protective sheet of the present invention contains a resin (R) other than the (meth)acrylate copolymer (A) and contains a methyl group having a iodine value of 0.01 to 50 (g/100 g). a carbon-carbon double bond derived from propylene. The solar cell protective sheet of the present invention comprises: an easy-to-bond layer formed of an easy-bonding agent for a solar cell protective sheet formed on the outermost surface, and a main surface on one side supporting the easy-adhesive layer Plastic film.

Description

Easy bonding agent for solar cell protection sheet, solar cell protection sheet, and solar cell module

The present invention relates to an easy bonding agent for a solar cell protective sheet. Further, the present invention relates to a solar cell protective sheet using the solar cell protective sheet easy-to-bond agent, and a solar cell module using the solar cell protective sheet.

In recent years, because of the high awareness of environmental issues, solar cells have attracted attention as clean energy without environmental pollution, and they have been keen on research and practicalization from the useful use of energy resources.

There are various forms of solar cell elements, and representative ones are known as: crystalline germanium solar cell elements, polycrystalline germanium solar cell components, amorphous germanium solar cell components, and copper indium selenide solar cell components. , compound semiconductor solar cell elements, and the like. Among these, the polycrystalline germanium solar cell element, the amorphous germanium solar cell element, and the compound semiconductor solar cell element can be flexibly researched and developed in various aspects because of the relatively low cost and large area. Moreover, among these solar cell elements, a layer of germanium is deposited on the conductor metal substrate. Further, a thin film solar cell element, which is a representative of an amorphous tantalum solar cell element on which a transparent conductive layer is formed, is expected to be seen because it is lightweight, and is resistant to punching and flexibility. Into the future form of solar cells.

Among the solar battery modules, a simple article is a configuration in which a sealing material and a protective material are sequentially laminated on both surfaces of a solar cell element. For example, a representative example of the protective material is a glass plate, a solar cell protective sheet (hereinafter also referred to as a "protective sheet"), and the like. The glass plate is excellent in transparency, weather resistance, and scratch resistance, but has problems in terms of cost, safety, and processability. On the other hand, the protective sheet is excellent in terms of cost, safety, and workability, and various protective sheets have been proposed (for example, Patent Document 1). In addition, an Ethylene-Vinyl Acetate copolymer (hereinafter referred to as "EVA") having high transparency and excellent moisture resistance can be used as the sealing material.

For example, (i) a single-layer film such as a polyester film, (ii) a vapor-deposited layer containing a metal oxide or a non-metal oxide in a polyester-based film, etc., (iii) A multilayer film obtained by laminating a film of a polyester film, a fluorine film, an olefin film, or an aluminum foil.

The multi-layered protective sheet can impart various properties by its multilayer construction. For example, a polyester film can be used for imparting insulation, and an aluminum foil can be used for imparting water vapor barrier properties (see Patent Documents 2 to 4).

Among the various properties required for the protective sheet, the bondability with the sealing material and the joint durability are basic and important required properties. When and sealant When the bonding property is insufficient, the protective sheet peels off so that the solar cell cannot be protected from moisture and external influences, thereby causing deterioration of the output of the solar cell.

The method of ensuring the bondability with the sealing material is, for example, (1) a method of performing an easy joining treatment on a protective sheet surface joined to the sealing material, and (2) a protective sheet surface joined to the sealing material, A method of using a film having high adhesion to a sealing material.

The method of the above (1) includes surface treatment such as corona treatment and easy-to-bond coating treatment by applying an easy-to-bond agent.

However, the surface treatment such as the corona treatment of the former can ensure the initial bonding property, but it is a problem due to deterioration of the bonding durability. The easy-bonding agent used in the case of the latter easy-to-bond coating treatment is disclosed in Patent Documents 1, 5, and 6.

Patent Document 5 discloses a crosslinking agent selected from the group consisting of an oxazoline-based polymer, a urea resin, a melamine resin, and an epoxy resin, and a polyester resin having a transfer point of 20 to 100 ° C from a glass or A coating liquid of a resin component other than the crosslinking agent selected from the acrylic resin (see claims 2 and 3 of the same document). More specifically, an example of using a coating liquid containing an epoxy resin and an acrylic resin is described (refer to Example 5 of the same document). However, the bonding force with the EVA sheet in this example is about 10 to 20 N at a width of 20 mm (that is, 7.5 to 15 N at a width of 15 mm) (refer to Table 2 of the same document). The joint property between the sealant and the protective sheet is required to greatly affect the output degradation of the solar cell, and thus the market has always required higher jointability, and the reliability of the joint performance under stricter conditions has been required. In the case of a joint force of about 20 N at a width of 20 mm, it has not been able to meet such market requirements. In Patent Document 1, although the joining force has been improved, there has been a demand for a higher-performance easy-to-bond agent on the market.

Patent Document 6 discloses that a polyester resin is provided with a crosslinking agent of an alkylated melamine or a polyisocyanate, and is composed of a polyester resin and a polyester polyurethane resin. A configuration in which a bonding improvement layer formed by crosslinking at least one type of resin selected in the group is bonded to a sealing material.

The method of the above (2) (method of using a film having high adhesion to a sealing material on a protective sheet surface joined to a sealing material), for example, the use of polybutylene phthalate (PBT) described in Patent Document 7 ) method.

However, since such a film generally has a thickness of several tens of μm, there is a problem that the cost is higher than the ease of bonding described above.

Patent Document 8 discloses a back sheet for a solar cell module which is formed on a surface to which a filler (sealing material) constituting a solar cell module is bonded, and which is formed by containing a general formula (I) An adhesive layer composed of an acrylic adhesive of an acrylic polymer obtained by polymerizing a monomer component of a monomer.

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.

Further, Patent Document 9 discloses a protective sheet for a solar cell element which has a fluorine-based copolymer, an acrylic copolymer, or a polyamine base. An acid ester copolymer (polymer a) and a polymerizable monomer and/or oligomer (monomer b) having one or more ethylenically unsaturated groups for photocuring, and/or inclusion in a molecule An undercoat layer composed of one or more compounds having an ethylenically unsaturated group and two or more isocyanate groups (polyisocyanate c).

Prior Technical Literature Patent Literature

(Patent Document 1) Japanese Patent Laid-Open Publication No. 2009-246360

(Patent Document 2) Japanese Patent Laid-Open Publication No. 2004-200322

(Patent Document 3) Japanese Patent Laid-Open Publication No. 2004-223925

(Patent Document 4) Japanese Patent Laid-Open Publication No. 2001-119051

(Patent Document 5) Japanese Patent Laid-Open Publication No. 2006-152013

(Patent Document 6) Japanese Patent Laid-Open Publication No. 2007-136911

(Patent Document 7) Japanese Patent Laid-Open Publication No. 2010-114154

(Patent Document 8) Japanese Patent Laid-Open Publication No. 2010-263193

(Patent Document 9) Japanese Patent Laid-Open Publication No. 2011-18872

An object of the present invention is to provide an easy-bonding agent for a solar cell protective sheet and a solar cell protective sheet which are excellent in bonding property and bonding durability, and to provide a solar cell module using the solar cell protective sheet.

The easy-bonding agent for a solar cell protective sheet of the present invention contains a resin (R) other than the (meth) acrylate-based copolymer (A), and is (meth) propylene. The amount of carbon-carbon double bonds derived from thiol is 0.01 to 50 (g/100 g) in terms of iodine value.

The easy-bonding agent for a solar cell protective sheet of the present invention may be a preferred embodiment as exemplified below.

In a preferred aspect of the above resin (R), the coefficient has an average molecular weight of 10,000 to 250,000 and a glass transition temperature of -40 to 100 °C.

Further, in a preferred aspect of the resin (R), the method includes a substance having at least one of a hydroxyl group and an amine group and a total of a hydroxyl group and an amine value of 2 to 100 (mgKOH/g).

Further, in a preferred aspect of the resin (R), the fluorine resin, the olefin resin, the polyester resin, the polyurethane resin, and the polyurethane urea system are included. The resin and the polyamide resin constitute the resin selected in the group.

Further, in the preferred aspect of the carbon-carbon double bond derived from the (meth) acrylonitrile group, the method includes: (i) comprising the resin (R), and (ii) not included in the foregoing The resin (R) is contained in at least one of the compound (B) having a (meth) acrylonitrile group; wherein the aforementioned resin (R) of the above (i) has a (meth) acrylonitrile group a resin other than the (meth) acrylate copolymer (A) having a carbon-carbon double bond (Ra), and the resin (R) of the above (ii) is a group having no (meth) acrylonitrile group (A) Resin (Rb) other than the acrylate-based copolymer (A).

Further, in a preferred aspect of the resin (R), the method comprises: an isocyanate group containing at least one of a hydroxyl group and an amine group, and a molar amount relative to the hydroxyl group and the amine group. For 0.1 to 10 moles A range of polyisocyanate compounds (C).

Further, in a preferred aspect of the easy-bonding agent for a solar cell protective sheet of the present invention, the resin (Ra) is at least one of the following (1-1) to (1-5) Resin (Ra-1) to (Ra-2) described.

(1-1) The resin (Rb) is at least one of a hydroxyl group and an amine group, and an isocyanate group is added to at least one of the hydroxyl group and the amine group of the resin (Rb) ( Resin (Ra-1) obtained from a methyl acrylate monomer.

(1-2) The resin (Rb) is a resin having a carboxyl group and a (meth)acrylate monomer having a glycidyl group added to the carboxyl group in the resin (Rb) (Ra- 2).

(1-3) The resin (Rb) is a resin having a glycidyl group and a (meth) acrylate monomer having a carboxyl group added to the glycidyl group in the resin (Rb) ( Ra-3).

(1-4) The resin (Rb) is a resin having an acid anhydride group and a (meth)acrylate monomer having a hydroxyl group added to the acid anhydride group in the resin (Rb) (Ra-4) ).

(1-5) having a functional group obtained by polymerization and having a component having a (meth)acryl fluorenyl group in a side chain and a component having no (meth) acryl fluorenyl group in a side chain A resin (Ra-5) having a carbon-carbon double bond derived from a (meth) acrylonitrile group in a side chain.

Moreover, in a preferred aspect of the easy-bonding agent for a solar cell protective sheet of the present invention, the method comprises the following (meth) having 0.1 to 20 parts by weight based on 100 parts by weight of the resin (Rb). Acrylate based compound (B).

Further, in a preferred aspect of the compound (B) having the above (meth) acrylonitrile group, it includes those having two or more (meth) acrylonitrile groups in the molecule.

The solar cell protective sheet (Z') of the present invention comprises: an easy-adhesive layer (D') formed on the outermost surface, and a plastic film (E) supporting the easy-bonding agent layer (D') on one side of the main surface The above-mentioned easy-to-bond layer (D') is formed of the easy-bonding agent for a solar cell protective sheet described in any of the above.

The solar cell module of the present invention comprises a solar cell unit (III), a solar cell surface protective material (I) located on the light-receiving surface side of the solar cell, and a sealing on the light-receiving side of the solar cell (III). The material (II), the sealing material (IV) on the non-light-receiving surface side of the solar battery cell (III), and the solar cell inner protective material (V) on the non-light-receiving surface side of the solar battery cell (III) a solar cell module, wherein the solar cell surface protective material (I) is an easy-bonding layer (D') disposed by the solar cell protective sheet (Z') disposed in the above-described aspect, and the foregoing sealing material (II) a material obtained by bonding the above-mentioned easy-to-bond layer (D'); and/or the solar cell inner protective material (V) is a solar cell protective sheet configured to be disposed in the above-described aspect The easy-to-bond layer (D') of (Z') is bonded to the sealing material (IV), and the easy-to-bond layer (D') is cured.

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 an organic peroxide-containing material.

Moreover, in a preferred aspect of the solar cell module of the present invention, the method comprises the following steps: at least one of the sealing material (II) and the sealing material (IV) is an ethylene-vinyl acetate copolymer ( EVA) is the main ingredient.

The use of the easy-bonding agent for a solar cell protective sheet of the present invention has an excellent effect of providing an easy-to-bonding agent for a solar cell protective sheet and a solar cell protective sheet which are excellent in bonding property and bonding durability, and A solar cell module using the solar cell protection sheet is provided. By using the solar cell protective sheet of the present invention, it is possible to provide a solar cell module in which the output is reduced even if exposed to a high temperature and high humidity environment for a long period of time.

I‧‧‧Solar cell surface protection material on the light-receiving side of solar cells

II‧‧‧ Sealing material on the light-receiving side of the solar cell unit

III‧‧‧Solar battery unit

IV‧‧‧ Sealing material on the non-light-receiving side of solar cells

V‧‧‧Inside solar cell protection material on the non-light-receiving side of solar cells

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a cross section of a solar cell module of the present invention.

"Forms for Implementing Inventions"

Hereinafter, the present invention will be described in detail. In addition, as long as it is the object of the present invention, it is needless to say that other embodiments are also included in the scope of the present invention. In addition, in the specification, "~" is used to specify a numerical range that includes a range in which the numerical values described before and after "~" are the lower limit and the upper limit. Further, in the present specification, "film" and "sheet" are not distinguished by thickness. In other words, the "sheet" of the present specification should also include a film having a thin thickness, and the "film" of the present specification should also include a sheet having a thickness.

In the present specification, the "(meth)acrylate copolymer" means "acrylic copolymer", "methacrylic copolymer", and "acrylic monomethacrylate copolymer"; And "(meth)acryloyl group" means "acryloyl group" and "methacryloyl group"; "(meth)acrylic group" includes "acrylic group" and "methacrylic group" meaning.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a solar cell module according to the present invention. The solar cell module includes at least a solar cell surface protective material (I), a light receiving surface side sealing material (II), a solar battery cell (III), a non-light receiving surface side sealing material (IV), and a solar cell inner protective material ( V). The light-receiving surface side of the solar battery cell (III) is transmitted through the sealing material (II) on the light-receiving surface side and is protected by the solar cell surface protective material (I). On the other hand, the non-light-receiving surface side of the solar battery cell (III) is transmitted through the sealing material (IV) on the non-light-receiving surface side and is protected by the solar cell inner protective material (V).

At least one of the solar cell surface protective material (I) and the solar cell inside protective material (V) is obtained by the following steps. That is, the solar cell surface protective material (I) is configured such that the easy-bonding agent layer (D') provided in a solar cell protective sheet (Z') to be described later is bonded to the sealing material (II), and is easily joined. The agent layer (D') is obtained by hardening; and/or the solar cell protective material (V) is disposed so as to be disposed in an easy-to-bond layer (D' of a solar cell protective sheet (Z') to be described later. It is obtained by bonding to the sealing material (IV) and hardening the easy-to-bond layer (D').

The solar cell protective sheet (Z') is not limited to those obtained in various known manners, but a preferred configuration, for example, may be, for example, The adhesive layer (D') having the easy-to-bond layer (D') formed on the surface layer and the plastic film (E) having the main surface on the other side supporting the easy-bonding agent layer (D'). The easy-bonding agent layer (D') is formed of the easy-to-bond agent for solar cell protective sheets of the present invention (hereinafter also referred to simply as "easy bonding agent").

The easy-bonding agent for a solar cell protective sheet of the present invention is characterized in that it contains a resin (R) other than the (meth) acrylate-based copolymer (A) and is derived from a (meth) acrylonitrile group. The amount of carbon-carbon double bonds is 0.01 to 50 (g/100 g) based on the iodine value.

Further, the easy-to-bond layer (D') formed by the easy-bonding agent for a solar cell protective sheet of the present invention is subjected to a crosslinking reaction by a heating and pressing step in forming a solar cell module. In the present invention, it is distinguished that the easy-bonding agent layer before the heat-pressing step is used as the easy-bonding agent layer (D'), and the cross-linked easy-adhesive layer after the heat-pressing step is used as the easy-to-bond layer. (D). The same area is divided into: a solar cell protective sheet before the heating and pressing step as a solar cell protective sheet (Z'), and a material after the heating and pressing step as a solar cell protective sheet (Z).

Hereinafter, the resin (R) other than the (meth)acrylate copolymer (A) (hereinafter also referred to simply as the resin (R)) in the present invention will be described.

The (meth) acrylate-based copolymer (A) referred to herein is obtained by polymerizing various monomers as exemplified below to form a main chain.

The single system includes, for example, a (meth) acrylate monomer having an alkyl group, a (meth) acrylate monomer having a hydroxyl group, a (meth) acrylate monomer having a carboxyl group, and glycidol A (meth) acrylate monomer or the like. Also, for example, such as with vinyl acetate, maleic acid A product obtained by copolymerization of an anhydride, vinyl ether, vinyl propionate, styrene or the like.

It can be used as a (meth) acrylate monomer having an alkyl group, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (methyl) Acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and the like.

It can be used as a (meth) acrylate monomer having a hydroxyl group, and for example, it can be 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl group. (Meth) acrylate, etc.

The (meth) acrylate monomer having a carboxyl group may, for example, be acrylic acid, methacrylic acid, crotonic acid, itaconic acid, citraconic acid or the like.

The (meth) acrylate monomer having a glycidyl group may be, for example, glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether or the like.

The resin (R) other than the (meth)acrylate copolymer (A) may be, for example, an olefin resin (r1), a fluorine resin (r2), or a polyester resin (for example). R3), a polyurethane resin (r4), a polyurethane urea resin (r5), a polyamine resin (r6), or the like. These may be used singly or in combination of plural types.

The olefin resin (r1) can be obtained by a conventional radical polymerization method to obtain a polymerizable ethylenic monomer. The olefin resin (r1) may be a homopolymer or a copolymer (copolymer), preferably a copolymer (copolymer).

Can be used as a polymerizable vinyl monomer, for example, for example It may be an olefin such as ethylene, propylene, n-butene, isobutylene, 2-butene, cyclopentene or cyclohexene; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether , vinyl ethers such as n-hexyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, vinyl acetate, vinyl hexanoate And vinyl esters such as vinyl laurate, vinyl palmitate, vinyl stearate, vinyl benzoate, vinyl cyclohexylcarboxylate, and the like.

These ethylenic single systems may be used singly or in combination of plural kinds. However, in the present invention, when the monomer used in the olefin-based resin (r1) contains a fluoroolefin monomer as described later, the resin should be a fluorine-based resin (r2).

It can be used as a product of the olefin resin (r1), for example, it can be "from Nistoru" (manufactured by Mitsui Chemicals Co., Ltd.), "Auro Ryan" (Nippon Paper Chemicals Co., Ltd. )))).

The fluorine-based resin (r2) can be obtained by a conventional radical polymerization method to obtain a polymerizable fluoroolefin monomer. The fluorine-based resin (r2) may be a homopolymer or a copolymer (copolymer), preferably a copolymer. The copolymer may be a copolymer of fluorine-containing monomers with each other, or a copolymer of a fluorine-containing monomer and a fluorine-free monomer.

The polymerizable fluoroolefin monomer, for example, may be fluorinated vinyl ester, trifluoroethylene, tetrafluoroethylene, perfluoroalkyl vinyl ether, hexafluoropropylene, chlorotrifluoroethylene, difluoroethylene Ethylene and the like.

These fluoroolefin single systems may be used singly or in combination of plural kinds. Also, depending on the need, the above-mentioned vinyl sheet may also be used. The bodies are mixed and used.

The product of the fluorine-based resin (r2) is, for example, "Lumifulong" (manufactured by Asahi Glass Co., Ltd.), "Fluoroate" (manufactured by DIC Co., Ltd.), and "Fluorine" (large) Gold Industry Co., Ltd.).

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

The carboxylic acid component constituting the polyester resin (r3) may be, for example, benzoic acid, p-tert-butylbenzoic acid, phthalic anhydride, isophthalic acid, p-citric acid, succinic anhydride, adipic acid or hydrazine. Acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric acid, itaconic acid, tetrachlorophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride, methylcyclohexene tricarboxylic anhydride , pyromellitic anhydride, ε-caprolactam, fatty acid.

The hydroxyl component constituting the polyester resin (r3) may be, for example, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, or pentylene. a diol component such as an alcohol, triethylene glycol, 3-methyl pentanediol or 1,4-cyclohexane dimethanol, in addition to glycerin, trimethylolethane or trimethylol A polyfunctional alcohol such as propane, hydroxymethylaminomethane, pentaerythritol or dipentaerythritol.

According to a usual method, the carboxylic acid component and the hydroxy component can be polymerized to form a predetermined polyester resin, and can be used as a polyester resin (r3).

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

An isocyanate compound constituting a polyurethane resin (r4), for example For example, it may be the same as the polyisocyanate compound (C) as described later. For example, it may be trimethylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), methylene bis(4,1-phenylene)=diisocyanate (MDI), 3-isocyanate methyl- Diisocyanate such as 3,5,5-trimethylcyclohexyl isocyanate (IPDI) or xylene diisocyanate (XDI). Further, for example, a trimethylolpropane adduct of such a diisocyanate, a trimer isocyanate of a trimer, and a biuret combination may be used. Further, for example, it may be a polymerized diisocyanate or the like.

The hydroxyl component constituting the polyurethane resin (r4) may be, for example, a polyester polyol, a polyether polyol, or a polycarbonate polyol. Further, a polyurethane polyol or the like which is a reaction product of the polyol and the diisocyanate may be used.

As the polyester polyol, for example, a compound having a hydroxyl group at the end of the polyester resin (r3) can be used.

As the polyether polyol, a known polyether polyol can be used. For example, it is possible to use ethylene oxide, propylene oxide, butylene oxide, by using a compound having two or more hydroxyl groups such as ethylene glycol or propylene glycol, or water as a starting agent. A polyether polyol obtained by polymerizing an alkylene oxide compound such as tetrahydrofuran. Specifically, a functional group having two or more functional groups such as polypropylene glycol, polyethylene glycol, or polytetramethylene glycol can be used.

The one used as the polycarbonate polyol may, for example, be (1) a reaction of a compound having two or more hydroxyl groups such as ethylene glycol or propylene glycol with a carbonate; (2) ) to make it as above A compound having two or more hydroxyl groups is obtained by reacting phosgene in the presence of a base or the like.

The carbonate used in the production method of the above (1) can be specifically used, and examples thereof include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

Further, the polyester polyol, the polyether polyol, the polyamine polyol of the reaction product of the polycarbonate polyol and the diisocyanate may be such that the polyol and the diisocyanate are allowed to be such that the both ends thereof become a hydroxyl group. It is obtained by performing a urethanation reaction. The diisocyanate may, for example, be trimethylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), methylene bis(4,1-phenylene)=diisocyanate (MDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), xylylene diisocyanate (XDI), and the like.

For use as a polyurethane urea resin (r5), for example, it is possible to use a hydroxyl component such as the above polyester polyol, polyether polyol, or polycarbonate polyol. The isocyanate compound synthesizes a urethane prepolymer in such a manner that both ends thereof become an isocyanate group, and further makes the urethane prepolymer and a compound having two or more amine groups ( Am) A resin that reacts. Further, the reaction stopping agent (S) may be used to control the reaction as needed.

As the compound (Am) having two or more amine groups, a known one can be used. For example, ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, triethylidene tetraamine, di stretch Ethyltriamine, triaminopropane, 2,2,4- An aliphatic polyamine such as trimethylhexamethylenediamine, tolyldiamine, anthracene or piperidine; isoflurane diamine, dicyclohexylmethane-4,4'-diamine and the like containing an alicyclic ring An aliphatic polyamine of the formula polyamine; an aromatic polyamine such as a phenyldiamine or a xylylenediamine; and a 1,3-diamino-2-propanol or a 1,4-diamino-2 -butanol, 1-amino-3-(aminomethyl)-3,5,5-trimethylcyclohexane-1-ol, 4-(2-aminoethyl)-4,7, 10-triazanonan-2-ol, 3-(2-hydroxypropyl)-o-xylene-α,α'-diamine, 1,11-diamino-6-undecyl alcohol, 1 -(3-Aminopropylamino)-3-aminopropan-2-ol, 1-bis(2-aminoethyl)amino-2-propanol, 2-[bis(2-amino) Ethyl)amino]ethanol, (2-hydroxyethyl)ethylenediamine, N-(2-hydroxyethyl)propenediamine, (2-hydroxyethyl)propenediamine, (di-2-hydroxyethyl) a diamino alcohol such as ethylene diamine, (di-2-hydroxyethyl) propylene diamine, (2-hydroxypropyl) ethylene diamine or (di-2-hydroxypropyl) ethylene diamine.

A compound which can be used as the reaction stopper (S), for example, a monofunctional alcohol, a secondary amine, a compound having a hydroxyl group and a secondary amine group can be used.

As the monofunctional alcohol, for example, it may be methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decyl alcohol, decyl alcohol, undecyl alcohol, ten Dialkyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, isobutanol, isoamyl alcohol, isohexanol, isoheptyl alcohol, isooctanol, isodecyl alcohol, iso a monofunctional aliphatic alcohol such as mercapto alcohol, is undecyl alcohol, isododecyl alcohol, isotridecyl alcohol, isotetradecyl alcohol, isopentadecanol or the like; Benzyl alcohol, methylphenylmethanol, methoxyphenylmethanol, ethylphenylmethanol, ethoxyphenylmethanol, butylphenylmethanol, butoxyphenylmethanol, phenylethyl alcohol, methylbenzene Ethanol, methoxyphenylethanol, ethylphenylethanol, ethoxyphenylethanol, butylphenylethanol, butoxyphenylethanol, phenylpropanol, methylphenylpropanol, methoxy Phenylpropanol, ethylphenylpropanol, ethoxyphenylpropanol, butylphenylpropanol, butoxyphenylpropanol, phenylbutanol, methylphenylbutanol, methoxy A monofunctional aromatic alcohol such as phenylbutanol, ethylphenylbutanol, ethoxyphenylbutanol, butylphenylbutanol or butoxyphenylbutanol.

As the secondary amine, for example, it may be dibutylamine, dipentylamine, dihexylamine, bis-(2-ethylhexyl)amine, diheptylamine, dioctylamine, Dimercaptoamine, dinonylamine, nonylundecylamine, anthracene dodecylamine, decyltridecylamine, decyltetradecylamine, decylpentadecylamine, diisobutylamine , diisoamylamine, diisohexylamine, diisoheptylamine, diisooctylamine, diisodecylamine, diisodecylamine, diisodecylamine, diisodecyl Amine, diisotridecylamine, diisotetradecylamine, diisopentadecylamine, butylpentylamine, butylhexylamine, hexylpentylamine, butyloctylamine, decyl An aliphatic secondary amine such as octylamine; dibenzylamine, bis-(methylbenzyl)amine, bis-(methoxybenzyl)amine, bis-(ethylbenzyl)amine, di-( Ethoxybenzyl)amine, bis-(butylbenzyl)amine, bis-(butoxybenzyl)amine, diphenylethylamine, bis-(methylphenethyl)amine, di-(A Oxyphenethyl)amine, bis-(ethylphenethyl)amine, bis-(ethoxyphenethyl)amine, bis-(butylphenethyl)amine, di-(butoxyphenylethyl) base Amine, diphenylallylamine, bis-(methylphenylallyl)amine, bis-(methoxyphenylallyl) Amine, bis-(ethylphenylallyl)amine, bis-(ethoxyphenylallyl)amine, bis-(butylphenylallyl)amine, bis-(butoxyphenylallyl) An aromatic secondary amine such as an amine.

As the compound having a hydroxyl group and a secondary amine group, for example, it may be monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, or tris(hydroxymethyl). Aminomethane, 2-amino-2-ethyl-1,3-propanediol, 2-aminopropanol, 3-aminopropanol.

Among the above reaction stoppers (S), a compound having a hydroxyl group and a secondary amine group is preferred because a polyurethane urethane resin (r5) having a hydroxyl group at the terminal can be obtained. The hydroxyl group which is present at the terminal can also serve as a cross-linking site when the polyisocyanurate-based resin (r5) is added to the polyisocyanate compound (C) to crosslink it. Further, a particularly preferred one is 2-amino-2-methyl-propanol because the reaction is easily controlled.

The polyamine resin (r6) can be obtained, for example, by reacting the above carboxylic acid component with a compound (Am) having two or more amine groups.

The reaction of the polyamine-based resin (r6) can be carried out, for example, by introducing a carboxylic acid component together with a compound (Am) having two or more amine groups in a solvent-free manner, and obtaining a dehydration condensation reaction. . Such a reaction can be carried out under any of normal pressure and reduced pressure.

The easy-to-bond agent of the present invention is important in that it contains a carbon-carbon double bond derived from a (meth) acrylonitrile group having an iodine value in the range of 0.01 to 50 (g/100 g). The iodine value is preferably in the range of 0.1 to 30 (g/100 g), and more preferably in the range of 0.5 to 20 (g/100 g). By making the iodine When it is 50 (g/100 g) or less, the crosslinking reaction of the easy-bonding agent can be appropriately performed, and the bonding force can be more effectively produced. Further, by setting it to 0.01 (g/100 g) or more, the crosslinking reaction can be sufficiently carried out to obtain an excellent bonding force.

Further, the iodine value referred to herein can be determined by the following measurement method.

In a conical flask, 0.3 to 1 g of the sample was weighed up to 0.1 mg, and 50 cm ³ of chloroform was added thereto, and the mixture was allowed to stand in a constant temperature water bath at 25 ° C for 30 minutes. The Erlenmeyer flask was taken out from the constant-temperature water tank, and a 25 cm ³ Wijs method solution was added using a dropping tube, and the plug was stoppered, gently shaken and mixed to make it uniform, and then allowed to stand in a constant temperature water bath at 25 ° C for 120 minutes. The Erlenmeyer flask was taken out from the constant temperature water bath, and 10 cm ³ of a potassium iodide aqueous solution having a concentration of 100 g/L was added thereto, and the plug was stoppered and vigorously shaken and mixed. Next, titration was carried out using a 0.1 mol/L aqueous sodium thiosulfate solution. When the upper tank turned a little yellow, a 1 cm ³ starch solution was added and the titration was continued until the purple color of the solution disappeared.

The iodine value is obtained by the following formula. The iodine value is a value (unit: g/100 g) which is converted into a solid component of the easy-bonding agent.

Iodine price (g/100g) = "{(V0-V1) × c × 12.69} / m" / (solid content concentration / 100)

However, m: the amount of sample taken (g)

V0: titration of empty test (cm ³ )

V1: titer of sample (cm ³ )

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

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

The Wei's solution used at the time of dropping the iodine value was prepared in the order shown below.

4.8 to 5.2 g of iodine trichloride was weighed to a unit of 0.1 g, and it was placed in a brown bottle containing 1 L of a plug covered with polytetrafluoroethylene. In a 1 L Erlenmeyer flask with a common plug, 5.5 g of iodine was weighed up to 0.1 g of the unit, and 640 cm ³ of acetic acid was added and dissolved. This solution was added to a brown bottle containing iodine trichloride and mixed to make it a Wei's solution. Further, in the present invention, the solution is stored in a cool place after solution preparation, and the solution is contained within 30 days after the solution preparation.

The sealing material (II) and the sealing material (IV) of the solar battery cell (III) are not particularly limited, and a suitable known material can be applied. Suitable materials may, for example, be EVA (ethylene-vinyl acetate copolymer), and polyvinyl butyral, polyurethane, polyolefin, and the like. Among them, from the viewpoint of cost, it is mainly to use EVA. Although the sealing material (II) and the sealing material (IV) are simple (including a film-like material), they may be a paste or the like.

At least one of the sealing material (II) and the sealing material (IV) may contain an organic peroxide. By containing the organic peroxide, when the solar cell (III) is held by the sealing material (II) and the sealing material (IV) and heated (heating and pressing), it can be efficiently performed: The radical reaction causes crosslinking of the sealing material (II), crosslinking of the sealing material (II) and the sealing material (IV), and crosslinking of the sealing material (IV). That is, the crosslinking reaction can be promoted.

By causing organic peroxygen to be contained in the sealing material (II) and/or the sealing material (IV) Compound, it can be observed that at the time of heat sealing, the carbon-carbon double bond in the easy-bonding layer (D') also acts with the organic peroxide, so that the sealing material and the easy-to-bond layer (D' Crosslinking and promoting cross-linking within the easy-to-bond layer (D'). From the viewpoint of promoting the bonding property of the solar cell protective sheet more favorably, it is preferred that the sealing material on the side joined to the solar cell protective sheet contains an organic peroxide.

Thus, the carbon-carbon double bond of the easy-bonding agent forming the easy-adhesive layer (D') of the present invention means a radical-reactive and mutually polymerizable carbon-carbon double bond moiety (C=C) instead of An inert reaction carbon-carbon double bond such as a benzene ring or a pyridine ring. Among them, a highly reactive carbon-carbon double bond such as a (meth) acrylonitrile group is important, and a reactivity of a carbon-carbon double bond such as a vinyl ester group is remarkably poor. In the present specification, the term "hardening treatment" refers to a process in which the sealing material (II, IV) and the solar cell protective sheet (Z') are superposed, and then these are joined.

The easy-to-bond layer of the present invention contains a method of a carbon-carbon double bond derived from a predetermined amount of a (meth) acrylonitrile group having an iodine value in the range of 0.01 to 50 (g/100 g), although each has a method A variety of methods are possible, however suitable examples can be exemplified below. That is, for example, (i) may be contained in the resin (R) or (ii) which is not contained in the resin (R) and is contained in the compound (B) having a (meth) acrylonitrile group.

In this case, the resin (R) of (i) is a resin (Ra) other than the (meth)acrylate copolymer (A) having a carbon-carbon double bond derived from a (meth) acrylonitrile group (hereinafter) , sometimes referred to as resin (Ra) for short; (ii) resin (R) is not A resin (Rb) other than the (meth) acrylate-based copolymer (A) having a (meth) acrylonitrile group (hereinafter sometimes referred to simply as "resin (Rb)").

(i) and (ii) may be used singly or in a mixture of (i) and (ii).

First, an example in which the carbon-carbon double bond derived from the (meth) acrylonitrile group is an incorporation type belonging to the resin (R) incorporated in (i) will be described. A suitable example of the resin (Ra) is, for example, a resin (Ra-1) to (Ra-5) described in any one of the following (1-1) to (1-5).

(1-1) Resin (Rb) is a substance having at least one of a hydroxyl group and an amine group; and a (meth) acrylate having an isocyanate group is added to at least one of a hydroxyl group and an amine group of the resin (Rb) A resin (Ra-1) obtained by a monomer. The resin (Ra-1) can be obtained by introducing a (meth)acrylonyl group as a base point of a hydroxyl group and/or an amine group of the resin (Rb).

The (meth) acrylate monomer having an isocyanate group used herein may, for example, be 2-isocyanoquinone ethyl acrylate, 2-isocyanoquinone ethyl methacrylate or the like; : Karanz AOI, Karanz MOI, etc., manufactured by Showa Denko Co., Ltd.

(1-2) Resin (Rb) is a resin having a carboxyl group; and a resin (Ra-2) obtained by adding a glycidyl group-containing (meth)acrylate monomer to a carboxyl group in the resin (Rb). By introducing a (meth)acrylonyl group based on the carboxyl group of the resin (Rb), a resin (Ra-2) can be obtained.

(1-3) Resin (Rb) is a resin having a glycidyl group and a (meth)acrylate monomer having a carboxyl group added to a glycidyl group in the resin (Rb) (Ra-3) . By using the glycidyl group of the resin (Rb) A (meth) acrylonitrile group is introduced at the base point to obtain a resin (Ra-3).

(1-4) The resin (Rb) is an acid anhydride group, and a (meth) acrylate monomer having a hydroxyl group is added to an acid anhydride group in the resin (Rb) to obtain a resin (Ra-4). The resin (Ra-4) can be obtained by introducing a (meth)acrylonyl group as a base point of the acid anhydride group of the resin (Rb).

(1-5) A functional group obtained by polymerization of each other, which is obtained by polymerizing a component having a (meth) acrylonitrile group in a side chain and a component having no (meth) acryl fluorenyl group in a side chain. A resin (Ra-5) having a carbon-carbon double bond derived from a (meth) acrylonitrile group in a side chain. (1-5) is particularly useful when the polyurethane resin (r4) or the polyurethaneurea resin (r5) is produced.

For example, in the case of a polyurethane resin (r4) or a polyurethane urea resin (r5), it is possible to use (meth)acryl fluorenyl group and 1 as a hydroxyl component. A urethane component (T) having two or more hydroxyl groups is used to synthesize a polyurethane resin (r4) having a (meth) acrylonitrile group.

A known catalyst can also be used for the addition reaction of the above (1-1) to (1-4). For example, a tertiary amine compound, an organometallic compound, etc. are mentioned.

It can be used as a tertiary amine compound, for example, triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-di Coupling ring-(5,4,0)-undecene-7 (DBU) and the like.

As the organometallic compound, for example, it may be a tin-based compound or a non-tin-based compound.

Can be used as a tin compound, for example, for example, can be Dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, Tributyltin oxide, tributyltin acetate, triethyltin ethoxylate, tributyltin ethoxylate, dioctyltin oxide, tributyltin chloride, tin tributyltin chloroacetate, 2-ethyltin hexanoate, and the like.

It can be used as a non-tin-based compound, for example, titanium such as dibutyl titanium dichloride, tetrabutyl titanate, butoxide titanium trichloride, lead oleate, 2 - lead such as lead ethyl hexanoate, lead benzoate or lead naphthenate, iron such as iron 2-ethylhexanoate or iron acetylate pyruvate, cobalt benzoate, cobalt 2-ethylhexanoate, etc. A zinc system such as cobalt, zinc naphthenate or zinc 2-ethylhexanoate or zirconium naphthenate.

The hydroxyl component (T) ((meth)acryloyl group and the hydroxyl group having two or more hydroxyl groups) used in the method of the above (1-5), for example, may have two The epoxy group of the above epoxy group compound is compounded with a (meth)acrylic acid compound (U), glycerin mono(meth)acrylate, trimethylolethane mono(meth)acrylate, or the like. Hydroxymethylpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, etc. . The hydroxyl component (T) may be used singly or in combination of two or more.

The above compound (U) (a compound in which a (meth)acrylic acid is added to an epoxy group of a compound having two or more epoxy groups) may be, for example, propylene glycol diglycidyl ether (for example) Methyl)acrylic acid Additive, (meth)acrylic acid addenda of 1,6-hexanediol diglycidyl ether, (meth)acrylic acid addenda of ethylene glycol diglycidyl ether, 1,4-butanediol (meth)acrylic acid addenda of diglycidyl ether, (meth)acrylic acid addenda of 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether ( (meth)acrylic acid addenda, (meth)acrylic acid addenda of 1,9-nonanediol diglycidyl ether, (meth)acrylic acid addenda of neopentyl glycol diglycidyl ether, (meth)acrylic acid addenda of bisphenol A diglycidyl ether, (meth)acrylic acid addenda of hydrogenated bisphenol A diglycidyl ether, (meth)acrylic acid group of glycerol diglycidyl ether Acid addenda, etc.

Next, the carbon-carbon double bond derived from a (meth) acrylonitrile group is a compound (B) having a (meth) acrylonitrile group (ii) (hereinafter, also simply referred to as "compound (B)" ) included in the addition. An example of the blending type will be described. In other words, the resin (R) contained in the easy-bonding agent is a resin (Rb) other than the (meth) acrylate-based copolymer (A) having no (meth) acrylonitrile group, and is contained as An example of the compound (B) having a (meth) acrylonitrile group of a carbon-carbon double bond derived from an acrylonitrile group will be described.

The compound (B) having a (meth) acrylonitrile group of the present invention is preferably any one having at least one (meth) acryl fluorenyl group in the molecule, and may be, for example, for example, It is a polyol such as trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate or the like. (meth) acrylate, di(meth) acrylate of bisphenol A diglycidyl ether, di(meth) acrylate of polyglycol diglycidyl ether Epoxy (meth) acrylate, etc.

Among these, from the viewpoint of reactivity, the compound (B) preferably has two or more (meth) acrylonitrile groups in the molecule, and more preferably has three or more molecules in the molecule.

Further, the compound (B) may contain a hydroxyl group and other functional groups to the extent that the crosslinking of the resin (Rb) and the polyisocyanate compound (C) is not impaired.

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, for example, may be tert-butylperoxyisopropyl carbonate, tert-butylperoxy-2-ethylhexylisopropyl carbonate, tert -butylperoxyacetate, tert-butyl cumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di-tert -butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(tert- Butylperoxy)hexane, 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-butylperoxy) Cyclohexane, 1,1-di(tert-hexylperoxy)cyclohexane, 1,1-di(tert-pentylperoxy)cyclohexane, 2,2-di(tert-butyl Oxy)butane, methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5-diperoxybenzoate, tert-butyl hydroperoxide, diphenyl Mercapto peroxide, p-chlorobenzhydryl peroxide, tert-butylperoxy isobutyrate, n-butyl-4,4-di(tert-butylperoxy)pentanoic acid Ester, ethyl-3,3-di(tert-butylperoxy)butyrate, hydroxyheptyl peroxide, dicyclohexanone peroxide 1,1-di(tert-butylperoxy) 3,3,5-trimethylcyclohexane, n-butyl-4,4-di(tert-butylperoxy)valerate, 2,2-two (tert- Butylperoxy)butane and the like. These organic peroxides can be added to the sealing material by, for example, adding and melting and kneading the resin of the sealing material.

The compound (B) having a (meth) acrylonitrile group preferably has a ratio of 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the resin (Rb). The best one is a ratio of 1 to 10 parts by weight. By setting the ratio to 0.1 part by weight or more, the bonding strength can be more effectively achieved, and by making it 20 parts by weight or less, the compound (B) having a (meth) acryl fluorenyl group can be appropriately disposed. The joint force is effectively improved for the bonding force of the substrate and the sealing material.

In the present invention, the resin (R) is preferably a number average molecular weight of 10,000 to 250,000 and a glass transition temperature of -40 to 100 °C.

By making the number average molecular weight of the resin (R) 250,000 or less, the bonding force to the sealing material can be effectively guided; and by making it 10,000 or more, the heat resistance of the coating film of the easy bonding agent can be changed. Good, and the bonding force of the sealing material after the damp heat test was kept good. The number average molecular weight of the resin (R) is preferably from 10,000 to 150,000, more preferably from 10,000 to 100,000, more preferably from 15,000 to 75,000, and particularly preferably from 20,000 to 60,000.

Further, the above-mentioned number average molecular weight (Mn) is a value converted into polystyrene by gel permeation chromatography (GPC) of the resin (R). For example, the temperature of the column (KF-805L, KF-803L, and KF-802 manufactured by Showa Denko Co., Ltd.) is set to 40 ° C, and THF is used as a precipitate, and the flow rate is set to 0.2 mL/min. Check out the setting to RI and set the sample concentration to 0.02% was carried out using styrene as a standard sample. The number average molecular weight of the present invention describes the value measured by the above method.

By setting the glass transition temperature of the resin (R) to 100 ° C or lower, it is possible to maintain a good hardness of the coating film of the easy-bonding agent and to improve the bonding strength to the sealing material. Further, by making it at -40 ° C or higher, the coating film of the easy-to-bond agent can be kept good in moist heat resistance, and the bonding force with respect to the sealing material after the damp heat test can be kept good. Further, when the surface of the coating film of the easy-to-bond agent is effectively prevented from sticking and the solar cell protective sheet is formed into a roll shape after the production, it becomes difficult to cause blocking. . The glass transition temperature of the resin (R) is preferably from -10 to 80 ° C, particularly preferably from 10 to 70 ° C.

The glass transition temperature refers to a value measured by a differential scanning calorimeter (DSC) for a resin having 100% of the dried solid component of the resin (R). For example, an aluminum pan containing a sample of about 10 mg of the sample and an aluminum pan not loaded with the sample are placed in a DSC apparatus, and in a nitrogen stream, liquid nitrogen is used, and it is rapidly cooled until -100. At °C, the temperature was raised at 20 ° C / min until 200 ° C, and the DSC curve was drawn. The baseline on the low temperature side of the DSC curve (the DSC curve portion of the temperature region where the test piece has not undergone transfer and reaction) extends to the line on the high temperature side, and the slope of the curve in the phase change portion of the glass transition becomes the largest point. At the intersection of the outgoing wires, the glass transition starting temperature (Tig) of the heterodyne is obtained, which is obtained by taking it as the glass transition temperature. The glass transition temperature described in the present invention is a value obtained by measurement by the above method.

In order to improve the adhesion between the plastic film (E) and the sealing material by crosslinking, and impart heat and humidity resistance to the easy-to-bond layer, the resin (R) preferably has a hydroxyl group and an amine group. At least either. 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), still more preferably 2 to 30 (mgKOH/g). By making the sum of the hydroxyl value of the resin (R) and the amine valence to be 100 (mgKOH/g) or less, the coating film of the easy-bonding agent can be appropriately cross-linked, and the bonding to the plastic film (E) can be made. The force is getting better. Further, it is possible to effectively prevent the crosslinking reaction from being carried out in the damp heat resistance test, and the joining force is reduced after the damp heat test. Further, by setting the sum of the hydroxyl value and the amine value to 2 (mgKOH/g) or more, the coating film of the easy-bonding agent can be appropriately cross-linked, the moist heat resistance of the coating film can be made good, and the damp heat test can be prevented. The bonding force of the sealing material is reduced.

The amine valence (mgKOH/g) in the present invention can be determined by the following measurement method.

0.1 to 3 g of the sample was weighed to 0.1 mg, and 10 mL of acetic acid was added to the beaker, and the mixture was slowly stirred until the sample was completely dissolved. The test solution was subjected to potentiometric titration with a 0.10 mol/L perchloric acid acetic acid solution using an automatic titrator until the end point of 600 mV.

The amine valence of the sample was calculated by the following formula.

Amine value (mgKOH/g) = {(V × F × 5.61) / m} / (solid content concentration / 100)

However, m: the amount of sample taken (g)

V: 0.10 mol/L perchloric acid acetic acid solution required for sample titration Capacity (mL)

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

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

The amine valence described in the present invention is a value measured by the above method.

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

The polyisocyanate compound (C) can be crosslinked with the resin (R) by reacting with a hydroxyl group and/or an amine group in the resin (R) to impart heat and humidity resistance to the easy-bonding layer. Further, the adhesion between the plastic film (E) constituting the solar cell protective sheet and the sealing material (II) and/or the sealing material (IV) can be improved. Therefore, the polyisocyanate compound (C) preferably has two or more isocyanate groups in one molecule. For example, an aromatic polyisocyanate, a chain aliphatic polyisocyanate, an alicyclic polyisocyanate, or the like. One type of the polyisocyanate compound (C) may be used, or two or more types of compounds may be used in combination.

As the aromatic polyisocyanate, for example, it may be 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4 , 4'-diphenylmethane diisocyanate, 2,4-tolyl diisocyanate, 2,6-tolyl diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene 1,3,5-triisocyanate benzene, dimethoxyaniline diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, and the like.

As the chain aliphatic polyisocyanate, for example, it may be, trimethylene diisocyanate, tetramethylene diisocyanate Ester, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 12 Methyl diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

As the alicyclic polyisocyanate, for example, it may be 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane II Isocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4, 4'-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatemethyl)cyclohexane, and the like.

Further, in addition to the above polyisocyanate, for example, an adduct of a polyhydric alcohol compound such as polyisocyanate and trimethylolpropane, or a biuret or trimeric isocyanate of the above polyisocyanate may be used; Further, it may be an adduct of the above polyisocyanate with a known polyether polyol or polyester polyol, an acrylic polyol, a polybutadiene polyol, a polyisobutylene polyol or the like.

Among these polyisocyanate compounds (C), from the viewpoint of design, a low-yellowing aliphatic or alicyclic polyisocyanate is preferred; from the viewpoint of moisture and heat resistance, it is preferably Trimeric isocyanate. More specifically, a trimer isocyanate of hexamethylene diisocyanate (HDI), a trimeric isocyanate of 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) is preferred. .

Further, by reacting almost the entire amount of the isocyanate groups of the polyisocyanate compound (C) with the blocking agent, block polymerization can be obtained. Isocyanate compound (C1). In the present invention, the easy-to-bond layer (D') before the hardening treatment obtained by applying the easy-to-bond agent for the solar cell protective sheet is preferably not bonded before the solar cell module is bonded to the sealing material. Therefore, the polyisocyanate compound (C) is preferably a blocked polyisocyanate compound (C1).

As the blocker, for example, it may be phenol, thiophenol, methyl thiophenol, dimethyl phenol, cresol, resorcin, nitrophenol, chlorophenol, etc. Anthraquinones such as phenols, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, Alcohols such as t-pentanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol, etc., 3,5-dimethylpyrazole, 1, a pyrazole such as 2-pyrazole, a triazole such as 1,2,4-triazole, a halogen-substituted alcohol such as chlorohydrin or 1,3-dichloro-2-propanol, or ε-caprolactone Amidoxime, acetonitrile, acetonitrile, ethyl acetate, ethyl acetoacetate, malonic acid An active methylene compound such as methyl ester or ethyl malonate. Other examples include, for example, amines, quinones, thiols, imines, ureas, diaryls, and the like. One type of the blocking agent may be used, or two or more types may be used in combination.

Preferred among these blockers is that the block agent has a dissociation temperature of from 80 ° C to 150 ° C. When the dissociation temperature is less than 80 ° C, there is a fear that the adhesion between the filler and the filler is reduced due to the progress of the hardening reaction when the easy-to-bond agent is applied and the solvent is volatilized. When the dissociation temperature exceeds 150 ° C, it may be in the vacuum thermocompression step at the time of constructing the solar cell module, The hardening reaction is not sufficiently performed to reduce the adhesion to the filler.

The block agent used as the dissociation temperature of 80 ° C to 150 ° C, for example, may be methyl ethyl ketone oxime (dissociation temperature: 140 ° C, the following also refers to the dissociation temperature), 3, 5- Dimethylpyrazole (120 ° C), diisopropylamine (120 ° C), and the like.

The amount of the polyisocyanate compound (C) in the easy-bonding agent of the present invention is preferably 1 mol% or less with respect to the sum of the hydroxyl group and the amine group of the resin (R) of 1 mol. The range of isocyanate groups, more preferably in the range of 0.5 to 5 moles. By making it at 0.1 mol or more, the crosslinking density can be made appropriate and has sufficient moist heat resistance. Further, by setting it at 10 m or less, it is possible to effectively prevent the excess isocyanate from reacting with the moisture in the air in the damp heat test to harden the coating film, thereby causing the plastic film to constitute the solar cell protective sheet (E). ) and the reason for the decrease in the bonding force between the sealing materials.

The easy-bonding agent of the present invention may contain 0.01 to 30 parts by weight of organic particles or inorganic particles to be described later, based on 100 parts by weight of the solid component. By adding particles, the viscosity of the surface of the easy-to-bond layer (D') before the hardening treatment can be reduced. In particular, it is more preferable that 5 to 30 parts by weight of the inorganic particles are added because the desired effect of increasing the moist heat resistance can be obtained at this time; and among the inorganic particles, the talc and the water are more preferable. Talc, mica, kaolin. When the content is less than 0.01 parts by weight, the tackiness of the surface of the easy-bonding agent layer (D') before the hardening treatment cannot be sufficiently reduced; by making it 30 parts by weight or less, the ease before the hardening treatment can be made The adhesion between the bonding agent layer (D') and the sealing material is well maintained and effective Improve the joint force.

Among the organic particles, those having a melting point or a softening point of 150 ° C or higher can be suitably used. When the melting point or softening point of the organic particles is less than 150 ° C, the particles may soften during the vacuum thermocompression bonding step of constituting the solar cell module to impede the bonding with the sealing material.

Specific examples of the organic-based particles include, for example, polymethyl methacrylate resin, polystyrene resin, Nylon (registered trademark) resin, melamine resin, guanamine resin, phenol resin, urea resin, hydrazine. Polymer particles such as resin, methacrylate resin, acrylate resin; or cellulose powder, nitrocellulose powder, wood powder, waste paper powder, rice bran powder, starch, and the like. The organic particle system may be used in one type or in combination of two or more types.

The polymer particles described above can be obtained by a polymerization method such as an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a soap-free polymerization method, a seed polymerization method, or a microsuspension polymerization method. Further, the organic particles may contain impurities without impairing the properties thereof. Further, the shape of the particles may be a shape such as a powder, a granule, a granule, a flat plate, a fiber or the like.

Specific examples of the inorganic particles may, for example, be oxides, hydroxides, sulfates, carbonates, and cesiums of metals such as magnesium, calcium, barium, zinc, zirconium, molybdenum, niobium, tantalum, and titanium. Inorganic particles such as acid salts. More specific examples, for example, may be silicone, alumina, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, zinc oxide, lead oxide, diatomaceous earth, zeolite. , aluminum silicate, talc, white carbon, mica, glass fiber, glass powder, glass beads, gypsum, ash, oxygen Inorganic particles such as iron, cerium oxide, titanium oxide, zinc antimony white, light stone powder, aluminum sulfate, zirconium silicate, barium carbonate, dolomite, molybdenum disulfide, sand iron, carbon black, and the like. One type of the inorganic particles may be used, or two or more types may be used in combination.

Further, the inorganic particles may contain impurities without impairing the properties thereof. Further, the shape of the particles may be a shape such as a powder, a granule, a granule, a flat plate, a fiber or the like.

Further, in the easy-bonding agent of the present invention, a crosslinking accelerator may be added as needed within a range that does not impair the effects of the present invention. The crosslinking accelerator is a catalyst which promotes the crosslinking reaction of the hydroxyl group and the amine group of the resin (R) other than the (meth)acrylate copolymer (A) and the isocyanate of the polyisocyanate compound (C). As the crosslinking accelerator, for example, it may be a tin compound, a metal salt, a base or the like; specific examples are, for example, tin octylate, dibutyltin diacetate, and dilaurin Dibutyltin acid, dioctyltin dilaurate, tin chloride, iron octoate, cobalt octoate, zinc naphthenate, triethylamine, triethylenediamine, and the like. These lines can be used alone or in combination.

Further, in the adhesive agent of the present invention, a filler, a thixotropic agent, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, and heat conduction may be added as needed without impairing the effects of the present invention. Various additives such as a sex improver, a plasticizer, an anti-sagging agent, an antifouling agent, a preservative, a bactericide, an antifoaming agent, a leveling agent, a hardener, a tackifier, a pigment dispersant, a decane coupling agent, and the like.

Further, by adding an epoxy resin (Ep) to the easy-bonding agent in the present invention, It is expected to have an effect of increasing the heat and humidity resistance. The amount of the epoxy resin (Ep) to be added is preferably 0.1 to 70 parts by weight, more preferably 0.5 to 60 parts by weight, more preferably 1 to 50 parts by weight, based on 100 parts of the resin (R). .

As the epoxy resin (Ep), for example, it may be a glycidyl ether compound, a glycidyl ester compound or the like.

As the glycidyl ether compound, for example, it may be a bisphenol type epoxy resin, a novolac type epoxy resin, a biphenol type epoxy resin, a dimethyl phenol type epoxy resin. Resin, trishydroxyphenylmethane type epoxy resin, tetraphenol ethane type epoxy resin, and the like.

For the above bisphenol type epoxy resin, for example, it may be bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin.

As the above-mentioned novolac type epoxy resin, for example, it may be a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a brominated phenol novolak type epoxy resin, or the like. A phenol novolac type epoxy resin having a naphthalene skeleton, a phenol novolac type epoxy resin containing a dicyclopentadiene skeleton, and the like.

As the glycidyl ester compound, for example, it may be diglycidyl tetraruthenate or the like. These epoxy resins may be used singly or in combination of two or more.

The easy-bonding agent which can be used in the present invention is a solvent.

Used as a solvent, although alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether, diethylene glycol methyl ether, etc. can be used; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; an ether such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether; Hydrocarbons such as pentane and octane; aromatics such as benzene, toluene, xylene, and cumene; and esters suitable for the resin composition among esters such as ethyl acetate and butyl acetate. If necessary, it is preferred to use a material having a boiling point of 50 ° C to 200 ° C. When the boiling point is higher than 50 ° C, when the easy-to-bond agent is applied, the solvent becomes easily volatilized, so that the solid content becomes high, and it is difficult to apply a uniform film thickness. When the boiling point is 200 ° C higher, it becomes difficult to dry the solvent. Further, two or more kinds of solvents may be used.

The easy-bonding agent of the present invention can be formed into a bonding layer (D') by applying it to the plastic film (E), thereby producing a bonding with the sealing material (II) and/or the sealing material (IV). Good solar cell protection sheet (Z').

As a method of applying the easy-bonding agent of the present invention to the plastic film (E), a conventionally known method can be used. Specifically, for example, a velcro coating method, a concave coating method, a reverse coating method, a roll coating method, a lip coating method, a spray coating method, and the like. The easy-bonding agent can be applied by such a method, and the solvent is volatilized by heat drying to form an easy-adhesive layer (D') before the hardening treatment.

The thickness of the easy-to-bond layer (D') before the hardening treatment is preferably 0.01 to 30 μm, more preferably 0.1 to 10 μm.

As the plastic film (E), for example, a polyester resin film such as polyethylene terephthalate, polybutylene phthalate or polyethylene naphthalate, polyethylene, polypropylene, or polycyclic ring can be used. An olefin film such as pentadiene or a polyvinyl fluoride, A fluorine-based film such as a polyvinylidene fluoride film, a polytetrafluoroethylene film, or an ethylene-tetrafluoroethylene copolymer film, an acrylic film, or a triethylenesulfonated cellulose film. From the viewpoint of film rigidity and cost, a polyester resin film is preferable, and among them, a polyethylene terephthalate film is preferable. The plastic film (E) may have a multilayer structure of one layer or two or more layers. Further, a vapor deposited film on which a metal oxide or a non-metal inorganic oxide is vapor-deposited may be laminated on the plastic film (E).

When a polyester resin film is used as the plastic film (E), the film preferably has a specific viscosity of 0.6 (dL/g) or more and a cyclic trimer content of 1% by weight or less. A polyester resin film formed of an ester resin. In addition, it is more preferable that the intrinsic viscosity is 0.6 to 1.2 (dL/g). Further, the content of the cyclic trimer is preferably as small as possible, but more preferably 0.5% by weight or less. By using such a film, it is possible to suppress the deterioration of strength due to hydrodecomposition such as long-term exposure to the outside.

The content of the cyclic trimer of the polyester resin forming the polyester resin film described above is obtained by dissolving 100 mg of the polyester resin in 2 mL of prochlorophenol and measuring the weight by a liquid chromatograph. Got it.

The intrinsic viscosity of the polyester resin forming the polyester resin film described above is obtained by the following formula.

That is, the amount ηsp/c extrapolated by the viscosity ηsp=(η/η0)-1 divided by the concentration c is obtained by extrapolating the concentration 0.

However, η0 is the viscosity of the solvent; c (g/mL) is the resin concentration in the solvent; η is the viscosity of the resin solution at c (g/mL); ηsp is the ratio of the viscosity of the resin solution to the viscosity of the solvent.

For use as a metal oxide or a non-metallic inorganic oxide for vapor deposition on a plastic film (E), for example, bismuth, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, An oxide such as ruthenium. Further, an alkali metal, an alkaline earth metal fluoride or the like may be used; these may be used singly or in combination.

These metal oxides or non-metal inorganic oxides can be vapor-deposited by a conventional PVD method such as vacuum vapor deposition, ion plating or sputtering, or a CVD method such as plasma CVD or microwave CVD.

When the solar cell protective sheet (Z') is used on the non-light-receiving side, the plastic film (E) constituting the solar cell protective sheet (Z') may be colorless or may contain a coloring component such as a pigment or a dye. . When the solar cell protective sheet (Z') is used on the light-receiving surface side, the plastic film (E) constituting the solar cell protective sheet (Z') is preferably colorless.

The method for containing the coloring component is, for example, a method of kneading a coloring component in advance of film formation, a method of printing a coloring component on a colorless transparent film substrate, and the like. Further, the colored film and the colorless transparent film may be bonded together and used.

The solar cell protective sheet (Z') may be a single layer or a plurality of layers of metal foil (F), weather resistant resin on the side of the side of the easy-to-bond layer (D') on which the plastic film (E) is not formed. a film layer or a coating layer of layer (G) or the like.

As the metal foil (F), aluminum foil, iron foil, zinc plate, etc. can be used, and among these, aluminum foil is preferable from a viewpoint of corrosion resistance. The thickness is preferably from 10 μm to 100 μm, more preferably from 20 μm to 50 μm. For the lamination of the metal foil (F), it is possible to use a conventionally known one. A variety of bonding agents.

As the weather resistant resin layer (G), a polyvinylidene fluoride film, a polyethylene terephthalate, a polybutylene terephthalate or a polyparaic acid can be used by laminating various binders known in the art. A film made of a polyester resin film such as naphthalene diester or a coating layer formed of a high weather resistant paint such as Lumiforon coated with Asahi Glass.

The solar cell module of the present invention can be laminated on a solar cell by transmitting a sealing material (II) before the hardening treatment on the light-receiving surface side of the solar cell unit with respect to the solar cell (III). The solar cell surface protective material (I) on the light-receiving surface side of the unit is further laminated with the sealing material (IV) before the hardening treatment on the non-light-receiving surface side of the solar cell unit to laminate the protective material (V) inside the solar cell. It is obtained by high-temperature heating and pressing under reduced pressure.

For use as a solar cell surface protective material (I) or a solar cell protective material (V), for example, a glass plate, a polycarbonate, a polyacrylate plastic plate, or the like can be used, but preferably At least one of them is formed of the solar cell protective sheet (Z') of the present invention.

The solar cell module of the present invention preferably uses a glass plate on a solar cell surface protective material (I) from the viewpoint of practical durability and flammability, and the solar cell inside protective material (V) ) is a material formed by the solar cell protective sheet (Z') of the present invention.

As the sealing material for EVA or the like used for the sealing materials (II) and (IV), it may contain an ultraviolet absorber or a light stabilizer for increasing weather resistance, or may contain a crosslinker for self-crosslinking of EVA. Organic peroxide additive.

For example, it may be an electrode provided on a photoelectric conversion layer of a compound semiconductor represented by crystalline germanium, amorphous germanium or copper indium selenide, for example, as the solar battery cell (III). Further, they are further laminated on a substrate such as glass.

≪Example≫

Hereinafter, the present invention will be described in further detail by way of examples, however, the invention should not be construed as limited only. In addition, in the embodiment, each "part" means "parts by weight", and each "%" means "% by weight".

Further, the iodine value, the number average molecular weight (Mn), and the amine value are values measured by the above-described method; and the glass transition temperature and the hydroxyl value are measured by the method described below.

<Measurement of glass transition temperature (Tg)>

The glass transition temperature was determined by the aforementioned differential scanning calorimetry (DSC) method. Further, the sample for Tg measurement was obtained by heating the above-mentioned acrylic resin solution at 150 ° C for about 15 minutes, and drying and solidifying it.

<Measurement of Hydrogen Price (OHV)>

In a co-plugged conical flask, a sample of about 1 g of a precisely weighed amount, and a mixed solution of 100 mL of toluene/ethanol (capacity ratio: toluene/ethanol = 2/1) were added and dissolved. Further, 5 mL of an acetamidine compound (a solution obtained by dissolving 25 g of acetic anhydride in pyridine to have a capacity of 100 mL) was added, and the mixture was stirred for about 1 hour. In which an indicator of the phenolphthalein test solution is added, Lasts for 30 seconds. Then, titration was carried out with a 0.1 N alcoholic potassium hydroxide solution until the solution appeared reddish.

The hydroxyl value is obtained by using the following formula. The hydroxyl value is a numerical value (unit: mgKOH/g) of the dry state of the resin.

Hydroxyl Price (mgKOH/g) = "{(b-a) × F × 28.25} / S" / (nonvolatile concentration / 100) + D

However, S: the amount of sample taken (g)

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

b: consumption of 0.1N alcoholic potassium hydroxide solution in blank experiment (mL)

F: the strength of the 0.1N alcoholic potassium hydroxide solution (effectiveness factor)

D: amine price (mgKOH/g)

<Olefin Resin R11 Solution>

2,000 g of butyl acetate, 420 g of vinyl 2,2-methylpropylvalerate, 100 g of vinyl benzoate, and 15 g of 4-hydroxybutyl vinyl ether were placed in a pressure-resistant autoclave at a high pressure. The inside of the kettle was replaced with a reduced pressure nitrogen. Next, 70 g of ethylene was again introduced under reduced pressure and the temperature was raised to 60 ° C, and then 20 g of t-butylperoxytrimethylacetate was further added to carry out a polymerization reaction. When the internal pressure of the reactor became a specific pressure, the reaction was stopped, and an olefin-based resin R11 having a number average molecular weight of 16,000, a hydroxyl value of 11.1 (mgKOH/g), and a Tg of 25 ° C was obtained. This was dissolved in toluene to form a solid content of 20%, which was used as an olefin resin R11 solution.

<Olefin-based resin R12~R14, R16~R18 solution>

In addition to the single sheet to be used in the synthesis of the olefin resin R11 solution The olefin resin R12 to R14 and the R16 to R18 solution were synthesized in the same manner as in the olefin resin R11 solution except that the composition of the body was changed as shown in Table 1. The Tg, the number average molecular weight, and the hydroxyl value of the obtained olefin resin are shown in Table 1.

<Olefin Resin R15 Solution>

It is made of Nisto P800 (manufactured by Mitsui Chemicals Co., Ltd.) as an olefin resin R15 solution. The Tg, the number average molecular weight, and the hydroxyl value of the olefin resin R15 are shown in Table 1.

In addition, the abbreviation in Table 1 shows the thing shown below.

ET: Ethylene

nBVE: n-butyl vinyl ether

CHVE: cyclohexyl vinyl ether

MPPV: 2,2-methylpropyl propionate

VBz: vinyl benzoate

HBVE: 4-hydroxybutyl vinyl ether

<Olefin-based resin R11' solution>

500 parts of the olefin resin R11 solution was placed in a three-necked flask equipped with a cooling tube, a nitrogen introduction tube, a stirring device, and a thermometer, and the temperature was raised to 40 ° C while stirring. 0.03 parts of dibutyltin dilaurate was added, and while stirring at 40 ° C, 7.1 parts of 2-isocyanoquinone ethyl methacrylate (hereinafter abbreviated as MOI) was dropped over 3 hours. It was confirmed by IR that the isocyanate peak (2260 cm ^-1 ) was disappeared to obtain a Tg of 23 ° C, a number average molecular weight of 16,000, a hydroxyl value of 5.0 (mgKOH/g), an iodine value of 2.3 (g/100 g), and a solid content of 20%. Olefin resin R11' solution.

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

The amount of 2-isocyanoquinone ethyl methacrylate (MOI) used in the synthesis of the olefin resin R11' solution was changed to that shown in Table 2, similarly to the olefin resin R11' solution. The olefin resin R12'~R19' solution was synthesized. The Tg, the number average molecular weight, the hydroxyl value, and the iodine value of the obtained olefin resin are shown in Table 2.

<Fluororesin R21 solution>

In a press-resistant autoclave, 2,000 g of butyl acetate, 350 g of vinyl 2,2-methylpropylvalerate, 50 g of vinyl benzoate, and 15 g of 4-hydroxybutyl vinyl ether were placed at a high pressure. The inside of the kettle was replaced with a reduced pressure nitrogen. Next, under reduced pressure, 100 g of trifluoroethylene and 70 g of ethylene were charged, and after raising the temperature to 60 ° C, 20 g of t-butylperoxytrimethylacetate was introduced to carry out a polymerization reaction. When the internal pressure of the reactor reached a specific pressure, the reaction was stopped to obtain a fluorine-based resin R21 having a number average molecular weight of 17,000, a hydroxyl value of 12.8 (mgKOH/g), and a Tg of 41 °C. This was dissolved in tar oil naphtha to form a solid component of 20%, which was used as a fluorine resin R21 solution.

<Fluorine resin R22~R24, R26~R28 solution>

The fluorine-based resin R22 to R24 and R26 to R28 solutions were synthesized in the same manner as in the fluorine-based resin R21 solution, except that the composition of the monomer used for the synthesis of the fluorine-based resin R21 solution was changed as shown in Table 3. The Tg, the number average molecular weight, and the hydroxyl value of the obtained fluorine-based resin are shown in Table 3.

<Fluorine resin R25 solution>

Lumifulong LF-200 (made by Asahi Kasei Chemicals Co., Ltd.) was used as a fluorine resin R25 solution. The Tg, the number average molecular weight, the hydroxyl value, and the amine value of the olefin resin R25 are shown in Table 3.

In addition, the abbreviation in Table 3 means an object which has appeared as in the front opening table, or shows an object as shown below.

TFE: Trifluoroethylene

CTFE: Chlorotrifluoroethylene

<Fluororesin R21' solution>

500 parts of a fluorine-based resin R21 solution was placed in a three-necked flask equipped with a cooling tube, a nitrogen introduction tube, a stirring device, and a thermometer, and the temperature was raised to 40 ° C while stirring. 0.03 parts of dibutyltin dilaurate was added, and 6.9 parts of 2-isocyanoquinone ethyl methacrylate (MOI) was dropped over 3 hours while stirring at 40 °C. It was confirmed by IR that the isocyanate peak (2260 cm ^-1 ) had disappeared, and a Tg of 40 ° C, a number average molecular weight of 17,000, a hydroxyl value of 7.9 (mgKOH/g), an iodine value of 2.3 (g/100 g), and a solid content of 20 were obtained. % of a fluorine resin R21' solution.

<Fluororesin R22'~R28' solution>

The amount of 2-isocyanoquinone ethyl methacrylate (MOI) used in the synthesis of the fluorine-based resin R21' solution was changed to that shown in Table 4, and was carried out in the same manner as the fluorine-based resin R21' solution. Synthesis of a fluorine resin R22'~R28' solution. The Tg, the number average molecular weight, the hydroxyl value, and the iodine value of the obtained fluorine-based resin are shown in Table 4.

<Polyester resin R31 solution>

In a polymerization tank equipped with a polymerization tank, a mixer, a thermometer, a water separation device, a reflux condenser, and a nitrogen introduction tube, 8 parts of citric acid, 8 parts of isononanoic acid, and 5 parts of hexamethylene Acid, 40 parts of sebacic acid, 10 parts of ethylene glycol, 11 parts of neopentyl glycol, and 17 parts of 1,6-hexanediol were put into a polymerization tank, and stirred under a nitrogen stream while being 160 Heat at ~240 ° C to carry out the transesterification reaction. Next, the polymerization tank is slowly depressurized to 1 to 2 torr, and the reaction under reduced pressure is stopped when the predetermined viscosity is reached, thereby obtaining a number average molecular weight of 18,000, a hydroxyl value of 6.5 (mgKOH/g), and Tg. The polyester polyol of -37 ° C was diluted with ethyl acetate to obtain a polyester resin R31 solution having a solid content of 50%.

<Polyester resin R32~R35, R37, R38 solution>

The polyester resin R32 to R35, R37, and R38 were synthesized in the same manner as the polyester resin R31 solution, except that the composition of the monomer used in the synthesis of the polyester resin R31 solution was changed as shown in Table 5. Solution. The Tg, the number average molecular weight, and the hydroxyl value of the obtained polyester resin are shown in Table 5.

<Polyester resin R36, R39 solution>

Bailong GK880 (manufactured by Toyobo Co., Ltd.) was dissolved in MEK to form a solid content of 50%, and this was used as a polyester resin R36 solution. Further, Elliott UE-9900 (manufactured by Nichika Co., Ltd.) was dissolved in toluene to form a solid content of 30%, and this was used as a polyester resin R36 solution. The Tg, the number average molecular weight, and the hydroxyl value of the obtained polyester resin are shown in Table 5.

In addition, the abbreviation in Table 5 means the following.

TPA: For tannic acid

IPA: isophthalic acid

AdA: adipic acid

SeA: azelaic acid

EG: ethylene glycol

NPG: neopentyl glycol

1,6-HD: 1,6-hexanediol

TMP: Trimethylolpropane

<Polyester-based resin R31' to R39' solution>

The amount of the resin solution and 2-isocyanoquinone ethyl methacrylate (MOI) to be used in the synthesis of the fluorine-based resin R21' solution was changed to that shown in Table 6, and the fluorine-based resin. The R21' solution was also subjected to synthesis to synthesize a polyester resin R31'~R39' solution. The Tg, the number average molecular weight, the hydroxyl value, and the iodine value of the obtained polyester resin are shown in Table 6.

<Polyurethane resin R41 solution>

In a four-necked flask equipped with a cooling tube, a nitrogen inlet tube, a stirring device, a thermometer, and a dropping funnel, 368 parts of C-2090 (manufactured by Kuraray Co., Ltd., polycarbonate polyol) and 32 parts of two were placed. Toluene diisocyanate and 100 parts of toluene were charged with 0.03 part of a catalyst of dibutyltin dilaurate, and the temperature was gradually raised to 100 ° C to carry out a reaction for 3 hours. After confirming that there was no NCO peak by IR measurement, 300 parts of ethyl acetate was added to obtain a polyamino group having a number average molecular weight of 23,000, a hydroxyl value of 4.9 (mgKOH/g), a Tg of -5 ° C, and a solid content of 50%. Acid ester resin R41 solution.

<Polyurethane resin R42~R47 solution>

In the same manner as in the case of the polyurethane resin R41, the composition of the hydroxy component and the isocyanate compound used in the synthesis of the polyurethane resin R41 solution was changed as shown in Table 7. The synthetic polyurethane resin R42~R47 solution was synthesized. The Tg, the number average molecular weight, and the hydroxyl value of the obtained polyurethane resin are shown in Table 7.

Further, the abbreviation in Table 7 is simply as shown in the table in which the pre-opening has occurred, or as shown below.

C-2090: Polycarbonate polyol, manufactured by Kuraray Co., Ltd.

PTMG-3000: Polytetramethylene ether glycol, Mitsubishi Chemical Co., Ltd.

CHDM: cyclohexane dimethanol

XDI: xylylene diisocyanate

HDI: hexamethylene diisocyanate

IPDI: Isophorone diisocyanate

<Polyurethane resin R41'~R47' solution>

In addition to the synthesis of the fluorine-based resin R21' solution, the amount of the resin solution used and 2-isocyanoquinone ethyl methacrylate (MOI) was changed to those shown in Table 8, and fluorine-based The resin R21' solution was similarly produced to synthesize a solution of the polyurethane resin R41' to R47'. The Tg, the number average molecular weight, the hydroxyl value, and the iodine value of the obtained polyurethane resin are shown in Table 8.

<Polyurethane urea resin R51 solution>

310 parts of C-2090 (manufactured by Kuraray Co., Ltd., polycarbonate polyol) and 64 parts of xylene were placed in a 4-necked flask equipped with a cooling tube, a nitrogen introduction tube, a stirring device, a thermometer, and a dropping funnel. The base diisocyanate and 100 parts of toluene were charged with 0.03 part of a catalyst of dibutyltin dilaurate, and the temperature was gradually raised to 100 ° C, and the reaction was carried out for 3 hours. After cooling to 40 ° C, 200 parts of ethyl acetate was added, and then 26 parts of isophorone diamine was added dropwise over 1 hour, and stirring was further continued for 1 hour. 2-Amino-2-methylpropanol was added, and it was confirmed by IR measurement that there was no NCO peak, and the mixture was diluted with ethyl acetate to obtain a number average molecular weight of 26,000, a hydroxyl value of 4.3 (mgKOH/g), and a Tg of 32 ° C. A 50% solid polyurethane urethane resin R51 solution.

<Polyurethane urea resin R52~R59 solution>

In addition to the synthesis of the polyurethane urethane resin R51 solution, the composition of the hydroxy component, the isocyanate compound, and the compound having two or more amine groups used is changed as shown in Table 9, and The polyurethane urethane resin R51 solution was similarly synthesized to synthesize a polyurethane urethane resin R52 to R59 solution. The Tg, the number average molecular weight, and the hydroxyl value of the obtained polyurethaneurea resin are shown in Table 9.

Further, in Table 9, simply referred to as the one shown in the table in which the opening has occurred, or the object shown below.

HAD: hexamethylenediamine

IPDA: isophorone diamine

XDA: xylylenediamine

DAB: 1,4-diamino-2-butanol

<Polyurethane urea resin R51'~R59' solution>

In addition to the synthesis of the fluorine-based resin R21' solution, the amount of the resin solution used and 2-isocyanoquinone ethyl methacrylate (MOI) was changed as shown in Table 10, and fluorine-based The resin R21' solution was also subjected to a polyurethane urethane resin R51' to R59' solution. The Tg, the number average molecular weight, the hydroxyl value, and the iodine value of the obtained polyurethane urethane resin are shown in Table 10.

<Polyurethane resin R61 solution>

In a flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, a reflux dehydration device, and a distillation tube, 180 parts of ion-exchanged water, 73 parts of adipic acid, 100 parts of sebacic acid, and 127 parts of hexamethylene group were charged. Diamine. Stirring was carried out until the temperature of heat generation became constant, and when the temperature was at a safe temperature, the temperature was raised to 110 °C. After confirming that the water had been distilled off, the temperature was raised to 120 ° C after 30 minutes, and then allowed to stand for 30 minutes, and the temperature was raised by 10 ° C each time until the temperature became 220 ° C. The reaction was continued at 220 ° C for 3 hours, and the reaction was terminated at a specific amine price, and diluted with toluene to obtain 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%. Polyamide resin R61 solution.

<Polyurethane resin R62~R66 solution>

In addition to the synthesis of the polyamido resin R61 solution, the composition of the carboxylic acid component and the compound having two or more amine groups used was changed to that shown in Table 11, and the polyamine resin R61 was used. The solution was similarly prepared to synthesize a polyamine-based resin R62-R67 solution. The Tg, the number average molecular weight, and the amine value of the obtained polyamine-based resin are shown in Table 11.

Further, the abbreviation in Table 11 is simply referred to as the one shown in the front opening table.

<Polyurethane resin R61'~R66' solution>

In addition to the synthesis of the fluorine-based resin R21' solution, the amount of the resin solution and 2-isocyanoquinone ethyl methacrylate (MOI) used was changed as shown in Table 12, and the fluorine-based resin. The R21' solution was similarly prepared to synthesize a solution of the polyamine resin R61' to R66'. The Tg, the number average molecular weight, the amine value, and the iodine value of the obtained polyamine-based resin are shown in Table 12.

<Modulation of Easy Bonding Agent Solution 1~221>

An olefin resin solution, a fluorine resin solution, a polyester resin solution, a polyurethane resin solution, a polyurethane urea resin solution, a polyamido resin solution, and (meth) The propylene fluorenyl compound (B), the polyisocyanate compound (C) solution, the epoxy resin (Ep), the inorganic particles (M), and the catalyst are in accordance with Tables 13-1, 13-2, 13-3, and 13- 4, 15-1A, 15-1B, 15-2, 15-3A, 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- The compositions shown in 2 and 23-3 were mixed to obtain an easy-to-bond solution 1 to 221.

<Easy to bond solution 1'~30’>

An olefin resin solution, a fluorine resin solution, a polyester resin solution, a polyurethane resin solution, a polyurethane urea resin solution, a polyamine resin solution, or an allyl compound (H), the polyisocyanate compound (C) solution and the catalyst are mixed according to the compositions shown in Tables 14, 16, 18, 20, 22, and 24 to obtain an easy-bonding agent solution 1' to 30'.

<Production of Polyester Film 1>

Using a polyester resin having an intrinsic viscosity of 0.67 (dL/g) and a cyclic trimer content of 0.5% by weight, a polyester having a thickness of 125 μm was produced at a set temperature of 250 ° C using a T-die squeezer. Film 1.

<Production of Solar Cell Protective Sheet>

The single surface of the polyester film 1 was subjected to corona treatment, and the easy-bonding agent solution 1 was applied to the treated surface by a concave coating method, and the solvent was dried to prepare an easy-adhesive layer having a coating amount of 1 g/m ² . Solar cell protection sheet 1.

In the same manner as the solar cell protective sheet 1, the solar cell protective sheets 2 to 221 were produced using the easy-to-bond solution 2 to 221 .

<Production of sample for joint strength evaluation>

In a manner in which the easy-adhesive layer of the solar cell protective sheet 1 is bonded to the EVA film, whiteboard glass or a vinyl acetate-ethylene copolymer film (manufactured by Sembil Co., Ltd., standard hardening type, and the following EVA film) are stacked in this order. ), solar cell protection sheet 1. Then, this laminated body was placed in a vacuum laminator, evacuated to a pressure of 1 Torr, heated at 150 ° C for 30 minutes under a pressurization pressure of 0.1 MPa, and further heated at 150 ° C for 30 minutes to prepare a laminate. Sample 1 for the joint strength evaluation of 10 cm × 10 cm square.

In the same manner as the sample 1 for the bonding strength evaluation, the solar cell protective sheets 2 to 56 were used to prepare the bonding force evaluation samples 2 to 56.

"Embodiment 1"

The bonding strength evaluation sample 1 was used, and the adhesion of the easy-bonding layer to the EVA film and the wet heat test (after 1000 hours, after 2000 hours) were evaluated by the method described later.

<Evaluation of jointability>

The solar cell protective sheet 1 of the sample 1 for bonding strength evaluation was cut into a width of 15 mm by a dicing blade, and the bonding force between the easy-adhesive layer formed on the solar cell protective sheet 1 and the sealing material of the EVA film was measured. The measurement was carried out using a tensile tester at a load rate of 100 mm/min for a 180 degree peel test. The obtained measured values were evaluated in accordance with the following.

◎: 50N/15mm or more

○: 30N/15mm or more ~ less than 50N/15mm

△: 10N/15mm or more ~ less than 30N/15mm

×: less than 10N/15mm

<Evaluation of jointability after moisture and heat resistance test>

The sample 1 for the bonding strength evaluation was allowed to stand for 1000 hours and 2000 hours under the environmental conditions of a temperature of 85° C. and a relative humidity of 85% RH, and the adhesion property after the moisture resistance test was evaluated in the same manner as the measurement of the adhesion property.

"Examples 2 to 221", "Comparative Examples 1 to 30"

In the same manner as in the first embodiment, the bonding strength evaluation samples 2 to 221 and 1' to 30' were used, and the adhesion of the easy-to-bond layer to the EVA film and the adhesion after the damp heat resistance test were evaluated. 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. , 17-1B, 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, 24.

The abbreviations in Tables 13-1 to 24 are those shown below.

<Compounds B1 to B6 with (meth)acryl fluorenyl group>

In the compounds B1 to B6 having a (meth) acrylonitrile group, the original compounds of the compounds described below are used.

B1: Aronicus M-215 (made by East Asia Synthetic Co., Ltd., EO-modified diacrylate of iso-cyanuric acid)

B2: Aronicus M-315 (made by East Asia Synthetic Co., Ltd., EO-modified triacrylate of iso-cyanuric acid)

B3: epoxy ester 70PA (manufactured by Kyoeisha Chemical Co., Ltd., Apollo 70P acrylic acid additive)

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

B5: TMPTA (trimethylolpropane triacrylate)

B6: DPHA (dipentaerythritol hexaacrylate)

<Polyisocyanate Compound Solution C>

The polyisocyanate compound solution (C) was obtained by diluting it to 75% with ethyl acetate by a trimeric isocyanate of hexamethylene diisocyanate having a 3,5-dimethylpyrazole block.

<Allyl-containing compound H1~H4>

The original compound of the compound described below was used for the allyl-containing compound H1 to H4.

H1: TAIC (manufactured by Nippon Kasei Co., Ltd., triallyl isocyanurate)

H2: neoallyl E-10 (manufactured by Dacao Co., Ltd., glycerol monoallyl ether)

H3: neoallyl T-20 (manufactured by Dacao Co., Ltd., trimethylolpropane diallyl)

H4: neoallyl P-30M (manufactured by Dacao Co., Ltd., pentaerythritol triallyl ether)

<Epoxy Resin Ep1~Ep3>

The original substance of the compound described below was used for the epoxy resin Ep1 to Ep3.

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

Ep2: YDCN-704 (made by Dongdu Huacheng Co., Ltd., cresol novolak type epoxy resin)

Ep3: Dinakolu EX-821 (made by Changchun Chemical Technology Co., Ltd., polyethylene glycol diglycidyl ether)

<Inorganic particles M1~M4>

In the inorganic particles M1 to M4, the original particles of the inorganic particles described below are used.

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

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

M3: Kaolinite SATINTONE W (made by Lin Huacheng Co., Ltd.)

M4: montmorillonite kunipa F (manufactured by National Mining Industry Co., Ltd.)

As shown in Tables 13-1 to 24, in Examples 1 to 221, since the easy-bonding agent for a solar cell protective sheet of the present invention was used, the bonding material (EVA film) had sufficient bonding property and bonding after the damp heat resistance test. Sex.

On the other hand, in Comparative Examples 1 to 30, since the easy-bonding agent having no (meth) acrylonitrile group was used, the bondability after the initial stage and the moist heat resistance test was not good.

Embodiment 222 <The manufacture of solar cell modules>

Whiteboard glass...Solar cell surface protection material (I)

EVA film... Sealing material on the light receiving side (II)

Polycrystalline germanium solar cell components... solar cell unit (III)

EVA film...sealing material on the non-light-receiving side (IV)

The above-mentioned (I)-(IV) and solar cell protective sheet 1 are sequentially stacked in such a manner that the easy-adhesive layer of the solar cell protective sheet 1 is joined to the sealing material (IV) on the non-light-receiving surface side. The vacuum laminator was introduced into a vacuum laminator and evacuated to about 1 Torr. After applying atmospheric pressure as a pressurizing pressure, the mixture was heated at 150 ° C for 30 minutes, and further heated at 150 ° C for 30 minutes to prepare 10 cm × 10 cm. See solar cell module 1 for photoelectric conversion efficiency evaluation.

<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 in accordance with JIS C8912 using a solar simulator (Yoshihiro Seiki, SS-100XIL).

In addition, the measurement was carried out in the same manner at a temperature of 85 ° C and a relative humidity of 85% RH. The photoelectric conversion efficiency after the humidity resistance test after standing for 500 hours, 1000 hours, 1500 hours, and 2000 hours under the environmental conditions. The ratio of the initial photoelectric conversion efficiency to the photoelectric conversion efficiency after the moisture heat resistance test was calculated and evaluated as follows.

○: The output is reduced by less than 10%

△: The output is reduced by more than 10% to less than 20%.

×: The output is reduced by 20% or more.

"Examples 223~245", "Comparative Examples 31~36"

In the same manner as in Example 222, solar cell protective sheets 11, 25, 34, 39, 49, 63, 71, 78, 87, 102, 110, 115, 125, 139, 146, 150, 160, 174, 183 were used. The solar cell modules 1 to 30 were produced by 189, 198, 211, 218, 5', 10', 15', 20', 25', 30', and the photoelectric conversion efficiency (initial, after the damp heat resistance test) was measured. The above results are shown in Table 25.

As shown in Table 25, in Examples 222 to 245, no significant decrease in the output force was observed, and in Comparative Examples 31 to 36, the bonding property between the EVA film and the solar cell protective sheet was insufficient, so that the solar cell element was caused by moisture infiltration. Degraded, and the photoelectric conversion efficiency is lowered.

Priority is claimed on the basis of Japanese Patent Application No. 2012-002616, filed on Jan. 10, 2012, the entire disclosure of which is incorporated herein by reference.

I‧‧‧Solar cell surface protection material on the light-receiving side of solar cells

II‧‧‧ Sealing material on the light-receiving side of the solar cell unit

III‧‧‧Solar battery unit

IV‧‧‧ Sealing material on the non-light-receiving side of solar cells

V‧‧‧Inside solar cell protection material on the non-light-receiving side of solar cells

Claims (13)

An easy-bonding agent for a solar cell protective sheet containing a resin (R) other than the (meth) acrylate-based copolymer (A) and a carbon-carbon double bond derived from a (meth) acrylonitrile group The amount is 0.01 to 50 (g/100 g) based on the iodine value. The easy-bonding agent for a solar cell protective sheet according to claim 1, wherein the resin (R) has a number average molecular weight of 10,000 to 250,000 and a glass transition temperature of -40 to 100 °C. The easy-bonding agent for a solar cell protective sheet according to claim 1 or 2, wherein the resin (R) has at least one of a hydroxyl group and an amine group, and a sum of a hydroxyl value and an amine value is 2 to 100 (mgKOH). /g). The easy-bonding agent for a solar cell protective sheet according to claim 1 or 2, wherein the resin (R) is a fluorine resin, an olefin resin, a polyester resin, a polyurethane resin, or a polyamine. The urethane urea resin and the polyamide resin constitute the resin selected in the group. The easy-bonding agent for a solar cell protective sheet according to claim 1 or 2, wherein the carbon-carbon double bond derived from the (meth) acrylonitrile group is: (i) included in the resin (R), And (ii) at least one of the compound (B) having a (meth) acrylonitrile group not contained in the resin (R); the resin (R) of the above (i) having a resin other than the (meth) acrylate copolymer (A) having a carbon-carbon double bond derived from (meth) acrylonitrile (Ra); and the resin (R) of the above (ii) having no (A) Acrylate Resin (Rb) other than the (meth) acrylate copolymer (A). The easy-bonding agent for a solar cell protective sheet according to claim 1 or 2, wherein the resin (R) is at least any one of a hydroxyl group and an amine group, and contains a molar relative to the hydroxyl group and the amine group. The isocyanate group is a polyisocyanate compound (C) in an amount of 0.1 to 10 mols in terms of the sum of the amounts. The resin (Ra) is a resin described in at least one of the following (1-1) to (1-5) (the resin (Ra)) Ra-1) to (Ra-5); (1-1) the resin (Rb) is at least one of a hydroxyl group and an amine group, and the aforementioned hydroxyl group of the resin (Rb) and the aforementioned amine group a resin (Ra-1) obtained by adding at least one (meth) acrylate monomer having an isocyanate group; (1-2) the resin (Rb) is a compound having a carboxyl group, and the above resin (Rb) a resin obtained by adding a glycidyl group-containing (meth) acrylate monomer to the carboxyl group (Ra-2); (1-3) the resin (Rb) is a glycidyl group-containing substance, and a resin (Ra-3) obtained by adding a (meth) acrylate monomer having a carboxyl group to the glycidyl group in the resin (Rb): (1-4) the resin (Rb) has an acid anhydride group And a resin (Ra-4) obtained by adding a (meth) acrylate monomer having a hydroxyl group to the acid anhydride group in the resin (Rb); (1-5) having a mutual polymerization Functional group, and consists of a component having a (meth)acryl fluorenyl group and a carbon-carbon derived from a (meth) acrylonitrile group in a side chain obtained by polymerization of a component having no (meth) acrylonitrile group in a side chain. Double bond resin (Ra-5). The easy-bonding agent for a solar cell protective sheet according to claim 5, which contains 0.1 to 20 parts by weight of the compound having a (meth)acryl fluorenyl group (B) per 100 parts by weight of the resin (Rb). ). The easy-bonding agent for a solar cell protective sheet according to claim 5, wherein the compound (B) having a (meth) acrylonitrile group has two or more (meth) acrylonitrile groups in the molecule. A solar cell protective sheet (Z') having an easy-to-bond layer (D') formed on the outermost surface and a plastic film (E) supporting the easy-bonding layer (D') on one side of the main surface The above-mentioned easy-to-bond layer (D') is formed by the easy-bonding agent for a solar cell protective sheet according to any one of claims 1 to 9. A solar cell module comprising a solar cell unit (III), a solar cell surface protective material (I) on a light receiving surface side of the solar cell unit (III), and a light receiving surface side of the solar cell unit (III) The sealing material (II), the sealing material (IV) on the non-light-receiving surface side of the solar battery cell (III), and the solar cell protection material (V) located on the non-light-receiving surface side of the solar battery cell (III) a solar cell module in which the aforementioned solar cell surface protective material (I) is configured such that The easy-bonding agent layer (D') provided in the solar cell protective sheet (Z') as recited in claim 10 is bonded to the above-mentioned sealing material (II), and the easy-bonding agent layer (D') is hardened. And the obtained material, and/or the solar cell protective material (V) is configured to be disposed so as to be disposed in the solar cell protective sheet (Z') as described in claim 10, and the easy-to-bond layer (D') The sealing material (IV) is joined to each other, and the easy-to-bond layer (D') is cured. The solar battery module according to claim 11, wherein at least one of the sealing material (II) and the sealing material (IV) contains an organic peroxide. The solar cell module according to claim 11 or 12, wherein at least one of the sealing material (II) and the sealing material (IV) is mainly composed of an ethylene-vinyl acetate copolymer (EVA).