JP2013071948A - Vinyl-based adhesive - Google Patents

Abstract

An adhesive having excellent blocking resistance, adhesion and weather resistance, a back sheet for a solar cell module having an adhesive layer made of the adhesive, a solar cell module, and a solar cell are provided.
A vinyl adhesive containing a vinyl polymer, wherein the vinyl polymer is a vinyl polymer having an ethylenically unsaturated double bond at the end of a side chain. A vinyl adhesive, a back sheet for a solar cell module having an adhesive layer made of the vinyl adhesive, a solar cell module, and a solar cell.
[Selection] Figure 1

Description

  The present invention relates to a vinyl adhesive. More specifically, the present invention can be suitably used for an adherend containing a polymer in which vinyl carboxylate is used as a monomer, particularly an adherend containing an ethylene-vinyl acetate copolymer. The present invention relates to a vinyl adhesive that can be used.

  Conventionally, polymers using vinyl carboxylate as a monomer, especially ethylene-vinyl acetate copolymer, have flexibility and excellent stability to water and ultraviolet rays, and also have rubber elasticity and flexibility. Excellent in toughness, low-temperature properties, weather resistance, transparency, rigidity, friction resistance, electrical insulation, etc., agricultural film, architectural civil engineering sheet, artificial turf, solar cell sealant It is widely used as a material for automobile exterior parts, food wrapping paper, and shoe soles.

  Examples of the material include polyester urethane-based adhesives (for example, see Patent Document 1), polyether urethane-based adhesives (for example, see Patent Document 2), urethane-modified acrylic resin-based adhesives (for example, see Patent Document 3), and the like. The urethane type adhesive is used. However, these adhesives have the disadvantage that they have poor adhesion and are inferior in weather resistance particularly in an environment used outdoors.

  Therefore, in recent years, development of an adhesive having excellent blocking resistance, adhesiveness, and weather resistance has been desired.

JP 2010-043238 A JP 2011-042756 A JP 2011-153204 A

  The present invention has been made in view of the prior art, and is an adhesive excellent in blocking resistance, adhesiveness and weather resistance, a back sheet for a solar cell module having an adhesive layer made of the adhesive, and a solar cell. An object is to provide a module and a solar cell.

The present invention
(1) A vinyl adhesive containing a vinyl polymer, wherein the vinyl polymer is a vinyl polymer having an ethylenically unsaturated double bond at the end of a side chain. Adhesives,
(2) At least one monomer selected from the group consisting of an epoxy group-containing monomer and an oxazoline group-containing monomer, wherein the vinyl polymer having an ethylenically unsaturated double bond at the end of the side chain A vinyl polymer obtained by reacting a polymer obtained by polymerizing a monomer component containing a monomer with a monomer having a carboxyl group and / or a hydroxyl group, and a monomer having a carboxyl group and / or a hydroxyl group A vinyl polymer obtained by reacting a polymer obtained by polymerizing a monomer component to be reacted with at least one monomer selected from the group consisting of an epoxy group-containing monomer and an oxazoline group-containing monomer A vinyl polymer obtained by reacting a monomer component containing a monomer having a carboxyl group and / or a hydroxyl group with an isocyanate group-containing monomer; A vinyl polymer obtained by reacting a monomer obtained by polymerizing a monomer component containing an anate group-containing monomer with a monomer having a carboxyl group and / or a hydroxyl group, and (meth) acrylic acid ( Vinyl adhesive according to (1), which is at least one vinyl polymer selected from the group consisting of vinyl polymers obtained by polymerizing monomer components containing vinyloxyalkoxy) alkyl;
(3) A back sheet for a solar cell module in which an adhesive layer made of the vinyl adhesive according to (1) or (2) is formed,
(4) A solar cell module comprising the back sheet for a solar cell module according to (3), and (5) a solar cell comprising the solar cell module according to (4). About.

  The vinyl adhesive of the present invention has an excellent effect of being excellent in adhesiveness and also in heat and moisture resistance and weather resistance.

It is a schematic sectional drawing which shows one embodiment of the back sheet | seat for solar cell modules in which the vinyl adhesive of this invention was used. It is a schematic sectional drawing which shows other one Embodiment of the solar cell module backsheet which uses the vinyl adhesive agent of this invention and has a barrier layer.

  As described above, the vinyl adhesive of the present invention contains a vinyl polymer, and the vinyl polymer has an ethylenically unsaturated double bond at the end of the side chain. In the present specification, the vinyl polymer means a polymer having a vinyl group.

The vinyl polymer having an ethylenically unsaturated double bond at the end of the side chain is, for example,
(A) a polymer obtained by polymerizing a monomer component containing at least one monomer selected from the group consisting of an epoxy group-containing monomer and an oxazoline group-containing monomer, and a carboxyl group And / or a vinyl polymer obtained by reacting with a monomer having a hydroxyl group (hereinafter referred to as polymer A),
(B) A polymer obtained by polymerizing a monomer component containing a monomer having a carboxyl group and / or a hydroxyl group, and selected from the group consisting of an epoxy group-containing monomer and an oxazoline group-containing monomer Vinyl polymer obtained by reacting with at least one monomer obtained (hereinafter referred to as polymer B),
(C) A vinyl polymer obtained by reacting a monomer component containing a monomer having a carboxyl group and / or a hydroxyl group with an isocyanate group-containing monomer. (Hereinafter referred to as polymer C),
(D) A vinyl polymer obtained by reacting a polymer obtained by polymerizing a monomer component containing an isocyanate group-containing monomer with a monomer having a carboxyl group and / or a hydroxyl group. (Hereinafter referred to as polymer D),
(E) a vinyl polymer obtained by polymerizing a monomer component containing (meth) acrylic acid (vinyloxyalkoxy) alkyl (hereinafter referred to as polymer E)
These vinyl polymers may be used alone or in combination of two or more.

  In the present specification, “(meth) acrylic acid” means acrylic acid and / or methacrylic acid.

(A) Polymer A
As described above, the polymer A is obtained by polymerizing a monomer component containing at least one monomer selected from the group consisting of an epoxy group-containing monomer and an oxazoline group-containing monomer. It is obtained by reacting a polymer obtained with a monomer having a carboxyl group and / or a hydroxyl group.

  Examples of the epoxy group-containing monomer include alkyl groups such as glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, β-ethylglycidyl acrylate, and β-ethylglycidyl methacrylate. Β-alkylglycidyl (meth) acrylate having 1 to 4 carbon atoms, allyl acrylate, allyl methacrylate, vinylbenzyl glycidyl ether, allyl (glycidyl) ether, 3-acryloyloxymethyl oxetane, 3-methacryloyloxymethyl oxetane 3-methyl-3-acryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl Examples include oxetane, (3,4-epoxycyclohexyl) methyl acrylate, methyl (3,4-epoxycyclohexyl) methyl methacrylate, and vinylcyclohexene oxide, but the present invention is not limited to such examples. . These epoxy group-containing monomers may be used alone or in combination of two or more. Among these epoxy group-containing monomers, glycidyl (meth) acrylate is preferable from the viewpoint of improving adhesiveness, weather resistance and blocking resistance.

  Examples of the oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. It is not limited to only. These oxazoline group-containing monomers may be used alone or in combination of two or more. Among these oxazoline group-containing monomers, 2-vinyl-2-oxazoline is preferable from the viewpoint of improving adhesiveness, weather resistance, and blocking resistance.

  The epoxy group-containing monomer and the oxazoline group-containing monomer may be used alone or in combination. The monomer component may be composed of only at least one monomer selected from the group consisting of an epoxy group-containing monomer and an oxazoline group-containing monomer, Other monomers may be included as long as the object of the present invention is not inhibited.

  Examples of the other monomer include a monomer having a carboxyl group, an acidic phosphate ester monomer, a monomer having a group having active hydrogen, a (meth) acrylic acid ester, and a nitrogen atom. Monomers, monomers having two or more polymerizable double bonds, aromatic monomers, monomers having halogen atoms, vinyl ester monomers, vinyl ether monomers, etc. However, the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of the monomer having a carboxyl group include aliphatic monocarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and maleic anhydride, but the present invention is not limited to such examples. Absent. These monomers having a carboxyl group may be used alone or in combination of two or more.

  Examples of acidic phosphate ester monomers include 2-acryloyloxymethyl acid phosphate, 2-methacryloyloxymethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, and the like. The present invention is not limited to such examples. These acidic phosphate ester monomers may be used alone or in combination of two or more.

  Examples of the monomer having a group having active hydrogen include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate. Examples include hydroxyl group-containing (meth) acrylic acid esters; α-hydroxymethyl acrylates such as methyl α-hydroxymethyl acrylate and ethyl α-hydroxymethyl acrylate, but the present invention is limited to such examples only. It is not a thing. These monomers having a group having active hydrogen may be used alone or in combination of two or more.

  Examples of (meth) acrylic acid esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and n-acrylate. Alkyl (meth) acrylates having 1 to 8 carbon atoms in alkyl groups such as -butyl, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate Cycloalkyl (meth) acrylate having 3 to 8 carbon atoms of cycloalkyl group such as isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate; cyclohexylmethyl acrylate, methacrylic acid Alkyl groups such as cyclohexylmethyl, cyclohexylethyl acrylate, cyclohexylethyl methacrylate, cyclohexylpropyl acrylate, cyclohexylpropyl methacrylate, 4-methylcyclohexylmethyl acrylate and 4-methylcyclohexylmethyl methacrylate have 1 to 8 carbon atoms. And cycloalkylalkyl (meth) acrylate having 3 to 8 carbon atoms in the cycloalkyl group, and the like. However, the present invention is not limited to such examples. These (meth) acrylic acid esters may be used alone or in combination of two or more.

  Examples of the monomer having a nitrogen atom include (meth) acrylamide such as acrylamide and methacrylamide, N, N′-dimethylaminoethyl acrylate, N, N′-dimethylaminoethyl methacrylate, and N, N acrylic acid. -Nitrogen atom-containing (meth) acrylic acid esters such as diethylaminoethyl, N, N-diethylaminoethyl methacrylate, acrylic imide, methacrylic imide, etc. are included, but the present invention is not limited to such examples only. Absent. These monomers having a nitrogen atom may be used alone or in combination of two or more.

  Examples of the monomer having two or more polymerizable double bonds include ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, and tripropylene glycol. Examples include dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and the like, but the present invention is not limited to such examples. These monomers having two or more polymerizable double bonds may be used alone or in combination of two or more.

  Examples of the aromatic monomer include styrene compounds such as styrene and α-methylstyrene, but the present invention is not limited to such examples. These aromatic monomers may be used alone or in combination of two or more.

  Examples of the monomer having a halogen atom include vinyl chloride, but the present invention is not limited to such examples. Only one type of monomer having a halogen atom may be used, or two or more types may be used in combination.

  Examples of the vinyl ester monomer include vinyl acetate, but the present invention is not limited to such examples. Only one type of vinyl ester monomer may be used, or two or more types may be used in combination.

  Examples of the vinyl ether monomer include butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, and the like, but the present invention is not limited to such examples. These vinyl ether monomers may be used alone or in combination of two or more.

  In addition, from the viewpoint of improving adhesiveness, weather resistance, and blocking resistance, the other monomers include UV-absorbing groups such as benzotriazole monomers, benzophenone monomers, and triazine monomers. A monomer having a UV-stable group may be included. A monomer having an ultraviolet absorbing group can be easily obtained commercially, for example, as Otsuka Chemical Co., Ltd., trade name: RUVA93, Osaka Organic Chemical Industry Co., Ltd., trade name: BP-1A, etc. Can do. Monomers having a UV-stable group can be easily obtained commercially, for example, as Adeka Stub series such as Adeka Stub LA-82, ADK STAB LA-87, and the like, manufactured by ADEKA Corporation.

The monomer component may contain acrylic acid having a basic structure of bisarylfluorene from the viewpoint of improving hydrolysis resistance and insulation resistance. Acrylic acid having bisarylfluorene as a basic structure is commercially easily available as, for example, Osaka Gas Chemical Co., Ltd., trade names: Ogsol EA-0200, Ogsol EA-0200, Ogsol EA-0500, Ogsol EA-1000, etc. Can be obtained. Examples of the monomer component include cyclohexyl alkyl ester of (meth) acrylic acid, dicyclopentenyl (meth) acrylic acid, dicyclopentenyloxyethyl (meth) as disclosed in JP-A-2002-69130. Acrylic acid, dicyclopentanyl (meth) acrylic acid, tricyclo [5.2.1.0 ^2.6 ] dec-8-yl (meth) acrylic acid, terpene (meth) acrylic acid, and the like can also be contained.

  The content of at least one monomer selected from the group consisting of an epoxy group-containing monomer and an oxazoline group-containing monomer in the monomer component is a viewpoint of improving adhesiveness, weather resistance and blocking resistance. Therefore, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, particularly preferably 5% by mass or more, and the upper limit is 100% by mass.

  When polymerizing the monomer component, a chain transfer agent may be used as necessary from the viewpoint of suppressing an increase in molecular weight distribution and gelation. Examples of the chain transfer agent include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, and n-octyl 3-mercaptopropionate. , Methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercapto Mercaptocarboxylic esters such as propionate); alkyl such as ethyl mercaptan, tert-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoethane Llucaptans; mercaptoalcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol and 2-naphthalenethiol; tris [(3- Mercaptoisocyanurates such as mercaptopropionyloxy) -ethyl] isocyanurate; disulfides such as 2-hydroxyethyl disulfide and tetraethylthiuram disulfide; dithiocarbamates such as benzyldiethyldithiocarbamate; dimers such as α-methylstyrene dimer Alkyl halides such as carbon tetrabromide, and the like, but the present invention is not limited to such examples. These chain transfer agents may be used alone or in combination of two or more. Among these chain transfer agents, mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkyl mercaptans are obtained because they are easily available, have excellent anti-crosslinking properties, and have a low degree of decrease in polymerization rate. Compounds having a mercapto group such as mercaptoalcohols, aromatic mercaptans and mercaptoisocyanurates are preferred.

  The amount of the chain transfer agent may be appropriately set according to the composition of the monomer component, the polymerization conditions such as the polymerization temperature, the molecular weight of the target polymer, etc., and is not particularly limited, but the weight average molecular weight is several thousand to When obtaining tens of thousands of polymers, the amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass per 100 parts by mass of the monomer component.

  Examples of the method for polymerizing the monomer component include a solution polymerization method, a bulk polymerization method, a dispersion polymerization method, a suspension polymerization method, and an emulsion polymerization method, but the present invention is limited only to such examples. It is not a thing.

  When the monomer component is polymerized by a solution polymerization method, examples of the solvent include aromatic solvents such as toluene and xylene; alcohol solvents such as isopropyl alcohol and n-butyl alcohol; propylene glycol methyl ether and dipropylene glycol methyl. Ether solvents such as ether, ethyl cellosolve, butyl cellosolve; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol; amide solvents such as dimethylformamide However, the present invention is not limited to such examples. These solvents may be used alone or in combination of two or more. The amount of the solvent may be appropriately determined in consideration of the polymerization conditions, the composition of the monomer components, the concentration of the resulting polymer, and the like.

  A polymerization initiator can be used when the monomer component is polymerized. Examples of the polymerization initiator include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), tert-butylperoxy-2-ethylhexano And 2,2′-azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, and the like, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator may be appropriately set according to the desired physical properties of the polymer to be obtained, but is usually preferably 0.01 to 50 parts by mass, more preferably 100 parts by mass of the monomer component. 0.05 to 20 parts by mass.

  The polymerization conditions for polymerizing the monomer components may be set as appropriate according to the polymerization method, and are not particularly limited. The polymerization temperature is preferably selected from the range of room temperature to 200 ° C, more preferably 40 to 140 ° C. What is necessary is just to set reaction time suitably so that the polymerization reaction of a monomer component may be completed. Moreover, it is preferable that the atmosphere in superposition | polymerization is inert gas, such as nitrogen gas and argon gas, for example.

  Next, the weight obtained by polymerizing the monomer component containing at least one monomer selected from the group consisting of an epoxy group-containing monomer and an oxazoline group-containing monomer as described above. The coalescence is reacted with a monomer having a carboxyl group and / or a hydroxyl group.

  Examples of the monomer having a carboxyl group and / or a hydroxyl group include a monomer having a carboxyl group, a monomer having a hydroxyl group, and a monomer having a carboxyl group and a hydroxyl group. These monomers may be used alone or in combination of two or more.

  Examples of the monomer having a carboxyl group include aliphatic monocarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and maleic anhydride, but the present invention is not limited to such examples. Absent. These monomers having a carboxyl group may be used alone or in combination of two or more.

  Examples of the monomer having a hydroxyl group include carbons of alkyl groups such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate. 1 to 4 (meth) acrylic acid hydroxyalkyl; caprolactone-modified 2-hydroxyethyl acrylate, caprolactone-modified 2-hydroxyethyl methacrylate and other alkyl groups having 1 to 4 carbon atoms such as caprolactone-modified hydroxyalkyl (meth) acrylate Hydroxyl group-containing (meth) acrylic acid ester having 1 to 4 carbon atoms of alkyl group; methyl α-hydroxymethyl acrylate, methyl α-hydroxymethyl methacrylate, ethyl α-hydroxymethyl acrylate , Α-hydroxyalkyl acrylates having 1 to 4 carbon atoms in each alkyl group such as ethyl α-hydroxymethyl methacrylate and the like are exemplified, but the present invention is not limited to such examples. These monomers having a hydroxyl group may be used alone or in combination of two or more. Caprolactone-modified hydroxy (meth) acrylate can be easily obtained commercially, for example, as trade name: Plaxel FM1, Plaxel FM1D, Plaxel FM2D, Plaxel FM3, Plaxel FA1DM, Plaxel FA2D, manufactured by Daicel Chemical Industries, Ltd. it can.

  Of the monomers having a carboxyl group and / or a hydroxyl group, (meth) acrylic acid is preferred from the viewpoint of improving adhesiveness, weather resistance and blocking resistance.

  The ratio of the polymer to the monomer having a carboxyl group and / or a hydroxyl group is such that the monomer having a carboxyl group and / or a hydroxyl group per mole of the total amount of the epoxy group and the oxazoline group possessed by the polymer. It is desirable to adjust so that the total amount of carboxyl group and hydroxyl group is preferably 0.1 to 3 mol, more preferably 0.5 to 1.5 mol.

  When reacting the polymer with a monomer having a carboxyl group and / or a hydroxyl group, it is preferable to add an esterification catalyst, a polymerization inhibitor, or the like to the monomer having a carboxyl group and / or a hydroxyl group.

  Examples of the esterification catalyst include organic acid metal salts such as zinc octenoate, phosphonium compounds such as triphenylphosphine, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, and tetrabutylphosphonium bromide. However, the present invention is not limited to such examples. These esterification catalysts may be used alone or in combination of two or more.

  Since the amount of the esterification catalyst varies depending on the type of the esterification catalyst, it cannot be determined unconditionally, but is usually preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass per 100 parts by mass of the polymer. 3 parts by mass.

  Examples of the polymerization inhibitor include methoxyphenol; quinones such as hydroquinone, benzoquinone, and p-tert-butylcatechol; 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert- Alkylphenols such as butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol; alkylated diphenylamine, N, N′-diphenyl -P-phenylenediamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,4-dihydroxy-2,2 , 6,6-tetramethylpiperidine, 1-hydroxy-4- Amines such as nzoyloxy-2,2,6,6-tetramethylpiperidine; copper dithiocarbamates such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate; 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2 , 6,6-tetramethylpiperidine 1-oxyl and the like, but the present invention is not limited to such examples. These polymerization inhibitors may be used alone or in combination of two or more.

  The amount of the polymerization inhibitor improves the yield, suppresses the polymerization of the monomer having a carboxyl group and / or a hydroxyl group, and maintains the reactivity with the polymer, so that the carboxyl group and / or the hydroxyl group is maintained. Preferably it is 0.01-10000 ppm, More preferably, it is 0.1-7000 ppm, More preferably, it is 1-5000 ppm with respect to the monomer which has this.

  The reaction between the polymer and a monomer having a carboxyl group and / or a hydroxyl group is carried out, for example, by adding a monomer having a carboxyl group and / or a hydroxyl group to the reaction mixture from which the polymer is obtained. be able to.

  The reaction conditions for reacting the polymer with a monomer having a carboxyl group and / or a hydroxyl group may be appropriately set according to the reaction method, and are not particularly limited. The reaction temperature is preferably selected from the range of room temperature to 200 ° C, more preferably 40 to 140 ° C. What is necessary is just to set reaction time suitably so that reaction may be completed. The atmosphere during the reaction is not particularly limited and may be air, for example, an inert gas such as nitrogen gas or argon gas, or a mixed gas of oxygen and inert gas. There may be.

  As described above, the polymer A is obtained by reacting the polymer with a monomer having a carboxyl group and / or a hydroxyl group. The weight average molecular weight of the polymer A is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and further preferably 30,000 to 300,000. The weight average molecular weight is a value when measured by gel permeation chromatography (GPC) with a polystyrene standard.

  The acid value or hydroxyl value of the polymer A (nonvolatile component) is preferably 0.1 to 200 mgKOH / g, more preferably 1 to 100 mgKOH / g, from the viewpoint of improving adhesiveness, weather resistance and blocking resistance. More preferably, it is 3-60 mgKOH / g.

(B) Polymer B
As described above, the polymer B includes a polymer obtained by polymerizing a monomer component containing a monomer having a carboxyl group and / or a hydroxyl group, an epoxy group-containing monomer, and an oxazoline group-containing monomer. It is obtained by reacting with at least one monomer selected from the group consisting of monomers.

  Examples of the monomer having a carboxyl group and / or a hydroxyl group include the same monomers as those having a carboxyl group and / or a hydroxyl group used in preparing the polymer A. More specifically, examples of the monomer having a carboxyl group and / or a hydroxyl group include a monomer having a carboxyl group, a monomer having a hydroxyl group, and a monomer having a carboxyl group and a hydroxyl group. These monomers may be used alone or in combination of two or more.

  Examples of the monomer having a carboxyl group include aliphatic monocarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and maleic anhydride, but the present invention is not limited to such examples. Absent. These monomers having a carboxyl group may be used alone or in combination of two or more.

  Examples of the monomer having a hydroxyl group include carbons of alkyl groups such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate. 1 to 4 (meth) acrylic acid hydroxyalkyl; caprolactone-modified 2-hydroxyethyl acrylate, caprolactone-modified 2-hydroxyethyl methacrylate and other alkyl groups having 1 to 4 carbon atoms such as caprolactone-modified hydroxyalkyl (meth) acrylate Hydroxyl group-containing (meth) acrylic acid ester having 1 to 4 carbon atoms of alkyl group; methyl α-hydroxymethyl acrylate, methyl α-hydroxymethyl methacrylate, ethyl α-hydroxymethyl acrylate , Α-hydroxyalkyl acrylates having 1 to 4 carbon atoms in each alkyl group such as ethyl α-hydroxymethyl methacrylate and the like are exemplified, but the present invention is not limited to such examples. These monomers having a hydroxyl group may be used alone or in combination of two or more. Caprolactone-modified hydroxy (meth) acrylate can be easily obtained commercially, for example, as trade name: Plaxel FM1, Plaxel FM1D, Plaxel FM2D, Plaxel FM3, Plaxel FA1DM, Plaxel FA2D, manufactured by Daicel Chemical Industries, Ltd. it can.

  Among monomers having a carboxyl group and / or a hydroxyl group, from the viewpoint of improving adhesion, weather resistance and blocking resistance, a hydroxyl group-containing (meth) acrylic acid ester preferably having an alkyl group having 1 to 18 carbon atoms More preferably, the hydroxyl group-containing (meth) acrylic acid ester having 1 to 12 carbon atoms in the alkyl group, even more preferably the hydroxyl group-containing (meth) acrylic acid ester having 1 to 6 carbon atoms in the alkyl group, more preferably alkyl. It is a hydroxyl group-containing (meth) acrylic acid ester having 1 to 4 carbon atoms.

  The monomer component may contain other monomers as long as the object of the present invention is not impaired. Other monomers include, for example, acidic phosphate ester monomers, (meth) acrylic acid esters, monomers having an epoxy group, monomers having a nitrogen atom, two or more polymerizable doubles Examples include a monomer having a bond, an aromatic monomer, a monomer having a halogen atom, a vinyl ester monomer, and a vinyl ether monomer, but the present invention is limited only to such examples. It is not something. These monomers may be used alone or in combination of two or more.

  The acidic phosphate ester monomer, (meth) acrylic acid ester, monomer having nitrogen atom, monomer having two or more polymerizable double bonds, aromatic monomer, halogen atom Examples of the monomer, vinyl ester monomer, and vinyl ether monomer that are included are the same as the other monomers used in preparing the polymer A.

  Examples of the monomer having an epoxy group include epoxy group-containing (meth) acrylic acid esters such as glycidyl acrylate and glycidyl methacrylate, but the present invention is not limited to such examples. . These monomers having an epoxy group may be used alone or in combination of two or more.

  Among the other monomers, from the viewpoint of improving adhesiveness, weather resistance, and blocking resistance, (meth) acrylic acid esters are preferable, and (meth) acrylic acid alkyl and (meth) acrylic acid cycloalkyl are more preferable. preferable.

  In addition, from the viewpoint of improving weather resistance and blocking resistance, the other monomer may be a monomer having an ultraviolet absorbing group such as a benzotriazole monomer, a benzophenone monomer, or a triazine monomer. A monomer; a monomer having an ultraviolet-stable group may be included. Examples of the monomer having a UV-absorbing group and the monomer having a UV-stable group are the same as those used in preparing the polymer A.

  The monomer component may contain acrylic acid having a basic structure of bisarylfluorene from the viewpoint of improving hydrolysis resistance and insulation resistance. Examples of the acrylic acid having bisarylfluorene as a basic structure are the same as those used in preparing the polymer A.

  The content of the monomer having a carboxyl group and / or a hydroxyl group in the monomer component is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably from the viewpoint of improving adhesiveness. It is 3% by mass or more, particularly preferably 5% by mass or more, and the upper limit is 100% by mass.

  When polymerizing the monomer component, a chain transfer agent may be used as necessary from the viewpoint of suppressing an increase in molecular weight distribution and gelation. Examples of the chain transfer agent are the same as those used in preparing the polymer A.

  The amount of the chain transfer agent may be appropriately set according to the composition of the monomer component, the polymerization conditions such as the polymerization temperature, the molecular weight of the target polymer, etc., and is not particularly limited, but the weight average molecular weight is several thousand to When obtaining tens of thousands of polymers, the amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass per 100 parts by mass of the monomer component.

  Examples of the method for polymerizing the monomer component include a solution polymerization method, a bulk polymerization method, a dispersion polymerization method, a suspension polymerization method, and an emulsion polymerization method, but the present invention is limited only to such examples. It is not a thing.

  Examples of the solvent used when the monomer component is polymerized by the solution polymerization method are the same as those used when the polymer A is prepared.

  A polymerization initiator can be used when the monomer component is polymerized. As a polymerization initiator, the same thing as used when preparing the said polymer A is illustrated. The amount of the polymerization initiator may be appropriately set according to the desired physical properties of the polymer to be obtained. Usually, it is preferably 0.05 to 30 parts by mass, more preferably 100 parts by mass of the monomer component. 0.15 to 10 parts by mass.

  The polymerization conditions for polymerizing the monomer components may be set as appropriate according to the polymerization method, and are not particularly limited. The polymerization temperature is preferably selected from the range of room temperature to 200 ° C, more preferably 40 to 140 ° C. What is necessary is just to set reaction time suitably so that the polymerization reaction of a monomer component may be completed. Moreover, it is preferable that the atmosphere in superposition | polymerization is inert gas, such as nitrogen gas and argon gas, for example.

  Next, a polymer obtained by polymerizing a monomer component containing a monomer having a carboxyl group and / or a hydroxyl group as described above, an epoxy group-containing monomer, and an oxazoline group-containing monomer And at least one monomer selected from the group consisting of:

  The epoxy group-containing monomer and the oxazoline group-containing monomer may be used alone or in combination of two or more.

  Examples of the epoxy group-containing monomer include alkyl groups such as glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, β-ethylglycidyl acrylate, and β-ethylglycidyl methacrylate. Β-alkylglycidyl (meth) acrylate having 1 to 4 carbon atoms, allyl acrylate, allyl methacrylate, vinylbenzyl glycidyl ether, allyl (glycidyl) ether, 3-acryloyloxymethyl oxetane, 3-methacryloyloxymethyl oxetane 3-methyl-3-acryloyloxymethyl oxetane, 3-methyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl Examples include oxetane, (3,4-epoxycyclohexyl) methyl acrylate, methyl (3,4-epoxycyclohexyl) methyl methacrylate, and vinylcyclohexene oxide, but the present invention is not limited to such examples. . These epoxy group-containing monomers may be used alone or in combination of two or more. Among these epoxy group-containing monomers, glycidyl (meth) acrylate is preferable from the viewpoint of improving adhesiveness, weather resistance and blocking resistance.

  Examples of the oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. It is not limited to only. These oxazoline group-containing monomers may be used alone or in combination of two or more. Among these oxazoline group-containing monomers, 2-vinyl-2-oxazoline is preferable from the viewpoint of improving adhesiveness, weather resistance, and blocking resistance.

  The reaction of the polymer with at least one monomer selected from the group consisting of an epoxy group-containing monomer and an oxazoline group-containing monomer can be carried out, for example, by adding epoxy to the reaction mixture from which the polymer is obtained. It can be performed by adding at least one monomer selected from the group consisting of a group-containing monomer and an oxazoline group-containing monomer.

  The reaction conditions for reacting the polymer with at least one monomer selected from the group consisting of an epoxy group-containing monomer and an oxazoline group-containing monomer are appropriately set according to the reaction method. There is no particular limitation. The reaction temperature is preferably selected from the range of room temperature to 200 ° C, more preferably 40 to 140 ° C. What is necessary is just to set reaction time suitably so that reaction may be completed. The atmosphere during the reaction is not particularly limited and may be air, for example, an inert gas such as nitrogen gas or argon gas, or a mixed gas of oxygen and inert gas. There may be.

  Polymer B is obtained by reacting the polymer with at least one monomer selected from the group consisting of an epoxy group-containing monomer and an oxazoline group-containing monomer as described above. The weight average molecular weight of the polymer B is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and still more preferably 30,000 to 300,000. The weight average molecular weight is a value when measured by gel permeation chromatography (GPC) with a polystyrene standard.

  The acid value or hydroxyl value of the polymer B (nonvolatile content) is preferably 0.1 to 200 mgKOH / g, more preferably 1 to 100 mgKOH / g, from the viewpoint of improving adhesiveness, weather resistance and blocking resistance. More preferably, it is 3-60 mgKOH / g.

(C) Polymer C
As described above, the polymer C is obtained by reacting a polymer obtained by polymerizing a monomer component containing a monomer having a carboxyl group and / or a hydroxyl group with an isocyanate group-containing monomer. can get.

  Examples of the monomer having a carboxyl group and / or a hydroxyl group include the same monomers as those having a carboxyl group and / or a hydroxyl group used in preparing the polymer A. More specifically, examples of the monomer having a carboxyl group and / or a hydroxyl group include a monomer having a carboxyl group, a monomer having a hydroxyl group, and a monomer having a carboxyl group and a hydroxyl group. These monomers may be used alone or in combination of two or more.

  Examples of the monomer having a carboxyl group include aliphatic monocarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and maleic anhydride, but the present invention is not limited to such examples. Absent. These monomers having a carboxyl group may be used alone or in combination of two or more.

  Examples of the monomer having a hydroxyl group include carbons of alkyl groups such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate. 1 to 4 (meth) acrylic acid hydroxyalkyl; caprolactone-modified 2-hydroxyethyl acrylate, caprolactone-modified 2-hydroxyethyl methacrylate and other alkyl groups having 1 to 4 carbon atoms such as caprolactone-modified hydroxyalkyl (meth) acrylate Hydroxyl group-containing (meth) acrylic acid ester having 1 to 4 carbon atoms of alkyl group; methyl α-hydroxymethyl acrylate, methyl α-hydroxymethyl methacrylate, ethyl α-hydroxymethyl acrylate , Α-hydroxyalkyl acrylates having 1 to 4 carbon atoms in each alkyl group such as ethyl α-hydroxymethyl methacrylate and the like are exemplified, but the present invention is not limited to such examples. These monomers having a hydroxyl group may be used alone or in combination of two or more. Caprolactone-modified hydroxy (meth) acrylate can be easily obtained commercially, for example, as trade name: Plaxel FM1, Plaxel FM1D, Plaxel FM2D, Plaxel FM3, Plaxel FA1DM, Plaxel FA2D, manufactured by Daicel Chemical Industries, Ltd. it can.

  Among monomers having a carboxyl group and / or a hydroxyl group, from the viewpoint of improving adhesion, weather resistance and blocking resistance, a hydroxyl group-containing (meth) acrylic acid ester preferably having an alkyl group having 1 to 18 carbon atoms More preferably, the hydroxyl group-containing (meth) acrylic acid ester having 1 to 12 carbon atoms in the alkyl group, even more preferably the hydroxyl group-containing (meth) acrylic acid ester having 1 to 6 carbon atoms in the alkyl group, more preferably alkyl It is a hydroxyl group-containing (meth) acrylic acid ester having 1 to 4 carbon atoms.

  The monomer component may contain other monomers as long as the object of the present invention is not impaired. Other monomers include, for example, acidic phosphate ester monomers, (meth) acrylic acid esters, monomers having an epoxy group, monomers having a nitrogen atom, two or more polymerizable doubles Examples include a monomer having a bond, an aromatic monomer, a monomer having a halogen atom, a vinyl ester monomer, and a vinyl ether monomer, but the present invention is limited only to such examples. It is not something. These monomers may be used alone or in combination of two or more.

  The acidic phosphate ester monomer, (meth) acrylic acid ester, monomer having nitrogen atom, monomer having two or more polymerizable double bonds, aromatic monomer, halogen atom Examples of the monomer, vinyl ester monomer, and vinyl ether monomer that are included are the same as the other monomers used in preparing the polymer A.

  Examples of the monomer having an epoxy group include epoxy group-containing (meth) acrylic acid esters such as glycidyl acrylate and glycidyl methacrylate, but the present invention is not limited to such examples. . These monomers having an epoxy group may be used alone or in combination of two or more.

  Among the other monomers, from the viewpoint of improving adhesiveness, weather resistance, and blocking resistance, (meth) acrylic acid esters are preferable, and (meth) acrylic acid alkyl and (meth) acrylic acid cycloalkyl are more preferable. preferable.

  In addition, from the viewpoint of improving weather resistance and blocking resistance, the other monomer may be a monomer having an ultraviolet absorbing group such as a benzotriazole monomer, a benzophenone monomer, or a triazine monomer. A monomer; a monomer having an ultraviolet-stable group may be included. Examples of the monomer having a UV-absorbing group and the monomer having a UV-stable group are the same as those used in preparing the polymer A.

  The monomer component may contain acrylic acid having a basic structure of bisarylfluorene from the viewpoint of improving hydrolysis resistance and insulation resistance. Examples of the acrylic acid having bisarylfluorene as a basic structure are the same as those used in preparing the polymer A.

  The content of the monomer having a carboxyl group and / or a hydroxyl group in the monomer component is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably from the viewpoint of improving adhesiveness. It is 3% by mass or more, particularly preferably 5% by mass or more, and the upper limit is 100% by mass.

  When polymerizing the monomer component, a chain transfer agent may be used as necessary from the viewpoint of suppressing an increase in molecular weight distribution and gelation. Examples of the chain transfer agent are the same as those used in preparing the polymer A.

  The amount of the chain transfer agent may be appropriately set according to the composition of the monomer component, the polymerization conditions such as the polymerization temperature, the molecular weight of the target polymer, etc., and is not particularly limited, but the weight average molecular weight is several thousand to When obtaining tens of thousands of polymers, the amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass per 100 parts by mass of the monomer component.

  Examples of the method for polymerizing the monomer component include a solution polymerization method, a bulk polymerization method, a dispersion polymerization method, a suspension polymerization method, and an emulsion polymerization method, but the present invention is limited only to such examples. It is not a thing.

  Examples of the solvent used when the monomer component is polymerized by the solution polymerization method are the same as those used when the polymer A is prepared.

  A polymerization initiator can be used when the monomer component is polymerized. As a polymerization initiator, the same thing as used when preparing the said polymer A is illustrated. The amount of the polymerization initiator may be appropriately set according to the desired physical properties of the polymer to be obtained. Usually, it is preferably 0.05 to 30 parts by mass, more preferably 100 parts by mass of the monomer component. 0.15 to 10 parts by mass.

  The polymerization conditions for polymerizing the monomer components may be set as appropriate according to the polymerization method, and are not particularly limited. The polymerization temperature is preferably selected from the range of room temperature to 200 ° C, more preferably 40 to 140 ° C. What is necessary is just to set reaction time suitably so that the polymerization reaction of a monomer component may be completed. Moreover, it is preferable that the atmosphere in superposition | polymerization is inert gas, such as nitrogen gas and argon gas, for example.

  Next, the polymer obtained by polymerizing the monomer component containing the monomer having a carboxyl group and / or a hydroxyl group as described above is reacted with the isocyanate group-containing monomer.

  Examples of the isocyanate group-containing monomer include acryloyloxymethyl isocyanate, methacryloyloxymethyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 3-acryloyloxypropyl isocyanate, and 3-methacryloyloxypropyl isocyanate. Examples of the alkyl group include (meth) acryloyloxyalkyl isocyanate having 1 to 4 carbon atoms and 3-isopropenyl-α, α-dimethylbenzyl isocyanate, but the present invention is not limited to such examples. . These monomers having a carboxyl group may be used alone or in combination of two or more.

  A catalyst is preferably used when the polymer and the isocyanate group-containing monomer are reacted.

  Examples of the catalyst include dialkyltin dicarboxylates such as dibutyltin dilaurate, dibutyltin dineodecanoate, and dibutyltin diacetate, but the present invention is not limited to such examples. Since the amount of the catalyst varies depending on the type and the like, it cannot be determined unconditionally. 0 to 1 part by mass.

  The reaction between the polymer and the isocyanate group-containing monomer can be performed, for example, by adding an isocyanate group-containing monomer to the reaction mixture from which the polymer is obtained.

  The ratio of the polymer and the isocyanate group-containing monomer is the equivalent ratio of the carboxyl group and / or hydroxyl group of the polymer to the isocyanate group of the isocyanate group-containing monomer (equivalent of NCO group / carboxyl group and The total equivalent weight of the hydroxyl groups) is preferably adjusted to be 0.1 to 5, more preferably 0.2 to 3.

  The reaction conditions for reacting the polymer with the isocyanate group-containing monomer are not particularly limited, and may be set as appropriate according to the reaction method. The reaction temperature is preferably selected from the range of room temperature to 200 ° C, more preferably 40 to 140 ° C. What is necessary is just to set reaction time suitably so that reaction may be completed. The atmosphere during the reaction is not particularly limited and may be air, for example, an inert gas such as nitrogen gas or argon gas, or a mixed gas of oxygen and inert gas. There may be.

  The polymer C is obtained by reacting the polymer with the isocyanate group-containing monomer as described above. The weight average molecular weight of the polymer C is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and still more preferably 30,000 to 300,000. The weight average molecular weight is a value when measured by gel permeation chromatography (GPC) with a polystyrene standard.

  In addition, the hydroxyl value of the polymer C (nonvolatile content) is preferably 0.4 to 200 mgKOH / g, more preferably 1 to 100 KOH / g, and still more preferably, from the viewpoint of improving adhesiveness, weather resistance and blocking resistance. Is 3-60 mg KOH / g.

(D) Polymer D
As described above, the polymer D is obtained by reacting a polymer obtained by polymerizing a monomer component containing an isocyanate group-containing monomer with a monomer having a carboxyl group and / or a hydroxyl group. Obtained by.

  As an isocyanate group containing monomer, the thing similar to the isocyanate group containing monomer used when preparing the said polymer C is illustrated. More specifically, for example, alkyl groups such as acryloyloxymethyl isocyanate, methacryloyloxymethyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 3-acryloyloxypropyl isocyanate, 3-methacryloyloxypropyl isocyanate, etc. Examples thereof include (meth) acryloyloxyalkyl isocyanate having 1 to 4 carbon atoms and 3-isopropenyl-α, α-dimethylbenzyl isocyanate, but the present invention is not limited only to such examples. These monomers having a carboxyl group may be used alone or in combination of two or more.

  The monomer component may contain other monomers as long as the object of the present invention is not impaired. Other monomers include, for example, acidic phosphate ester monomers, (meth) acrylic acid esters, monomers having nitrogen atoms, monomers having two or more polymerizable double bonds, aromatics Examples include group-based monomers, monomers having halogen atoms, vinyl ester monomers, vinyl ether monomers, and the like, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Acid phosphate ester monomer, (meth) acrylic acid ester, monomer having epoxy group, monomer having nitrogen atom, monomer having two or more polymerizable double bonds, aromatic Examples of the monomer, the monomer having a halogen atom, the vinyl ester monomer and the vinyl ether monomer are the same as the other monomers used in preparing the polymer C. The

  Among the other monomers, from the viewpoint of improving adhesiveness, weather resistance, and blocking resistance, (meth) acrylic acid esters are preferable, and (meth) acrylic acid alkyl and (meth) acrylic acid cycloalkyl are more preferable. preferable.

  In addition, from the viewpoint of improving weather resistance and blocking resistance, the other monomer may be a monomer having an ultraviolet absorbing group such as a benzotriazole monomer, a benzophenone monomer, or a triazine monomer. A monomer; a monomer having an ultraviolet-stable group may be included. Examples of the monomer having a UV-absorbing group and the monomer having a UV-stable group are the same as those used in preparing the polymer A.

  The monomer component may contain acrylic acid having a basic structure of bisarylfluorene from the viewpoint of improving hydrolysis resistance and insulation resistance. Examples of the acrylic acid having bisarylfluorene as a basic structure are the same as those used in preparing the polymer A.

  The content of the isocyanate group-containing monomer in the monomer component is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, from the viewpoint of improving adhesiveness. Especially preferably, it is 5 mass% or more, and the upper limit is 100 mass%.

  When polymerizing the monomer component, a chain transfer agent may be used as necessary from the viewpoint of suppressing an increase in molecular weight distribution and gelation. Examples of the chain transfer agent are the same as those used in preparing the polymer A.

  The amount of the chain transfer agent may be appropriately set according to the composition of the monomer component, the polymerization conditions such as the polymerization temperature, the molecular weight of the target polymer, etc., and is not particularly limited, but the weight average molecular weight is several thousand to When obtaining tens of thousands of polymers, the amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass per 100 parts by mass of the monomer component.

  Examples of the method for polymerizing the monomer component include a solution polymerization method, a bulk polymerization method, a dispersion polymerization method, a suspension polymerization method, and an emulsion polymerization method, but the present invention is limited only to such examples. It is not a thing.

  Examples of the solvent used when the monomer component is polymerized by the solution polymerization method are the same as those used when the polymer A is prepared.

  A polymerization initiator can be used when the monomer component is polymerized. As a polymerization initiator, the same thing as used when preparing the said polymer A is illustrated. The amount of the polymerization initiator may be appropriately set according to the desired physical properties of the polymer to be obtained. Usually, it is preferably 0.05 to 30 parts by mass, more preferably 100 parts by mass of the monomer component. 0.15 to 10 parts by mass.

  The polymerization conditions for polymerizing the monomer components may be set as appropriate according to the polymerization method, and are not particularly limited. The polymerization temperature is preferably selected from the range of room temperature to 200 ° C, more preferably 40 to 140 ° C. What is necessary is just to set reaction time suitably so that the polymerization reaction of a monomer component may be completed. Moreover, it is preferable that the atmosphere in superposition | polymerization is inert gas, such as nitrogen gas and argon gas, for example.

  Next, the polymer obtained by polymerizing the monomer component containing the isocyanate group-containing monomer as described above is reacted with a monomer having a carboxyl group and / or a hydroxyl group.

  Examples of the monomer having a carboxyl group and / or a hydroxyl group include the same monomers as those having a carboxyl group and / or a hydroxyl group used in preparing the polymer A. More specifically, examples of the monomer having a carboxyl group and / or a hydroxyl group include a monomer having a carboxyl group, a monomer having a hydroxyl group, and a monomer having a carboxyl group and a hydroxyl group. These monomers may be used alone or in combination of two or more.

  Examples of the monomer having a carboxyl group include aliphatic monocarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and maleic anhydride, but the present invention is not limited to such examples. Absent. These monomers having a carboxyl group may be used alone or in combination of two or more.

  Examples of the monomer having a hydroxyl group include carbons of alkyl groups such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate. 1 to 4 (meth) acrylic acid hydroxyalkyl; caprolactone-modified 2-hydroxyethyl acrylate, caprolactone-modified 2-hydroxyethyl methacrylate and other alkyl groups having 1 to 4 carbon atoms such as caprolactone-modified hydroxyalkyl (meth) acrylate Hydroxyl group-containing (meth) acrylic acid ester having 1 to 4 carbon atoms of alkyl group; methyl α-hydroxymethyl acrylate, methyl α-hydroxymethyl methacrylate, ethyl α-hydroxymethyl acrylate , Α-hydroxyalkyl acrylates having 1 to 4 carbon atoms in each alkyl group such as ethyl α-hydroxymethyl methacrylate and the like are exemplified, but the present invention is not limited to such examples. These monomers having a hydroxyl group may be used alone or in combination of two or more. Caprolactone-modified hydroxy (meth) acrylate can be easily obtained commercially, for example, as trade name: Plaxel FM1, Plaxel FM1D, Plaxel FM2D, Plaxel FM3, Plaxel FA1DM, Plaxel FA2D, manufactured by Daicel Chemical Industries, Ltd. it can.

  Among monomers having a carboxyl group and / or a hydroxyl group, from the viewpoint of improving adhesion, weather resistance and blocking resistance, a hydroxyl group-containing (meth) acrylic acid ester preferably having an alkyl group having 1 to 18 carbon atoms More preferably, the hydroxyl group-containing (meth) acrylic acid ester having 1 to 12 carbon atoms in the alkyl group, even more preferably the hydroxyl group-containing (meth) acrylic acid ester having 1 to 6 carbon atoms in the alkyl group, more preferably alkyl. It is a hydroxyl group-containing (meth) acrylic acid ester having 1 to 4 carbon atoms.

  When the polymer is reacted with a monomer having a carboxyl group and / or a hydroxyl group, a catalyst is preferably used.

  Examples of the catalyst include dialkyltin dicarboxylates such as dibutyltin dilaurate, dibutyltin dineodecanoate, and dibutyltin diacetate, but the present invention is not limited to such examples. Since the amount of the catalyst varies depending on the type and the like, it cannot be determined unconditionally, but usually, per 100 parts by mass of the monomer having a carboxyl group and / or a hydroxyl group, preferably 0.005 to 5 parts by mass, More preferably, it is 0.01-3 mass parts.

  The reaction between the polymer and a monomer having a carboxyl group and / or a hydroxyl group is carried out, for example, by adding a monomer having a carboxyl group and / or a hydroxyl group to the reaction mixture from which the polymer is obtained. be able to.

  The ratio between the polymer and the monomer having a carboxyl group and / or a hydroxyl group is equivalent to the carboxyl group and / or the hydroxyl group of the polymer and the isocyanate group of the monomer having a carboxyl group and / or a hydroxyl group. The ratio (equivalent of NCO group / total equivalent of carboxyl group and hydroxyl group) is preferably adjusted to be 0.1 to 5, more preferably 0.2 to 3.

  The reaction conditions for reacting the polymer with a monomer having a carboxyl group and / or a hydroxyl group may be appropriately set according to the reaction method, and are not particularly limited. The reaction temperature is preferably selected from the range of room temperature to 200 ° C, more preferably 40 to 140 ° C. What is necessary is just to set reaction time suitably so that reaction may be completed. The atmosphere during the reaction is not particularly limited and may be air, for example, an inert gas such as nitrogen gas or argon gas, or a mixed gas of oxygen and inert gas. There may be.

  As described above, the polymer D is obtained by reacting the polymer with a monomer having a carboxyl group and / or a hydroxyl group. The weight average molecular weight of the polymer D is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and still more preferably 30,000 to 300,000. The weight average molecular weight is a value when measured by gel permeation chromatography (GPC) with a polystyrene standard.

  Further, the hydroxyl value of the polymer D (nonvolatile component) is preferably 0.4 to 200 mgKOH / g, more preferably 1 to 100 KOH / g, and further preferably, from the viewpoint of improving adhesiveness, weather resistance and blocking resistance. Is 3-60 mg KOH / g.

(E) Polymer E
As described above, the polymer E is obtained by polymerizing a monomer component containing (meth) acrylic acid (vinyloxyalkoxy) alkyl.

  Examples of (meth) acrylic acid (vinyloxyalkoxy) alkyl include, for example, methyl (vinyloxymethoxy) acrylate, vinyloxymethacrylate methacrylate, vinyloxyethoxy ethyl methacrylate, and vinyloxyethoxy methacrylate. Examples include (meth) acrylic acid (vinyloxyalkoxy) alkyl having 1 to 4 carbon atoms in the alkoxy group such as ethyl and 1 to 4 carbon atoms in the alkyl group. It is not limited. In addition, (meth) acrylic acid (vinyloxyalkoxy) alkyl can be easily obtained commercially as, for example, Nippon Shokubai Co., Ltd., product number: VEEA [2- (2-vinyloxyethoxy) ethyl acrylate]. be able to.

  The monomer component may contain other monomers as long as the object of the present invention is not impaired. Other monomers include, for example, a monomer having a carboxyl group, an acidic phosphate monomer, a monomer having a group having active hydrogen, a (meth) acrylic acid ester, and a monomer having an epoxy group. Monomer, monomer having nitrogen atom, monomer having two or more polymerizable double bonds, aromatic monomer, monomer having halogen atom, vinyl ester monomer, vinyl ether Although a monomer etc. are mentioned, this invention is not limited only to this illustration.

  The acidic phosphate ester monomer, (meth) acrylic acid ester, monomer having nitrogen atom, monomer having two or more polymerizable double bonds, aromatic monomer, halogen atom Examples of the monomer, vinyl ester monomer, and vinyl ether monomer that are included are the same as the other monomers used in preparing the polymer A. Moreover, as the monomer which has the said epoxy group, the same thing as the other monomer used when preparing the said polymer C is illustrated.

  Among the other monomers, vinyl ether monomers are preferable, and alkyl vinyl ethers having 1 to 8 carbon atoms and alkyl groups such as butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, and the like. The cycloalkyl vinyl ether of -12 is more preferable, and the alkyl vinyl ether whose alkyl group has 4-8 carbon atoms is more preferable.

  In addition, from the viewpoint of improving adhesiveness, weather resistance, and blocking resistance, the other monomers include UV-absorbing groups such as benzotriazole monomers, benzophenone monomers, and triazine monomers. A monomer having a UV-stable group may be included. Examples of the monomer having a UV-absorbing group and the monomer having a UV-stable group are the same as those used in preparing the polymer A.

  In addition, the monomer component may contain acrylic acid having bisarylfluorene as a basic structure from the viewpoint of improving adhesiveness, hydrolysis resistance, and insulation resistance. Examples of the acrylic acid having bisarylfluorene as a basic structure are the same as those used in preparing the polymer A.

  The content of (meth) acrylic acid (vinyloxyalkoxy) alkyl in the monomer component is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 3 from the viewpoint of improving adhesiveness. The upper limit is 100% by mass or more, particularly preferably 5% by mass or more.

  When polymerizing the monomer component, a chain transfer agent may be used as necessary from the viewpoint of suppressing an increase in molecular weight distribution and gelation. Examples of the chain transfer agent are the same as those used in preparing the polymer A.

  The amount of the chain transfer agent may be appropriately set according to the composition of the monomer component, the polymerization conditions such as the polymerization temperature, the molecular weight of the target polymer, etc., and is not particularly limited, but the weight average molecular weight is several thousand to When obtaining tens of thousands of polymers, the amount is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass per 100 parts by mass of the monomer component.

  Examples of the polymerization method of the monomer component include a solution polymerization method, a bulk polymerization method, a dispersion polymerization method, a suspension polymerization method, and an emulsion polymerization method, but the present invention is limited only to such examples. is not.

  When the monomer component is polymerized by a solution polymerization method, examples of the solvent include aromatic solvents such as toluene and xylene; alcohol solvents such as isopropyl alcohol and n-butyl alcohol; propylene glycol methyl ether and dipropylene glycol methyl. Ether solvents such as ether, ethyl cellosolve, butyl cellosolve; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol; amide solvents such as dimethylformamide However, the present invention is not limited to such examples. These solvents may be used alone or in combination of two or more. The amount of the solvent may be appropriately determined in consideration of the polymerization conditions, the composition of the monomer components, the concentration of the resulting polymer, and the like.

  The polymerization of the monomer component can be performed by an ionic polymerization method such as a cationic polymerization method. Examples of the polymerization initiator used in the cationic polymerization include heteropoly acid, perchloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, picrylsulfonic acid, trifluoromethanesulfonic acid, trichloroacetic acid, trifluoroacetic acid and the like. Protonic acid, boron trifluoride, aluminum bromide, aluminum chloride, antimony pentachloride, ferric chloride, tin tetrachloride, titanium tetrachloride, mercury chloride, zinc chloride and other Lewis acids, iodine, triphenylchloromethane, etc. Although mentioned, this invention is not limited only to this illustration.

  The heteropolyacid has, for example, a Keggin structure having an atom such as tungsten, molybdenum, or vanadium at the center of the acid, and the heteroatom is an atom such as phosphorus, silicon, germanium, titanium, zirconium, boron, arsenic, or cobalt. Polyacid. Examples of the heteropoly acid include phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, borotungstic acid, boromolybdic acid, cobalt molybdic acid, cobalt tungstic acid, arsenic tungstic acid, germanium tungstic acid, and phosphororib. Examples include detungstic acid and boro-rib tungstic acid, but the present invention is not limited to such examples. Among these, phosphotungstic acid is preferable because it is uncolored, has high solubility in organic solvents, and is excellent in polymerization initiation ability.

  The amount of the polymerization initiator is preferably 1 ppm to 30% by mass, more preferably 5 ppm, based on the monomer component, from the viewpoint of allowing the polymerization reaction to be quickly performed and the polymerization reaction to be easily controlled. -20% by mass, more preferably 10 ppm to 10% by mass.

  The polymerization conditions for polymerizing the monomer components may be set as appropriate according to the polymerization method, and are not particularly limited. The polymerization temperature is preferably selected from the range of room temperature to 200 ° C, more preferably 40 to 140 ° C. What is necessary is just to set reaction time suitably so that the polymerization reaction of a monomer component may be completed. Moreover, it is preferable that the atmosphere in superposition | polymerization is inert gas, such as nitrogen gas and argon gas, for example.

  After the monomer component is polymerized, the polymerization reaction may be stopped by adding a polymerization reaction terminator to the obtained reaction mixture, if necessary. Examples of the polymerization reaction terminator include organic bases such as amines such as ammonia and triethylamine, and inorganic bases such as sodium hydroxide and potassium hydroxide, but the present invention is not limited to such examples only. Absent.

  Polymer E is obtained by polymerizing the monomer components as described above. The weight average molecular weight of the polymer E becomes like this. Preferably it is 1000-1 million, More preferably, it is 1500-500,000, More preferably, it is 2000-300,000. The weight average molecular weight is a value when measured by gel permeation chromatography (GPC) with a polystyrene standard.

  The number of ethylenically unsaturated double bonds present at the end of the side chain per molecule of the vinyl polymer having an ethylenically unsaturated double bond at the end of the side chain is good for adhesion, weather resistance and blocking resistance. From the viewpoint of improving, it is preferable to have 4 or more, more preferably 7 or more, and still more preferably 10 or more. The upper limit of the number of ethylenically unsaturated double bonds that the polymer has at the end of the side chain is not particularly limited.

  As described above, the vinyl adhesive of the present invention contains a vinyl polymer having an ethylenically unsaturated double bond at the end of the side chain. The content of the vinyl polymer (nonvolatile content) having an ethylenically unsaturated double bond at the end of the side chain in the vinyl adhesive is preferably 5 to 80% by mass from the viewpoint of improving adhesiveness and weather resistance. More preferably, it is 5-60 mass%. The content of the vinyl polymer (nonvolatile component) in the vinyl adhesive can be adjusted by adjusting the amount of the organic solvent contained in the vinyl adhesive. Examples of the organic solvent include organic solvents used when preparing the polymer A, but the present invention is not limited by the type of the organic solvent.

  The non-volatile content of the vinyl adhesive may be composed only of a vinyl polymer having an ethylenically unsaturated double bond at the end of the side chain, but within the range not impairing the object of the present invention. For example, other polymers may be included.

  The vinyl adhesive of the present invention may contain a curing agent from the viewpoint of improving hydrolysis resistance and insulation resistance.

  Examples of the curing agent include (block) polyisocyanate compounds, epoxy resins, oxazoline group-containing resins, aminoplast resins, and the like, but the present invention is not limited to such examples. These curing agents may be used alone or in combination of two or more. Among the curing agents, at least one monomer selected from the group consisting of a (block) polyisocyanate compound, an epoxy resin, and an oxazoline group-containing resin is preferable from the viewpoint of curability and weather resistance. ) Polyisocyanate compounds are more preferred.

  The (block) polyisocyanate compound means a polyisocyanate compound and / or a block polyisocyanate compound.

  Examples of the polyisocyanate compound include compounds having at least two isocyanate groups in the molecule. Specific examples of the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, Polyisocyanates such as 1,3-bis (isocyanatomethyl) cyclohexane, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate; modified polyisocyanates such as adducts, burettes and isocyanurates of these polyisocyanates (Derivatives) and the like can be mentioned, but the present invention is not limited to such examples.

  The block polyisocyanate compound crosslinks the adhesive by heating, but has properties and adhesiveness that improve storage stability at room temperature. In addition, the block polyisocyanate compound is not only used in an environment actually used as a solar cell, but also in a case where an accelerated test is performed in a high-temperature and high-humidity atmosphere studied when evaluating a solar cell module. It is further excellent in adhesion to the filler used in the battery. The block polyisocyanate compound is usually one in which the isocyanate group of the polyisocyanate compound is blocked with a blocking agent. Examples of the blocking agent include ε-caprolactam, phenol, cresol, oxime, alcohol, and the like, but the present invention is not limited to such examples. Among the block polyisocyanate compounds, a non-yellowing polyisocyanate compound having no isocyanate group directly bonded to an aromatic ring is preferable from the viewpoint of preventing yellowing of the adhesive layer.

  (Block) Polyisocyanate compounds are, for example, manufactured by Sumika Bayer Urethane Co., Ltd., trade names: Death Module N3200, Death Module N3300, Death Module BL3175, Death Module N3400, Death Module N3600, Death Module VPLS2102, Sumidur BL3575MPA / X: manufactured by Asahi Kasei Chemicals Co., Ltd., trade names: Duranate E-402-90T, Duranate E-405-80T, Duranate TPA-B80E, Duranate MF-B60X, Duranate MF-K60X, etc. Can do.

  The amount of the (block) polyisocyanate compound is not particularly limited. For example, the amount of isocyanate groups in the (block) polyisocyanate compound per mole of hydroxyl group in the vinyl polymer is preferably 0.6 moles from the viewpoint of improving the hydrolysis resistance and insulation resistance of the adhesive layer. Above, more preferably 0.8 mol or more, from the viewpoint of preventing the adhesive layer from foaming or whitening due to the reaction of unreacted isocyanate groups with moisture in the air, preferably 1.4 It is less than mol, more preferably less than 1.2 mol.

  Examples of the epoxy resin include Japan Epoxy Resin Co., Ltd., trade names: Epicoat 828, Epicoat 1001X70, Epicoat 815; Asahi Denka Kogyo Co., Ltd., trade name: Adeka Resin EP-4100. Is not limited to such examples.

  Examples of the oxazoline group-containing resin include those manufactured by Nippon Shokubai Co., Ltd., trade names: Epocross K-2000 series, Epocross WS-500, Epocross WS-700, etc., but the present invention is limited to such examples. It is not something.

  An aminoplast resin is an addition condensate of a compound having an amino group such as melamine or guanamine with formaldehyde, and is also called an amino resin.

  Examples of aminoplast resins include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, fully alkyl methylated melamine, fully alkyl butylated melamine, fully alkyl isobutylated melamine, completely Melamine resins such as alkyl mixed etherified melamine, methylol group methylated melamine, imino group methylated melamine, methylol group mixed etherified melamine, imino group mixed etherified melamine; butylated benzoguanamine, methyl / ethyl mixed alkyl Benzoguanamine, methyl / butyl mixed alkylated benzoguanamine, guanamine resins such as butylated glycoluril, and the like, but the present invention is limited only to such examples. Not to.

  Aminoplast resins are commercially available, for example, as Mitsui Cytec Co., Ltd., trade names: Cymel 1128, Cymel 303, My Coat 506, Cymel 232, Cymel 235, Cymel 771, Cymel 325, Cymel 272, Cymel 254, Cymel 1170, and the like. Can be easily obtained.

  The amount of aminoplast resin is not particularly limited. The mass ratio of the solid content of the vinyl polymer and the aminoplast resin (vinyl polymer / aminoplast resin) is preferably 6/4 or more from the viewpoint of improving the adhesion, and the water resistance of the adhesive layer. From the viewpoint of improving decomposability and adhesion, the ratio is preferably 9/1 or less.

  Since the amount of the curing agent varies depending on the type of the curing agent and the like, it cannot be determined unconditionally. Usually, the adhesive per 100 parts by mass of the vinyl polymer having an ethylenically unsaturated double bond at the end of the side chain. From the viewpoint of hydrolysis resistance and insulation resistance of the agent layer, it is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and from the viewpoint of improving adhesiveness, preferably 60 parts by mass or less, more preferably 50 parts by mass or less, more preferably 30 parts by mass or less.

  The vinyl adhesive of the present invention can be cured under various curing conditions depending on its use and the type of curing agent used in the vinyl adhesive. The vinyl adhesive of the present invention can be used as a room temperature curing type, a heat curing type, an ultraviolet curing type or an electron beam curing type. Moreover, there is no limitation in particular in the quantity of a hardening | curing agent, its addition method, a dispersion method, etc. For example, when a vinyl polymer having an ethylenically unsaturated double bond at the end of the side chain has a plurality of hydroxyl groups in one molecule, the amount of the curing agent is adjusted according to the vinyl polymer. Or an addition method or a dispersion method may be selected.

  If necessary, the vinyl adhesive of the present invention may contain a curing catalyst for accelerating the crosslinking reaction between the vinyl polymer having an ethylenically unsaturated double bond at the end of the side chain and the curing agent. May be. Although there is no limitation in particular as a curing catalyst, For example, when using a (block) polyisocyanate compound, dibutyltin dilaurate, a tertiary amine, etc. are preferable. Further, when an aminoplast resin is used, an acidic or basic curing catalyst is preferable.

  The vinyl adhesive of the present invention may contain additives. Examples of the additive include additives generally used in resin compositions that form films and coating films. Specific examples of additives include leveling agents; inorganic fine particles such as colloidal silica and alumina sol; organic fine particles based on polymethyl methacrylate; antifoaming agents; anti-sagging agents; silane coupling agents; titanium white, complex oxide pigments Pigment dispersants; Phosphorus antioxidants, antioxidants such as phenolic antioxidants; viscosity modifiers; UV stabilizers; metal deactivators; Flame retardants; Reinforcers; Plasticizers; Lubricants; Rust preventives; Fluorescent brighteners; Organic and inorganic UV absorbers, inorganic heat absorbers; Organic and inorganic barriers Examples include flame retardants; organic and inorganic antistatic agents; and dehydrating agents such as methyl orthoformate, but the present invention is not limited to such examples.

  Note that the amounts of the curing catalyst, the solvent, and the additive vary depending on the type of the curing catalyst, and cannot be determined unconditionally. Therefore, it is preferable to appropriately adjust according to the properties required for the adhesive layer.

  In the present invention, from the viewpoint of improving adhesiveness, for example, a polyester-based resin, a modified polyolefin-based resin, an ethylene-vinyl acetate copolymer (EVA), a polyvinyl butyral (PVB), a silicone resin, A thermoplastic resin such as vinyl chloride resin, polyurethane, and amino group-containing resin, and a tackifier may be included.

  Examples of the polyester resin include Toyobo Co., Ltd., Byron (registered trademark) 103, 240, 500, GK110, GK640, etc .; Nippon Synthetic Chemical Industry Co., Ltd., Nichigo Polyester (registered trademark) TP- 220, TP-235, TP-236, TP-290, and the like are included, but the present invention is not limited to such examples.

  Examples of the modified olefin resin include Nippon Paper Chemicals Co., Ltd., Aurolen (registered trademark) 100, 200, 350, S-5189, etc .; Sanyo Chemical Industries, Ltd., Umex 1001, 1010, 2000, and the like. Although mentioned, this invention is not limited only to this illustration.

  Examples of the ethylene-vinyl acetate copolymer include Tosoh Corporation, Mersen (registered trademark) H-6051, H-6410, etc .; Sumitomo Chemical Co., Ltd., Sumitate (registered trademark) KA-31, KA. Although -42 etc. are mentioned, this invention is not limited only to this illustration.

  Examples of the polyvinyl butyral (PVB) include Kuraray Co., Ltd., Mowital (registered trademark) series B30H, B45M, and B60H. However, the present invention is not limited to such examples.

  Examples of the silicone resin include Shin-Etsu Chemical Co., Ltd., product numbers: KE-103 and KE-1013, but the present invention is not limited to such examples.

  Examples of the vinyl chloride resin include Sekisui Chemical Co., Ltd., trade name: Sekisui PVCTS, but the present invention is not limited to such examples.

  Examples of the polyurethane include DIC Bayer Polymer Co., Ltd., trade name: Desmopan DP6580A, but the present invention is not limited to such examples.

  Examples of the amino group-containing resin include those manufactured by Nippon Shokubai Co., Ltd., trade names: Poliment NK-350, NK-380, etc., but the present invention is not limited to such examples.

  Examples of the tackifier include rosin tackifiers; rosin ester tackifiers, terpene tackifiers, terpene phenol tackifiers, saturated hydrocarbon resins, coumarone tackifiers, Coumarone indene tackifier, styrene resin tackifier, xylene resin tackifier, phenol resin tackifier, petroleum resin tackifier, etc. Each agent may be used alone or in combination of two or more.

  Examples of the rosin-based tackifier include those manufactured by Harima Kasei Co., Ltd. and trade name: Harrier Star DS-90, but the present invention is not limited to such examples.

  Examples of the rosin ester tackifier include Arakawa Chemical Industries, Ltd., trade names: Pine Crystal KE-100, KE-311, and the like, but the present invention is limited to such examples. It is not a thing.

  Examples of the terpene tackifier include Yasuhara Chemical Co., Ltd., Clearon (registered trademark) M-115, P-115, and the like, but the present invention is not limited to such examples.

  Examples of the terpene phenol tackifier include Arakawa Chemical Industries, Ltd., trade name: Tanomaru 803L, and the like, but the present invention is not limited to such examples.

  Examples of the saturated hydrocarbon resin include Arakawa Chemical Industries, Ltd., trade names: Alcon P-90 and P-100, but the present invention is not limited to such examples.

  Examples of the styrene resin-based tackifier include Mitsui Chemicals, Inc., product number: FTR-6000, but the present invention is not limited to such examples.

  The amount of the tackifier may be appropriately adjusted according to the desired tackiness, and is not particularly limited, but is preferably 3 from the viewpoint of improving the tackiness to the adherend per 100 parts by mass of the vinyl polymer. From the viewpoint of suppressing the decrease in adhesive strength, it is preferably 200 parts by mass or less, and more preferably 150 parts by mass or less.

  As an adherend to which the vinyl adhesive of the present invention can be applied, for example, an adherend composed of a polymer obtained by polymerizing a monomer component containing a carboxylic acid vinyl ester, or polyester. Adherend made of polycarbonate, adherend made of fluororesin, adherend made of (meth) acrylic resin, etc., but the present invention is not limited to such examples. Absent. Among these adherends, polyester base materials and fluororesin base materials are preferable from the viewpoint of weather resistance and cost.

  The vinyl adhesive of this invention has the advantage that it can be used conveniently for the to-be-adhered body which consists of a polymer obtained by polymerizing the monomer component containing carboxylic acid vinyl ester. Examples of the vinyl carboxylate include vinyl acetate, vinyl monochloroacetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, and vinyl stearate. Saturated aliphatic carboxylic acid vinyl esters which may have a substituent such as halogen atoms such as vinyl pivalate and vinyl octylate; alicyclic carboxylic acid vinyl esters such as cyclohexyl vinyl carboxylate; divinyl adipate; Examples thereof include unsaturated aliphatic carboxylic acid vinyl esters such as (meth) vinyl acrylate, vinyl crotonate, and vinyl sorbate; and aromatic carboxylic acid vinyl esters such as vinyl benzoate and vinyl cinnamate. Limited to illustration only Not intended to be.

  When the vinyl adhesive of the present invention is used for an adherend composed of a polymer obtained by polymerizing a monomer component containing a carboxylic acid vinyl ester, the vinyl adhesive of the present invention and There is an advantage that the adherend can be firmly bonded. The reason why the vinyl adhesive of the present invention and the adherend can be firmly bonded in this way is not clear, but is probably at the end of the side chain contained in the vinyl adhesive of the present invention. This is considered to be based on the fact that the ethylenically unsaturated double bond of the vinyl polymer having an ethylenically unsaturated double bond is cleaved to form a chemical bond with the ester group of the adherend.

  Further, in the present invention, in addition to the above-mentioned adherend, in view of heat resistance, strength physical properties, electrical insulation, hydrolysis resistance, etc., polyolefin resin, polyamide resin, polyarylate resin, etc. An adherend made of a resin can be used.

  Examples of the form of the adherend include a molded body formed into a predetermined shape including a film, a plate, and the like, but the present invention is not limited to such an example. A suitable adherend in the present invention includes a film made of a resin containing an ethylene-vinyl acetate copolymer.

  Applications of adherends include, for example, solar cell encapsulants, agricultural resin films, construction civil engineering resin sheets, automotive exterior parts, food packaging paper, laminated materials with a paper-coated resin surface, artificial grass The present invention is not limited only to such illustrations.

  Moreover, the solar cell module backsheet in which the adhesive layer which consists of the said vinyl adhesive agent was formed by apply | coating the vinyl adhesive of this invention to the backsheet used for a solar cell module can be manufactured. . In the back sheet for a solar cell module on which the adhesive layer is formed, the surface on which the adhesive layer is formed is a surface to be bonded to the filler constituting the solar cell module. As a back sheet, what is normally used for a solar cell should just be used, and this invention is not limited by the kind of the said back sheet.

  Examples of the filler include ethylene-vinyl acetate copolymer (EVA), polyvinyl butyral, silicone resin, vinyl chloride resin, polyurethane, and the like, but the present invention is not limited to such examples. Among these, an ethylene-vinyl acetate copolymer (EVA) is preferable from the viewpoint of weather resistance and flame retardancy and from the viewpoint of increasing the adhesive strength. From the viewpoint of adhesion and weather resistance, the thickness after drying of the adhesive layer made of the vinyl adhesive of the present invention formed on the surface to be bonded to the filler constituting the solar cell module is preferably 0.00. 1 μm or more, more preferably 0.3 μm or more, and further preferably 1 μm or more. From the viewpoint of preventing embrittlement, it is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 30 μm or less, and even more preferably 10 μm or less. is there.

  FIG. 1 is a schematic cross-sectional view showing the configuration of a back sheet for a solar cell module in which the substrate is bonded with an adhesive. FIG. 1 has the simplest structure of a solar cell module backsheet. The two base materials 1 and 1 are bonded together with an adhesive 2. The base materials 1 and 1 may be base materials made of the same material, or may be base materials made of different materials.

  Examples of the adhesive 2 include the vinyl adhesive of the present invention, vinyl adhesives other than the vinyl adhesive of the present invention, polyester adhesives, polyurethane adhesives, and polycarbonate adhesives. The present invention is not limited to such examples. The adhesive 2 is preferably the vinyl adhesive of the present invention from the viewpoints of adhesiveness and weather resistance. An adhesive layer 4 made of the vinyl adhesive of the present invention is formed on one surface of the two substrates 1 and 1.

  The vinyl-based adhesive of the present invention is not only the environment actually used as a solar cell, but also when performing an accelerated test in a high-temperature and high-humidity atmosphere that is considered when evaluating a solar cell module. It has excellent adhesion and weather resistance to fillers used in solar cells, maintains electrical output characteristics, and exhibits excellent effects that it is difficult to cause poor appearance of the backsheet.

  FIG. 2 is a schematic cross-sectional view showing another embodiment when the barrier layer 3 is interposed in the solar cell module backsheet. In FIG. 2, adhesives 2 and 2 are applied to one surface of each of the two substrates 1 and 1, and an adhesive layer formed by the adhesives 2 and 2 on the two substrates 1 and 1 Two base materials 1 and 1 are integrated with a barrier layer 3 such as a gas barrier layer interposed therebetween, and the vinyl adhesive of the present invention is attached to the surface to be bonded to the filler constituting the solar cell module. An adhesive layer 4 made of is formed. Also in the solar cell module backsheet of this embodiment, since the adhesive layer 4 made of the vinyl adhesive of the present invention is formed, not only the environment actually used as a solar cell, but also the solar cell module Even when an accelerated test is performed in a high-temperature and high-humidity atmosphere, which is considered when evaluating, excellent adhesion and weather resistance to fillers used in solar cells, maintaining electrical output characteristics, An excellent effect is exhibited that it is difficult to cause poor appearance.

  Among the back sheet shown in FIG. 1 and the back sheet shown in FIG. 2, the back sheet shown in FIG. 1 is preferable from the viewpoint of cost reduction.

  Examples of the gas barrier layer 3 shown in FIG. 2 include a vapor deposition substrate on which an oxide such as a metal foil, a metal vapor deposition film, and an oxide vapor deposition film is vapor-deposited.

  Examples of the metal foil include an aluminum foil. As a metal vapor deposition film, metal vapor deposition films, such as an aluminum vapor deposition film which vapor-deposited metals, such as aluminum, to a polyester film and a polyolefin-type stretched film, for example are mentioned.

  Examples of the oxide vapor-deposited film include a film obtained by vapor-depositing aluminum oxide, silicon dioxide, tin oxide, magnesium oxide, indium oxide, and complex oxides thereof on a polyester film, and is transparent and has a gas barrier such as oxygen and water vapor. The thing which has property etc. are mentioned. In these, the film which vapor-deposited silicon dioxide on the polyester film and the film which vapor-deposited aluminum oxide on the polyester film are preferable.

  In the oxide vapor deposition film, the thickness of a suitable oxide vapor deposition layer varies depending on the type and composition of the oxide, but in general, from the viewpoint of forming a uniform oxide vapor deposition layer, preferably 5 nm or more, more preferably Is 10 nm or more, and is preferably 300 nm or less, more preferably 150 nm or less, from the viewpoint of imparting flexibility and preventing cracks from being generated by external stress.

  Examples of the method for forming an oxide deposition layer include a vacuum deposition method, a thin film formation method such as a sputtering method, an ion plating method, and a plasma vapor deposition method (CVD). However, the present invention is not limited to such examples.

  Before applying the vinyl adhesive of the present invention to an adherend, an organic peroxide is applied to the surface of the adherend from the viewpoint of improving the adhesive strength between the vinyl adhesive of the present invention and the adherend. It is preferably applied, or the organic peroxide is contained in the vinyl adhesive of the present invention, or the organic peroxide is preliminarily contained in the adherend. In particular, when an adherend composed of a polymer obtained by polymerizing a monomer component containing a carboxylic acid vinyl ester is used as the adherend, an organic peroxide is formed on the surface of the adherend. The adhesive strength between the vinyl adhesive of the present invention and the adherend can be improved by coating the organic peroxide or adding the organic peroxide to the vinyl adhesive of the present invention.

  Examples of the organic peroxide include diacyl peroxides such as dibenzoyl peroxide, diisobutyl peroxide, ditrimethoxyhexanoyl peroxide, dilauroyl peroxide, disuccinic acid peroxide, di (methylbenzoyl) peroxide, and diisononyl peroxide. Oxides; ketone peroxides such as methyl ethyl ketone peroxide, cyclohexane peroxide, acetylacetone peroxide; tert-butylperoxyneodecanoate, tert-butylperoxybenzoate, tert-butylperoxyneoheptanoate, tert-butylperoxide Oxypivalate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, te t-butylperoxyacetate, tert-butylperoxyisononanoate, tert-hexylperoxypivalate, tert-hexylperoxy-2-ethylhexanoate, tert-hexylperoxyisopropylmonocarbonate, tetramethylbutyl Alkyl peroxyesters such as peroxyethylhexanoate and 2,5-dimethyl-2,5-di (ethylhexanoylperoxy) hexanoate; di-n-propylperoxycarbonate, tert-butylperoxy-2-ethylhexyl Carbonate, diisopropylperoxycarbonate, di (4-tert-butylcyclohexyl) peroxycarbonate, di (2-ethylhexyl) peroxydicarbonate, disec-butylperoxydi -Bonate, tert-butylperoxy-2-ethylhexyl carbonate, tert-butylperoxyisopropyl carbonate, 1,6-bis (tert-butylperoxycarboxy) hexane, bis (4-tert-butylcyclohexyl) peroxydicarbonate, Peroxycarbonates such as tert-amylperoxy-2-ethylhexyl carbonate, di (sec-butyl) peroxydicarbonate; dicumyl peroxide, tert-butylperoxy-2-ethylhexyl carbonate, di (isopropyl) peroxycarbonate , Di (4-tert-butylcyclohexyl) peroxycarbonate, di (2-ethylhexyl) peroxydicarbonate, di (sec-butyl) peroxydicar Tert-butylperoxy-2-ethylhexyl carbonate, tert-butylperoxyisopropyl carbonate, 1,6-bis (tert-butylperoxycarboxy) hexane, bis (4-tert-butylcyclohexyl) peroxydicarbonate, Although dialkyl peroxides, such as tert-amyl peroxy-2-ethylhexyl carbonate, are mentioned, this invention is not limited only to this illustration. These organic peroxides may be used alone or in combination of two or more.

When applying the organic peroxide to the surface of the adherend, if necessary, the organic peroxide may be dissolved in an organic solvent to a desired concentration, and the resulting solution may be applied to the adherend. . The coating amount (solid content) of the organic peroxide on the adherend cannot be unconditionally determined because it varies depending on the type of the organic peroxide, but is usually about 0.01 to 1 g / m ^2. It is preferable that In addition, when an organic peroxide is contained in the vinyl adhesive of the present invention, the content of the organic peroxide in the vinyl adhesive of the present invention varies depending on the type of the organic peroxide, etc. Although it cannot be determined, it is usually preferably about 0.01 to 10% by mass.

  Further, from the viewpoint of stabilizing and improving the gas barrier property of the vinyl adhesive of the present invention, for example, an undercoat layer made of an acrylic polyol, an isocyanate compound and a silane compound may be provided on the adherend. An overcoat layer composed of a portion of polyvinyl alcohol or a completely saponified product and a silane compound may be provided on the deposited layer.

  The vinyl adhesive of the present invention is applied on the adherend by a method such as gravure coating, roll coating, bar coating, reverse coating, etc., so that the film thickness after drying is 0.1 to 20 μm, After bonding another substrate on the substrate by a method such as dry lamination, by forming an adhesive layer made of a vinyl-based adhesive on the surface to be bonded to the filler constituting the solar cell module, A solar cell module can be manufactured. At this time, the substrate may be subjected to a surface treatment for improving adhesiveness such as corona treatment, flame treatment, and plasma treatment, if necessary. For example, when a base material made of a fluororesin is used as the base material, it is preferable to perform plasma treatment or the like on the base material.

  The solar cell module in which the vinyl adhesive of the present invention is used performs not only the environment where it is actually used as a solar cell, but also an accelerated test in a high-temperature and high-humidity atmosphere that is considered when evaluating the solar cell module. Even in such a case, it has excellent adhesiveness and weather resistance to the filler used in the solar cell, maintains electric output characteristics, and has an excellent effect that it is difficult to cause poor appearance of the backsheet.

  The solar cell module in which the vinyl adhesive of the present invention is used can be easily configured by replacing the vinyl adhesive of the present invention as a back sheet in a generally used solar cell module, for example. Moreover, the solar cell of this invention can be easily comprised by replacing a solar cell module with the solar cell module of this invention in the solar cell generally used, for example.

  Therefore, the vinyl adhesive of the present invention can be suitably used as an adhesive for solar cell modules for bonding a back sheet and a filler used for solar cell modules. The back sheet in which the adhesive layer made of the vinyl adhesive of the present invention is formed on the surface bonded to the filler constituting the solar cell module can be suitably used as a back sheet for the solar cell module. The solar cell module having this solar cell module backsheet can be suitably used for solar cells.

  EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to this Example.

The following were used as the substrate or filler.
<Base material 1>
Teijin DuPont Films Co., Ltd., trade name: Tetron U298W [white polyethylene terephthalate (hereinafter referred to as PET) film]
<Substrate 2>
Product name: Tech Barrier (silicon dioxide vapor-deposited PET film), manufactured by Mitsubishi Plastics, Inc.
<Base material 3>
Product name: Lumirror X10S (heat-resistant oligomer PET film), manufactured by Toray Industries, Inc.
<Filler>
Product name: Fast cure, product number: RC02B (EVA sheet having a thickness of 400 μm), manufactured by Mitsui Chemicals Fabro Co., Ltd.

Production Example 1
200 g of butyl acetate was charged into a 1000 ml flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, and nitrogen gas was introduced and the butyl acetate was heated to 120 ° C. while stirring. A mixture of 307 g of cyclohexyl methacrylate, 17 g of glycidyl methacrylate, 3 g of butyl methacrylate and 15 g of tert-butylperoxy-2-ethylhexanoate as a polymerization initiator was added dropwise to the flask over 4 hours. Heated.

  Next, while blowing nitrogen gas and oxygen gas into the flask, the internal temperature of the flask was lowered to 110 ° C., 6 g of acrylic acid, 0.68 g of zinc octenoate as an esterification catalyst, and 4-hydroxy-2,2 as a polymerization inhibitor. A mixture of 0.06 g of 6,6-tetramethylpiperidine-1-oxyl was dropped into the flask over 30 minutes. After completion of dropping, the reaction was further continued for 6 hours to obtain a solution having a nonvolatile content of 61% by mass of the vinyl polymer having an acryloyl group at the end of the side chain. The resulting vinyl polymer (hereinafter referred to as polymer 1) had an acid value of 10 mgKOH / g and a weight average molecular weight of 45,000.

Production Example 2
Into a 1000 ml flask equipped with a stirrer, a dripping port, a thermometer, a cooling tube and a nitrogen gas inlet, 200 g of butyl acetate was charged, nitrogen gas was introduced, and butyl acetate was heated to about 120 ° C. while stirring. . A mixture of 306 g of cyclohexyl methacrylate, 18 g of acrylic acid, 3 g of butyl methacrylate and 15 g of tert-butylperoxy-2-ethylhexanoate as a polymerization initiator was dropped into the flask over 4 hours. Heated for hours.

  Next, while blowing nitrogen gas and oxygen gas into the flask, the internal temperature of the flask was lowered to 110 ° C., and 24 g of 2-vinyl-2-oxazoline was dropped into the flask over 30 minutes. After completion of the dropwise addition, the reaction was further continued for 6 hours to obtain a solution having a nonvolatile content of 62% by mass of the vinyl polymer having a vinyl group at the end of the side chain. The resulting vinyl polymer (hereinafter referred to as polymer 2) had an acid value of 10 mgKOH / g and a weight average molecular weight of 47,000.

Production Example 3
In a 500 milliliter flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, 60 g of ethyl acetate was charged, nitrogen gas was introduced, and the mixture was refluxed at about 80 ° C. In this flask, a mixture consisting of 89 g of cyclohexyl methacrylate, 2 g of 2-ethylhexyl acrylate, 9 g of 2-hydroxyethyl methacrylate, 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 40 g of ethyl acetate. Was continuously dropped into the flask over 2 hours. Furthermore, the solution whose content rate of the non volatile matter of a polymer is 50.1 mass% was obtained by heating for 3 hours. The weight average molecular weight of the obtained polymer was 120,000, and the hydroxyl value was 42 mgKOH / g.

In a 500 ml flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, 150 g of the polymer obtained above and 3 g of 2-acryloyloxyethyl isocyanate were charged, and the resulting mixture was added to the mixture. Stirring was carried out while blowing a mixed gas in which nitrogen gas and air were mixed at a volume ratio of 2: 1, and the internal temperature of the flask was raised to about 70 ° C. Thereafter, 0.03 g of dibutyltin dilaurate as a catalyst was added to the flask, reacted at 70 ° C. for 3 hours, and then subjected to a Fourier transform infrared spectrophotometer (FT-IR) to have a wave number of 2273 cm ⁻¹ derived from an isocyanate group. The disappearance of the peak was confirmed, and a solution having a non-volatile content of 49.8% by mass of the vinyl polymer having an acryloyl group at the end of the side chain was obtained. The obtained vinyl polymer (hereinafter referred to as polymer 3) had a weight average molecular weight of 110,000 and a hydroxyl value of 21 mgKOH / g.

Production Example 4
In a 500 milliliter flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, 60 g of ethyl acetate was charged, nitrogen gas was introduced, and the mixture was refluxed at about 80 ° C. This flask is composed of 93 g of cyclohexyl methacrylate, 2 g of 2-ethylhexyl acrylate, 5 g of 2-acryloyloxyethyl isocyanate, 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 40 g of ethyl acetate. The mixture was continuously dropped into the flask over 2 hours. By heating for another 3 hours, a solution having a non-volatile content of the polymer of 50.0% by mass was obtained. The weight average molecular weight of the obtained polymer was 130,000.

In a 500 milliliter flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, 150 g of the polymer obtained above and 5 g of 2-hydroxyethyl methacrylate were charged, and nitrogen was added to the resulting mixture. Stirring was carried out while blowing a mixed gas in which gas and air were mixed at a volume ratio of 2: 1, and the internal temperature of the flask was raised to about 70 ° C. Thereafter, 0.03 g of dibutyltin dilaurate as a catalyst was added to the flask, reacted at 70 ° C. for 3 hours, and then subjected to a Fourier transform infrared spectrophotometer (FT-IR) to have a wave number of 2273 cm ⁻¹ derived from an isocyanate group. The disappearance of the peak was confirmed, and a solution having a non-volatile content of 49.9% by mass of the vinyl polymer having an acryloyl group at the end of the side chain was obtained. The resulting vinyl polymer (hereinafter referred to as polymer 4) had a weight average molecular weight of 120,000.

Production Example 5
150 g of ethyl acetate was added to a four-necked flask equipped with a stirrer, a thermometer, a dropping line, and a nitrogen / air mixed gas introduction tube, and the temperature was raised to 50 ° C. After raising the temperature, a mixture of 2- (2-vinyloxyethoxy) ethyl acrylate [manufactured by Nippon Shokubai Co., Ltd., product number: VEEA] and 150 g of 2-ethylhexyl vinyl ether, a mixture of 25 g of ethyl acetate and 13 mg of phosphotungstic acid, Were dropped into the flask over 3 hours to polymerize. Thereafter, triethylamine was added into the flask to complete the polymerization reaction. The content of nonvolatile components of the vinyl polymer (hereinafter referred to as polymer 5) in the obtained reaction mixture was 53% by mass, and the weight average molecular weight of polymer 5 was 8,000.

Production Example 6
In a 500 milliliter flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, 60 g of ethyl acetate was charged, nitrogen gas was introduced, and the mixture was refluxed at about 80 ° C. In this flask, a mixture consisting of 89 g of cyclohexyl methacrylate, 2 g of 2-ethylhexyl acrylate, 9 g of 2-hydroxyethyl methacrylate, 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator and 40 g of ethyl acetate. Was continuously dropped into the flask over 2 hours. By further heating for 3 hours, a solution in which the nonvolatile content of the vinyl polymer was 50.1% by mass was obtained. The resulting vinyl polymer (hereinafter referred to as polymer 6) had a weight average molecular weight of 120,000 and a hydroxyl value of 42 mgKOH / g.

Example 1
Polymer 1 and poly 1 in a proportion of 2 parts by mass of polyisocyanate curing agent (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Desmodur N3200) per 100 parts by mass of the non-volatile content of polymer 1 obtained in Production Example 1. The adhesive 1 was obtained by putting an isocyanate hardening | curing agent in a container, and diluting with ethyl acetate so that a non volatile matter density | concentration might be 10 mass%.

Example 2
Polymer 2 and poly (polystyrene) in a proportion of 2 parts by mass of polyisocyanate curing agent (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Desmodur N3200) per 100 parts by mass of the nonvolatile content of polymer 2 obtained in Production Example 2. An isocyanate curing agent was put in a container, and diluted with ethyl acetate so that the nonvolatile content concentration was 10% by mass, whereby an adhesive 2 was obtained.

Example 3
Polymer 3 and poly (polystyrene) in a proportion of 4 parts by mass of polyisocyanate curing agent (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Desmodur N3200) per 100 parts by mass of the nonvolatile content of polymer 3 obtained in Production Example 3. An isocyanate curing agent was placed in a container, and diluted with ethyl acetate so that the nonvolatile content concentration was 10% by mass, whereby an adhesive 3 was obtained.

Example 4
The polymer 4 obtained in Production Example 4 was placed in a container, and diluted with ethyl acetate so that the nonvolatile content concentration was 10% by mass, whereby an adhesive 4 was obtained.

Example 5
The polymer 5 obtained in Production Example 5 was put in a container, and diluted with ethyl acetate so that the nonvolatile content concentration was 10% by mass, whereby an adhesive 5 was obtained.

Comparative Example 1
Polymer 4 and poly 4 in a proportion of 7 parts by mass of polyisocyanate curing agent (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Desmodur N3200) per 100 parts by mass of the nonvolatile content of polymer 4 obtained in Production Example 6. The adhesive 6 was obtained by putting an isocyanate hardening | curing agent in a container and diluting with ethyl acetate until the non volatile matter density | concentration became 10 mass%.

Experimental example (Preparation of back sheet for solar cell module)
As shown in Table 1, any one of the adhesives 1 to 6 was used, and the adhesive was applied to the substrate 1 so that the coating amount after drying was 1 g / m ² and dried at 100 ° C. for 1 minute. By doing so, an adhesive layer was formed. Thereafter, in order from the filler side to the base materials 1 to 3, the surface of the base material 1 on which the adhesive layer is not formed is overlapped with the adhesive X, so that the base material 1 / adhesive X / base material 2 By laminating in the order of / adhesive X / base material 3 and laminating by a dry laminating method, a laminate was obtained. The obtained laminated body was cured at 50 ° C. for 5 days to produce a back sheet for a solar cell module.

As the adhesive X, a main component of a polyester-based adhesive (manufactured by Dainippon Ink and Chemicals, product number: LX703VL) and a polyisocyanate curing agent (manufactured by Dainippon Ink and Chemicals, product number: KE90). The coating amount after drying of the adhesive X was adjusted to 10 g / m ² .

  Next, the physical properties of the solar cell module backsheet obtained above were examined by the following methods. The results are shown in Table 1.

[Blocking resistance]
The back sheet for a solar cell module obtained above was cut into a width of 5 cm and a length of 20 cm, the surface on which the adhesive layer surface of the cut sheet was formed, and an untreated heat-resistant oligomer PET film [manufactured by Toray Industries, Inc. , Product name: Lumirror X10S] (hereinafter referred to as untreated PET film), a weight of 5 kg is placed on the resulting laminate, and the laminate is placed in an oven at a temperature of 40 ° C. For 24 hours. Then, the laminated body was taken out from the oven, the adhesive layer of the laminated body was visually observed, and blocking resistance was evaluated based on the following evaluation criteria.

(Evaluation criteria)
○: The adhesive layer is not transferred to the untreated PET film (passed).
X: The adhesive layer is transferred to the untreated PET film (failed).

〔Adhesiveness〕
One sheet obtained by cutting the back sheet obtained above to a width of 60 mm and a length of 200 mm, and an EVA sheet (manufactured by Mitsui Chemicals Fabro Co., Ltd., product number: RC02B, thickness: 400 μm) to a width of 60 mm and a length of 90 mm One sheet cut and tempered glass (width: 10 mm, length: 100 mm, thickness: 3 mm) were prepared.

The back sheet / EVA sheet / tempered glass plate were laminated in this order so that the surface of the back sheet for solar cell module to be evaluated was in contact with the EVA sheet. The obtained laminate was evacuated under a pressure of 5 N / cm ² at a temperature of 150 ° C. for 3 minutes, stored in an oven heated to 150 ° C. for 8 minutes, and the crosslinking reaction was allowed to proceed. Obtained.

  In an atmosphere where the temperature is 23 ° C. and the relative humidity is 65%, the tempered glass plate and EVA sheet of the unbonded portion of the sample obtained above are respectively attached to the upper and lower clips of the autograph (manufactured by Shimadzu Corporation). The peeling strength (initial value) at a crosshead speed of 300 mm / min with a width of 25 mm was measured by sandwiching and 180-degree peeling method, and the adhesiveness was evaluated based on the following evaluation criteria.

  Furthermore, after leaving a sample different from the sample whose peel strength was measured in an atmosphere of 85 ° C. and 85% relative humidity for 1000 hours or 2000 hours, the peel strength was measured under the same conditions as described above. The adhesiveness was evaluated based on the evaluation criteria.

(Evaluation criteria)
EX: Peel strength of 80 N / 10 mm or more (remarkably excellent adhesion)
A: Peel strength is 40 N / 10 mm or more and less than 80 N / 10 mm (excellent adhesiveness)
B: Peel strength is 20 N / 10 mm or more and less than 40 N / 10 mm (adhesiveness is good)
C: Peel strength is 10 N / 10 mm or more and less than 20 N / 10 mm (adhesiveness is slightly good)
D: Peel strength is less than 10 N / 10 mm (adhesion is poor) (failed)

[Weather resistance, electrical output characteristics and appearance of back sheet]
(1) Weather resistance An A4 size EVA sheet (made by Mitsui Chemicals Fabro Co., Ltd., product number: RC02B, thickness: 400 μm) on the A4 size tempered glass plate as a filler for a solar cell module. After placing the solar cells made of polycrystalline silicon sandwiched between the layers, the back sheet obtained above was further provided thereon so that the adhesive layer was in contact with the EVA sheet, thereby obtaining a laminate. .

Next, each laminate obtained above was evacuated under a pressure of 5 N / cm ² at a temperature of 150 ° C. for 3 minutes, and then stored in an oven heated to 150 ° C. for 8 minutes to carry out a crosslinking reaction. Proceeded. Then, the sample was produced by performing a frame with an aluminum frame.

The sample is irradiated with ultraviolet rays for 100 hours or 150 hours at 100 mW / cm ² at a temperature of 60 ° C. and a relative humidity of 50% using an i-super UV tester (manufactured by Iwasaki Electric Co., Ltd., product number: SUV-W151). Thus, a weather resistance acceleration test was conducted.

Next, the peel strength at a crosshead speed of 300 mm / min was measured by a 180 degree peel method using an autograph (manufactured by Shimadzu Corporation), and the formula:
[Retention rate (%)]
= [(Peel strength after accelerated test) ÷ (Peel strength before accelerated test)] × 100
Based on the above, the retention rate was determined, and the weather resistance was evaluated based on the following evaluation criteria.

(Evaluation criteria)
○: Retention rate is 50% or more (pass)
X: Retention rate is less than 50% (failed)

(2) Electrical output characteristics The maximum output of the sample before and after the weather resistance promotion test was measured according to JIS C8913, and the formula:
[Change rate of maximum output (%)]
= [(Maximum output after accelerated test) / (Maximum output before accelerated test)] x 100
The change rate of the maximum output was obtained based on the above, and the electrical output characteristics were evaluated based on the following evaluation criteria.

(Evaluation criteria)
○: Change rate of maximum output is 95% or more (pass)
Δ: Change rate of maximum output is 90% or more and less than 95% (pass)
×: Change rate of maximum output is less than 90% (failed)

(3) Appearance of Back Sheet The sample was observed visually for the appearance of the back sheet of the sample after the weather resistance promotion test, and evaluated based on the following evaluation criteria.

(Evaluation criteria)
○: No abnormality (pass)
X: There is a float between the EVA sheet and the base material (failed)

  From the results shown in Table 1, all of the vinyl adhesives obtained in each example are excellent in blocking resistance, and as a solar cell in comparison with the vinyl adhesive obtained in Comparative Example 1. Adhesion and weather resistance to fillers used in solar cells, even in the case of accelerated tests in hot and humid atmospheres that are considered when evaluating solar cell modules as well as the actual usage environment It can be seen that it has excellent properties, maintains electrical output characteristics, and is excellent in the appearance of the backsheet. Therefore, it can be seen that any of the vinyl adhesives obtained in each Example can be suitably used for solar cell modules and solar cells.

1: Base material 2: Adhesive 3: Barrier layer 4: Adhesive layer

Claims (5)

  A vinyl adhesive containing a vinyl polymer, wherein the vinyl polymer is a vinyl polymer having an ethylenically unsaturated double bond at the end of a side chain. .   The vinyl polymer having an ethylenically unsaturated double bond at the end of the side chain contains at least one monomer selected from the group consisting of an epoxy group-containing monomer and an oxazoline group-containing monomer. Monomer containing a vinyl polymer obtained by reacting a polymer obtained by polymerizing monomer components with a monomer having a carboxyl group and / or a hydroxyl group, and a monomer having a carboxyl group and / or a hydroxyl group A vinyl polymer obtained by reacting a polymer obtained by polymerizing a body component with at least one monomer selected from the group consisting of an epoxy group-containing monomer and an oxazoline group-containing monomer, a carboxyl group And / or a vinyl polymer obtained by reacting a monomer component containing a monomer having a hydroxyl group with an isocyanate group-containing monomer, an isocyanate A vinyl polymer obtained by reacting a monomer component containing a group-containing monomer with a monomer having a carboxyl group and / or a hydroxyl group, and (meth) acrylic acid (vinyl chloride). 2. The vinyl adhesive according to claim 1, which is at least one vinyl polymer selected from the group consisting of vinyl polymers obtained by polymerizing a monomer component containing (roxyalkoxy) alkyl.   A back sheet for a solar cell module, wherein an adhesive layer made of the vinyl adhesive according to claim 1 or 2 is formed.   A solar cell module comprising the back sheet for a solar cell module according to claim 3.   A solar cell comprising the solar cell module according to claim 4.