TW201229177A - Active energy ray curable adhesive, and back protective sheet for solar cell - Google Patents

Abstract

Provided is an active energy ray curable adhesive having excellent properties of adhesive force and resistance to heat and humidity between a sheet-like member, high quality and yield, and high producibility. The active energy ray curable adhesive of the present invention comprises a (meth)acryloyl-containing urethane resin (D) and an epoxy resin (E), wherein resin (D) is obtained from reacting a polyol (A) comprising an essential polyether polyol (A1) without (meth)acryloyl group having a number average molecular weight from 500 to 5000, with a polyol (B) having a (meth)acryloyl group and 2 or more hydroxyl groups, and a polyisocyanate component (C).

Description

201229177 VI. Description of the Invention: [Technical Field] The present invention relates to an active energy ray-curable adhesive containing an amino phthalate resin having a (fluorenyl) acrylonitrile group. Further, the present invention relates to a back surface protective sheet for a solar cell comprising the above active energy ray-curable adhesive. Further, the present invention relates to a urethane resin having a (fluorenyl) acrylonitrile group which is suitable for use as an adhesive for inks, coatings, back protective sheets for solar cells, and the like. [Prior Art] In recent years, solar cells have been used as a source of clean energy without environmental pollution. However, they have been focused on practical energy resources as a useful energy resource. The solar cell element provided in the solar cell is provided on the surface opposite to the incident surface of the sunlight to protect the solar power; and the element is (4) the solar power back surface. In order to achieve the properties such as fullness, hydrothermal gas barrier properties, electrical insulation properties, mechanical properties, sealing work 4, etc., the solar cell back protective sheet is usually laminated with several types of sheet-like members. The patent document has been proposed in the patent document; the hydrolyzable polyglycolic acid g is used as a binder for the production of tablets. Further, Patent Document 2 discloses an amine-based (tetra) resin, and a solar cell element in the sunlight is a sheet-like shape of a surface protective sheet for a solar cell module. In the case of the active energy ray-curable resin composition containing an untwisted base, it is suitable for a primer or the like. In addition, about the polyfilament (four) lyophile, because of its Wei characteristics 4/53

S 201229177 has been widely used in various fields such as paints, adhesives, amine-based foams, fiber products, artificial leather, and the like, and has been proposed in various fields (for example, Patent Document 4). 5). [Advanced Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2-253463 (Patent Document 3). [Patent Document 4] Japanese Patent Laid-Open Publication No. SHO 57-8218 [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. In the case of the back protective sheet, after the sheet-like members are stacked, there is a step of winding the strips into a roll. In the wire, the hardening reaction of the polyamine-adhesive agent has a problem that the hard layer of the adhesive layer in the laminated body which is wound into a roll is likely to be insufficient, and the sheet-like member is easily deformed. Due to the deformation of the 'four-piece member, the incidence of defective products is increased, and the yield is deteriorated. 0 In order to sufficiently harden the polyurethane-based adhesive, it is necessary to have three values and mature in the warehouse. day. Therefore, there is also a problem that the production cost S such as the electricity cost for maintaining the temperature of the warehouse is reduced. And the isocyanate compound of the hardener not only reacts with the main agent, but also reacts with the water of the air towel, and there is a shout, that is, there is a reaction with water. The decarboxylation reaction occurs, and after 5/53 201229177 ==:::, bubbles appear in the adhesive layer, resulting in an appearance, and the composition of the adhesive for the back protective sheet for the battery is more ==. The active energy described in 3—the seed is thin and the finisher' is provided for the purpose of providing excellent resistance to life, high quality, good yield, energy-curing adhesive with back protective sheet, and solar cell [to solve Means for the subject] The active energy ray-curable strait of the present invention comprises an amino carboxylic acid vinegar resin (D) and an epoxy resin (6) having a methyl propylene group, wherein The urethane resin (9) is a polyhydric alcohol component (VIII) having a (meth)acrylic acid group having a number average molecular weight of 500 to 5 mm, an alcohol (4), and having no (meth)acrylic group. A polyol component (8) having two or more radicals is reacted with the polyisocyanate g|component (c). Preferable examples of the polyether polyol (A1) having a number average molecular weight of 500 to 5 and ruthenium are as shown in the following general formula (1). General formula (1): ho(-ro) „-h (wherein R may have a hydrocarbon group having 3 to 8 carbon atoms of a side chain substituent, and n represents an arbitrary integer. As a side chain substituent, a The urethane resin (D) preferably has a preferred number average molecular weight of 5,0 Å to 15 Å, and the amine group of the aforementioned urethane resin (D) The preferred range of the formate bond equivalent is 6/53 201229177. The range is 200 to 3,000. The preferred range of the above-mentioned base propylene oxime equivalent in the urethane resin is 500 to 40,000. The preferred range of the number average molecular weight is 450 to 5,000. The preferred content of the amino phthalate resin (D) is 50 to 85% by weight based on the solid content of the active energy ray-curable adhesive. The preferred content of the epoxy resin (E) is 5 to 40% by weight. As a preferred example of the polyol component (B), those having two or more (meth) acrylonitrile groups may be mentioned. Preferable examples of the polyol component (B) include (meth)acrylic acid added to an epoxy group of a compound having two or more oxy groups. Further, the back surface protective sheet for a solar cell of the present invention protects a solar cell back surface protective sheet provided on a surface of the solar cell element of the solar cell opposite to the solar light emitting surface, and has a sheet shape of 2 or more. And a laminate layer of the member, and an adhesive layer formed by the active energy ray-curable adhesive formed by the active energy ray-curable adhesive of the above-described aspect. Preferably, the sheet-like member constituting the layered body has a water-falling gas barrier layer. The water vapor barrier layer is preferably selected from the group consisting of gold (4), a plastic film with a metal oxide layer, and a non-gold-viewing layer. The group of the plastic film is formed. The preferred range of the glass transition of the active energy ray hardening treatment is _5 〇 30 ° C. [Effect of the invention] 7/53 201229177 The present invention provides An active energy ray-curable connection containing a (meth) acrylamide-based urethane resin (D) with excellent wettability, productivity, quality, and excellent adhesion between members and good yield The present invention has an excellent effect. [Embodiment] [Embodiment for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be described in detail. Fan Cai, for the use of "(meth) propylene" for certain compounds, the compound contains the compound when "(曱) propylene" is called "propylene", and Any of the compounds in the case of "methacrylofluorene". Further, "(meth)(tetra)acid" soil and "(mercapto)acrylate" are also defined in the same manner. Further, the description of "arbitrary number A to arbitrary number B" in the present specification means the range of the number A and the number from the number a to the number B and less than the number B. Further, the ratios of the members in the drawings and the like are for convenience of explanation and are not limited in any way. The urethane resin (D) having a (meth)acryl fluorenyl group of the present invention (hereinafter also referred to as "amino phthalate resin (D)") may be an average molecular stem of the necessary number. 500~5, a polyhydric alcohol (A) having no (fluorenyl) acrylonitrile group, a polyhydric alcohol having a (fluorenyl) acrylonitrile group and having two or more hydroxyl groups The component (B) is obtained by reacting with the polyisocyanate component (c). Further, the active energy ray-curable adhesive of the present invention comprises the above-described amino phthalate resin having a (meth) acryl oxime group and an epoxy resin (E). Further, the back surface of the solar cell of the present invention Protective film protection setting 8/53 201229177 The surface of the solar cell element on the opposite side of the solar radiation surface, which has at least 2 in the shape of the slab-shaped member of the laminated body The active energy ray-curable adhesive 2: two, using the previously completed adhesive layer. The active fraction of the heart is set at the hardening of the wire. The amount of the amine-based ester resin (D) is particularly preferably _. By making the amount even higher, it is possible to suppress the swelling caused by the water vapor caused by the insufficient cohesive force of the hardening treatment in the heat and humidity resistance test, and to maintain the adhesion between the pieces. Moreover, by making the amount of the flat amount less than 150,000, it is possible to take a knives and go to the Geng knives to increase the smear and make the smear more favorable, and thus the solubility of the ship and the active energy ray may deteriorate. . Further, when the active energy ray hardener is replenished to the sheet-like member, the wettability of the next member can be favorably maintained, and as a result, the connection between the sheet-like members can be more effectively maintained, and the number of the present specification is increased. The value of the average molecular weight is a value obtained by using GPC (gel permeation chromatography) "Hpc__" manufactured by Tosoh Corporation and using tetrachloroethylene as solvent "in terms of standard polystyrene. The amine phthalate resin (D) is preferably from 500 to 40,000, preferably from the point of the adhesion between the sheet-like members and the moist heat. _〇~3〇, _. From the viewpoint of the adhesion between the more excellent sheet-like members and the moist heat resistance, it is preferably 130 to 20, _, more preferably 2, _~1 〇, _ 'extra is 2, 4 〇 〇~8二': The so-called (indenyl) propyl group equivalent is the number average molecular weight of the parent (meth) propylene base in the amino phthalic acid lysate molecule 9/53 201229177. In other words, the (meth) propylene oxime equivalent of jin = is obtained by dividing the number average molecular weight of the urethane resin (〇) by the molecule of the lysine lysate (D) ( The value obtained by the average enthalpy of the number of methyl propylene groups. By setting the (meth)acrylonitrile group equivalent to 5 Å or more, it is possible to effectively suppress the decrease in the force between the sheet-like members due to the hardening shrinkage at the time of f-twisting. In addition, by setting the (meth) propylene base equivalent to (8) 下, it is possible to suppress the paste which is caused by the insufficient cohesive force of the adhesive layer which is completed by the hardening treatment during the heat and humidity resistance test, and The adhesion between the sheet members can be maintained more satisfactorily. The urethane resin (D) may have a terminal end group, an isocyanate end, a saturated hydrocarbon group containing an ethylenically unsaturated group, an unsaturated hydrocarbon group, and the like. If the amine (iv) vinegar resin (9) towel has an isocyanide group, the age of the heterogeneous group reacts with the moisture in the gas and the viscosity increases and gels. Therefore, from the viewpoint of more effectively improving the stability over time of the amino phthalate resin, it is preferred that the terminal or side chain does not have an isocyanate group. In order to make the terminal of the amino phthalate resin (D) a hydroxyl group, for example, a polyol component (A) having no (fluorenyl) acrylonitrile group, a (meth) acryl fluorenyl group, and having two or more hydroxyl groups. The polyol component (B) and the polyisocyanate group (C)' may be reacted under conditions in which the isocyanate group is relatively small. The total of the hydroxyl groups in the polyol components (A) and (B) is relatively lower than the isocyanic acid of the polyisocyanate component oxime. The reaction is carried out under the condition that the hydroxy group has a different acid hydroxy group. The resin is further reacted with the above-mentioned isocyanato group, for example, with a compound having a trans group or an amine group, whereby a terminal-saturated hydrocarbon group or an unsaturated hydrocarbon group can be obtained. Further, the 'amino phthalate resin (D) is preferably from 2 〇〇 to 3 in terms of the adhesion between the sheet-like members and the heat and humidity resistance of 10/53 201229177. 〇, preferably 250~2,000, more preferably 3〇〇~15〇〇, especially good 35〇~. Here, the amino acid carboxylic acid S is a number average molecular weight per one of the amino phthalic acid lysates in the bond equivalent amine phthalic acid styling resin (9). In other words, 'so-called? The carboxylic acid ketone bond equivalent is obtained by dividing the number average molecular I of the amino phthalic acid resin (9) by the number of monthly urethane bonds contained in one molecule of the urethane resin (D). The value obtained. By setting the bond equivalent of the carbamic acid guanidine to a finer or more, it is possible to suppress the cohesive force of the adhesive layer which is completed by the curable adhesive layer or the hardening treatment, and to form the adhesive layer which is completed in the curable adhesive layer or the hardening treatment. At the time of the upper layer-like member (10), the agent layer has good wettability to the sheet-like member, and can be effectively protected, and the force is further improved by using the amine-based citric acid g as a surface equivalent. Even after the <wet heat test, a decrease in the adhesion force between the members can be caused. In addition, the term "hard "selenium" refers to the adhesive layer before the active energy ray irradiation, and the so-called "adhesive layer" refers to the hard acid after the active energy. The number of atoms in the main chain f frame is preferably 3 or more, and the second is 5 or more. The number of atoms in the main chain skeleton between the amino-A-bonds is 3, which can be caused by agglomeration of the amino acid valerate bond: the hard bond segment due to cross-linking, which is protected in the adhesive film. The cohesive force is better exhibited in each of the segmented towels. The result is good, and the swelling caused by water vapor can be suppressed, and the adhesion between the sheet-like members can be more retained. Average: The formation of the amine-based resin (d), the necessary amount is 500~5, the polysinomeric alcohol (A1) of _ does not have (meth) propylene 11/53 201229177 The alcohol component (A) must be a polyhydric alcohol (A1) in an amount of 500 to 5, _, and can be used in combination with the urethane resin (D). ^ (4) polyol (4)), (4) known as polyether polyol (Α1) can be exemplified by ethylene glycol, propylene glycol, propylene glycol: dipropylene glycol, Trimethylolpropane, glycerol or the like; alcohol; B using an organic catalyst, a cationic catalyst, or more than one or more of the epoxy ring-opening polymerization. The materials for synthesizing the polysquaria polyol (Α1) can be used independently, and the materials can be used in combination of two or more kinds. As an epoxy institute, the carbon number of 3 or more can be exemplified by epoxy propylene, U. epoxide, 2, 3. epoxide = ::: m, tetrahydro butterfly' Separate two: 2 = base; propylene glycol, "base-1,3. propylene glycol, - sub-8 壬-alcohol, di-A, P _ polyvalent alcohol or a mixture of these are taken off: three These may be used alone or in combination of two or more. It is preferable to use two or more kinds of thirst resistance: the polyether polyol which is not in the formula (1) has a good general formula (1): Η〇 (cut λ_Η '丁-酉(wherein R can also have a side chain substituent representing any (four) number. Doing & ^ 8 minus, η by using a number of flat ^, ethyl, etc.) followed by a layer of agent or hardened Prevents hardenability from '_化_=:== 12/53 201229177

A polyhydric alcohol such as a diol having an alicyclic structure such as hydrogen bisphenol A or hydrogenated bisphenol F, or a di-L-methyl group having a carboxyl group such as dihydroxymethylbutyric acid, pentaerythritol or propylene glycol. The component (A2) may be used singly or in combination of two or more. When a diol component having an alicyclic structure is used, although the wet heat property is excellent at the subsequent strength, the initial adhesive strength (the adhesive strength before the wet heat resistance test) tends to decrease. Therefore, an appropriate alicyclic structure can be introduced as required. When the polyol components (A1) and (A2) are used in combination, the ratio of the polyol component (A2) other than (A1) to the total amount thereof is preferably 40% by weight or less based on the total polyol component (A). It is preferably 30% by weight or less, more preferably 20% by weight or less. In other words, the proportion of the polyol component (A1) is preferably 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more. By setting the ratio of (A1) to 6% by weight or more, the effect of the adhesion to the polyether polyol skeleton can be favorably maintained, and the excellent moist heat resistance and excellent adhesion can be more effectively achieved. Further, as (A2), when the low molecular weight 13/53 201229177 alcohol day is used, by increasing the ratio of (A1), the amine phthalate bond equivalent can be increased, the solubility deterioration can be suppressed, and the hardening can be suppressed. The cohesive force of the adhesive layer or the adhesive layer completed by the hardening treatment becomes large. Further, when the sheet-like member is laminated on the adhesive layer or the adhesive layer which is subjected to the curing treatment, the wettability of the adhesive layer to the sheet-like member can be favorably maintained, and the contact force can be more effectively maintained. The polyol component (B) having a (meth) acrylonitrile group has two or more hydroxyl groups. By using the polyol component (B), not only a (mercapto) acryl group can be introduced into the main chain end of the amino phthalate resin (D), but also a (meth) acryl fluorenyl group can be introduced into the side chain. By controlling the compositions of the polyol components (A)), (A2) and the polyol component (B), the amount of introduction of the (meth) acrylonitrile group can be controlled. When the polyterpene alcohol component (B) is a compound having two or more (fluorenyl) acrylonitrile groups, even a high molecular weight urethane resin can be efficiently incorporated into a (meth) acrylonitrile group. Therefore, it has an advantage that the active energy ray hardenability can be improved and the moist heat resistance can be improved. The polyol component (B) having a (meth) acrylonitrile group and two or more hydroxyl groups in one molecule may be exemplified by a compound having two or more epoxy groups.

The epoxy group is compounded with a (methyl)-propyl compound (called glycerol mono-W-based) acrylic acid, a trimethyl-methyl-b-monomethyl (meth) acrylate vinegar, and a tri-methyl propyl group. Monomer (meth)acrylic acid vinegar, pentaerythritol mono(meth)acrylic acid vinegar, quaternary tetradecyl-(f-)acrylic acid vinegar, dipentaerythritol tetrakis(meth)acrylic acid vinegar, dipentaerythritol tris(methyl) Acrylic is intended to be used alone or in combination. = (meth)acrylic acid compound (B1) is added to the epoxy group of the compound having two or more epoxy groups, and, for example, (meth)acrylic acid addition of propylene glycol dicondensate oil scale is mentioned. ,], 6. hexanediol diglycidyl 14/53 201229177 base) acrylic acid adduct, ethylene glycol diglycidyl ether (mercapto) acrylic acid adduct, 1,4-butanediol diglycidyl (meth)acrylic acid adduct of ether, (meth)acrylic acid adduct of pentanediol diglycidyl ether, (meth)acrylic acid adduct of 6-hexanediol diglycidyl ether, hydrazine , (meth)acrylic acid adduct of 9-decanediol 'diglycidyl ether, (meth)acrylic acid adduct of neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether An acrylic acid adduct, a (meth)acrylic acid adduct of hydrogenated bisphenol A diglycidyl ether, a (mercapto)acrylic acid adduct of propylene glycol diglycidyl ether, and the like. The polyisocyanate component (C) used in the present invention may, for example, be 2?-indole diisocyanate, 2,6-toluene diisocyanate, benzodiisocyanate, dimethane diisocyanate or isophorone diisocyanate. , a monomer of the selected isocyanate compound such as 5-naphthalene diisocyanide owed to Sa, hexyl diisocyanate, hydrogenated diphenylnonane diisocyanate, or at least one or more selected isocyanate compounds The adduct, the digestive gland, and the isocyanuric acid compound may be used singly or in combination of two or more kinds. From the viewpoint of weather resistance, the diisocyanate component is preferably an alicyclic-isocyanate. The urethane resin (1) having a (fluorenyl) acrylonitrile group of the present invention can be produced by reacting a raw material in the absence of a solvent, or can be produced by reacting in an organic solvent. As the organic solvent, a ketone compound such as acetone, methyl ethyl ketone, methyl isobutyl ketone or the like; methyl acetate, ethyl acetate, butyl acetate, citric acid, and methoxyethyl acetate can be used. An ester compound such as diethyl ether or diol dimethyl ether; an aromatic compound such as toluene or xylene; an aliphatic compound such as pentane or hexane; dioxane; Various solvents such as a halogenated hydrocarbon compound such as chlorine gas. 15/53 201229177, y base A __ (D), if necessary, plus catalyst. For example, dibutyltin dilaurate can be used, dioctyltin dilaurate, - butyl succinate - butyl tin 1-2, diol, 丨 '8 _ _ _ bicyclo (10)) decene quinone dinitrogen Miscellaneous = (=, 〇) decene · 5,6-dibutylamino oxadiazolidine (10)) octa- _ such a tertiary amine; such as triethanolamine-like reaction can be used alone or together 2 or more types. And the moon god temple. Next, the active energy ray-curable adhesive of the present invention will be described. The active energy ray-curable adhesive containing the above-mentioned amine-based oxime resin 1) and epoxy resin (Ε). -2 In the invention of the Lang Yi (6), can be like double age 双 type double brew / day / double FF oxygen resin, double # S type epoxy resin, evolution tf epoxy resin, hydrogenated double age A ring Oxygen resin, double-type epoxy dimethyl diene age-old epoxy resin, age _ varnish type epoxy resin, - cone lacquer type epoxy resin, bromination _ secret varnish type epoxy tree A _ varnish type Epoxy resin, tri-phenyl phenyl-form-type ring ^ Qianji B (tetra) epoxy resin, containing naphthalene bone _ system _ =, 5% oxygen resin, containing dicyclopentadiene skeleton age secret varnish type jujube 2 fat缩 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Glycine amines such as epoxide tree 曰 'N, N, N', N', glycerol dimethyl phenyl diamine, or glycerol, (mercapto) propylene _ and compounds having ethylenic unsaturated double bonds An epoxy compound such as a copolymer or the like. These may be used alone or in combination, and the resin (E) may be contained in the active energy ray-curable adhesive, 16/53 201229177, in the heat and humidity resistance test due to the amino carboxylic acid group and the epoxy group. The reaction can suppress the subsequent suppression of the subsequent suppression of the force.曰 'Knife 1 is lowered, and the nature of the property / nitrite _ (9) is dissolved by ~5, _ double number average molecular weight epoxy resin, more preferably ~ 5, _ = ί ^ 5,000 Type _ ~ side of the double _ epoxy resin. For the sake of difficulty, it is particularly preferable that the molecular weight is 450 or more, and the number of the hardening adhesive and other components can be suppressed. The compound of the (meth) fluorenyl group other than the active energy ray-curable adhesive agent of the present invention can be effectively prevented. In the present invention, a compound having a group having a quaternary amount of a urethane sulphate is included, for example, a relatively low-grade prepolymer and a m-acid cool monomer, or a molecular weight to some extent. The (meth)acrylic acid sulphuric acid monomer in the lower two sub-groups can be exemplified by (methicillin), and the (meth)acrylic acid (meth)acrylic acid, (mercapto) acrylic acid. And monofunctional (methyl) propylene vinegar monomer such as acryl-based keline; lysine, 禾'〇/壬Ϊ* alcohol di(meth) acrylate vinegar, bispan A bis(fluorenyl) Acrylic acid ^: "Four drunk three (methic acid vinegar, ginseng ((mercapto) propylene oxyethyl) cyanate §, and dipentaerythritol hexa(meth) acrylate _ and other polyfunctional IT I) Acrylate monomer 17/53 201229177 As a prepolymer and a polymer, for example, poly (meth) acrylate vinegar, polyamino decanoic acid _ (曱 基, poly epoxy (methyl) a radically polymerizable prepolymer or a polymer having a (meth) acrylonitrile group such as acrylic acid vinegar or (mercapto)acrylic acid maleic acid modified polybutylene dichloride or the like. Used alone or in combination 2 In the active energy ray-curable adhesive of the present invention, a compound which does not have a photopolymerization initiator, a money increase, or an active energy ray-curable property can be appropriately contained. As a photopolymerization initiator, a well-known photopolymerization can be used. Starting agent. Example =, benzophenone,]-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-], 2-dipyridyl ethyl ketone, 2,4,6-trimethyl benzophenone Styrene diphenyl lanthanum oxide, 2-' yl-2 dimethylamino ι_(4 morpholinophenyl) butanone _u_ ketomethyl-1-phenyl propyl 1-ketone, 2-methyl-o-mercaptophenylthio>>2_morphine-based phenyl benzoin methyl scale, benzoin ethyl ether, benzoin isobutyl _, benzoin Propylene, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2-hydroxy-2-methyl-(4-(1-methylvinyl)phenyl)propene Alcohol oligomer, isopropyl thioxanthone, (4-(T-phenylphenylthio)phenyl)phenylmethane, 2,4-diethyl thioxanthone, 2·. gas-based thioxanthone, B Further, these may be used alone or in combination of two or more. It may also be used together with a photopolymerization initiator as n-butylamine, diethylamine, p-didecylamine. An aliphatic amine or an aromatic amine such as ethyl acetoate. The active energy ray-curable adhesive of the present invention may further contain another compound having no active energy ray curability, and may be a compound having no active energy ray curability. A resin such as an acrylic resin, a polyester resin, an amine resin, a bismuth benzene resin or a petroleum resin, a hardener such as an isocyanate compound or an aziridine compound, an aluminum chelate compound, a decane coupling agent, and ultraviolet light 18/53 201229177 A line absorber, an antioxidant, a leveling agent, an antifoaming agent, a bonding aid, a dispersing agent, a drying regulator, an anti-friction agent, etc. The active energy of the present invention is based on the solid content of the active energy ray-curable adhesive The wire hardening adhesive preferably contains: 5 〇 to 85 〇 〇 /. , a phthalic acid ester resin (D), a 5 to 4% by weight epoxy resin, a compound having a (fluorenyl) acrylonitrile group other than the heavy amine oleic acid vinegar resin (D), More preferably, it contains 60 to 85% by weight of an amino phthalate resin (D), = 34% by weight of an epoxy resin (6), and 〇 15% by weight of an amino formic acid brewing tree (D) A compound having a (fluorenyl) acrylonitrile group other than the compound. "When the urethane resin (D) is 50% by weight or more, it is possible to suppress the drop in the collector layer, and it is possible to more effectively maintain the adhesion and the heat and humidity resistance. When it is 85% by weight or less, the heat resistance to thirst can be more favorably maintained. By making the epoxy resin (6) 5% by weight or more, it is possible to make the heat and humidity more excellent by making it 40% by weight or less. Aminomethyl-based resin having a (meth)propene oxime (sinter-hardening, how to maintain the heat-resistant and heat-resistant properties more favorably. By having a (meth)-propyl group other than the amino carboxylic acid vinegar resin (9) The amount of the compound is 30% by weight, and it is possible to effectively prevent the decrease in the adhesive force due to hardness. Further, the adhesive layer which is formed by the active energy ray hardening treatment of the back surface protective sheet for solar battery of the present invention is preferably a glass. The transfer temperature is _5〇7j〇C. In other words, when the active energy ray-curable adhesive is subjected to the active energy 4′′, and the shot is hardened, the lighter surface transition temperature is better. Then the agent layer. It is better to pick ~25〇C, _35 C 0C is better _35C 1GC, particularly preferably _35. 匚~: 5. (: 19/53 201229177 By laminating the sheet-like member when the glass transition temperature is 30 ° C or less, when the hardener layer or the hardening treatment is completed When the adhesive layer is insufficient in the wettability of the sheet-like member, the adhesion between the sheet-like members can be more satisfactorily ensured. Further, by setting the glass transition temperature to _5 〇 C or more, it is possible to suppress the subsequent adhesion. The cohesive force of the agent layer is lowered, and the adhesion force and the moist heat resistance can be more effectively maintained. Next, the back surface protective sheet for a solar cell of the present invention will be described. First, a schematic example of a solar cell module according to the present invention is shown. As shown in the figure, the solar cell module includes a solar cell tank of 7L solar cell b, a solar cell surface protection sheet 2, and a light-receiving surface side sealing material layer 3, as shown in the figure. The non-light-receiving side sealant layer 4 and the back surface protective sheet 5 for a solar cell. The solar cell tank is attached to the light-receiving surface side layer 3 located in the solar cell cell, and is located in the solar cell. Battery bay The non-light-receiving surface side sealing material layer 3 is sealed between the non-light-receiving surface side sealing material layers 4, and the light-receiving surface side sealing material layer 3 is protected by the solar cell surface protection sheet 2, and the non-light-receiving surface side sealing material 4 is protected. The solar cell module of the present invention is not limited to the drawings and can be variously modified. The solar cell back protective sheet 5 is used for knocking, for example, weather resistance. The characteristics of the screen ship, Wei miscellaneous, mechanical characteristics, county, etc. are usually composed of a laminate of a plurality of lamellar members. Fig. 2A to Fig. 2F_ show the purchase of the hair _ solar cell (9) = slice 5 _ mode section _. The solar electric protection sheet 5a of Fig. M has a first sheet-like member u and a second layer of sheet-like members. The first material member η and the second 籼 =; ^ 20/53

S 201229177 is an adhesive layer 51 which has been processed by a living (four) amount-curable adhesive _ (hereinafter, only "the next month = "conformation and bonding. The second sheet-like member η and the second shape = agent layer 51" ” Plastic film, metal falling, metal layer with 2 layers can be oxidized: plastic film of layer, with non-metal oxide layer: genus and plastic thin material (4) with nitrogen cut layer. Suitable examples of the layered product TM Fig. 2A include, for example, a plastic film sheet-like member 11, a plastic film 21 provided with a metal compound, a oxidized paste non-metal oxide, and a nitrogen layer 22 provided with a material. In the example of the second sheet-like member i2, the vapor-deposited layer 22 made of a metal oxide such as alumina or the like of the member 12 of the solar cell back surface protective sheet shown in FIG. 2B may be used. It is placed on the side of the 金属 f metal ^ ι 楼 者 剂 layer 51. Further, as shown in FIG. 2C, a metal case 2 2 sheet-like member 12 of (four) or the like may be used. In this case, the coating layer 24 of a white coating or the like may be provided in the non-light receiving of the gold (four) 23 . The coating layer 24 can be carried out as needed, and in the case of Figs. 2A to 2C, the second sheet-like member 12 has a water vapor shielding layer. The fresh sheet-like member u's sheet-like member may also be composed of a plastic film or the like. The laminate 2 _ sheet' can effectively satisfy the characteristics required for the back surface protection sheet for solar cells. Further, the film referred to in the present specification is not particularly limited in thickness. The back surface protective sheet 5d for solar cells of the figure has a three-layered sheet-like member of the ^-shaped member η, the second sheet-like member 12, and the third sheet-like member 13. The first! The sheet-like member η is joined to the second sheet-like member 12 21/53 201229177 = the first layer of the adhesive layer 5i, and the second member layer U and the second adhesive layer member U and the third child' are all exemplified. The plastic film is used as an example of the sheet-like member 13 of Fig. 2D. Further, as shown in the figure, the sheet-like member is represented by a metal, a metal oxide, or a non-metal oxide, and is a sheet-like member. Further, as shown in Fig. 2C, the thinner member may itself be a metal case such as a case. By the way, the flaky structure is designed to be more effective, 9-layered sheets, and plural characteristics. The second sheet-like member shown in FIG. 2E is a fourth sheet-like member having the first fourth sheet-like member 第. (2) The sheet-like member 1 is formed by the first adhesive layer 51, and the second sheet-like member 12 and the third sheet-like member are joined by the second 52, the third The thin 糸 2 接着 接着 接着 接着 接着 接着 接着 E E E E E E E E E E E E E E E E E E E E E E E E E 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The third sheet-like structure shielding material is composed of a metal case made of _ or the like, and the third material-like member 13 has a characteristic layer of the back surface protection sheet which is used as a layer of the layer. The battery back surface protection sheet 5f is used for the solar cell τ 34th sheet member shown in Fig. 2F. 3 can also be used in a thin plastic material, and a non-metal oxide layer formed by oxygen cutting or the like. The I used on the plastic film 32 to vaporize a metal or metal oxide to replace the non-metal oxide layer. Further, the arrangement, the number of layers, the configuration, and the like of each of the sheet-like members in Figs. 2A to 2F are one example, and various types of deformations of 22/53 201229177 may be employed. Examples of the film to be formed include a polyacetal resin phase such as a polypyrene pair, a naphthalene diester, a hydrazine, a water polyethylene resin, a polypropylene resin, a fat resin, and a polysiloxane resin film B. Di-based acrylic acid I-based resin film, 秘月曰 _, poly (methyl fluorinated yttrium, polypyridyl bristles, taken & one > tetrafluoroethylene, polytetrafluoroethylene, tetrafluoroethylene A fluorine-based tree such as a di- or hexa-ene copolymer. "The secret film is formed by coating a layer of acrylic acid or an aged coating. ===ene::lipid=co-extruded adhesive layer The above-mentioned metal foil may be exemplified by aluminum foil, copper foil, etc. For example, if the stone is a oxide or a non-metal inorganic oxide, an oxide of the example can be used. , wrong, 鍅, 纪, etc. ' & meet the performance as a solar cell module, 'new, water vapor barrier, electrical insulation, mechanical properties, sealing: generation = performance' to layer a poly-p-type resin film which is resistant to temperature, a poly-type resin film such as naphthalene diester, and a polycarbonate film; Preventing the solar cell cell from being affected by water, and reducing the output to laminate a metal foil such as a metal film or a non-metal inorganic oxide vapor-deposited plastic film or aluminum foil; and to prevent light It is preferable that a fluorine-based resin film protective sheet having a good back surface property for a solar cell formed by the laminate is resistant to 23/53 201229177. The combination of the intermediate Yang & _ _ sheet member is It is preferably a self-protecting film for the face of the sun: a light-weighted solar cell back == a polypropylene resin film, a fluororesin film, etc.: an acid resin layer or the like, and a layered layer is thicker than a thick one. a lipid film; then a metal oxide with a water vapor barrier or a gold bond with a non-metallic reduction of (4) thin or (4); followed by a weathering resistance for the occurrence of poor appearance due to sap The sheet for back surface protection for a solar cell of the present invention can be obtained, for example, by the following production method. The line-curable adhesive is applied to any one of the four sheets, and after the formed active energy ray-curable adhesive layer overlaps the other four sheet-like members, the sheet-like member side from the side or the two sheets = the side of the sheet The active energy lining is irradiated to form an adhesive layer which is subjected to active energy ray hardening treatment in a two (four) configuration, or [2] by applying an active energy ray-curable adhesive to any of the sheet-like members, An active energy ray-curable adhesive layer is formed, and the active enthalpy line is irradiated from the side of the wire-curable adhesive layer side and/or from the side of the flaky member, after the formation of the active energy ray hardening-treated adhesive layer , laminating other laminar members on the adhesive layer completed by the active energy ray hardening treatment, or 24/53 201229177 H-slice hardening on the sheet-like member, followed by arbitrarily arbitrarily igniting the energy line hardening == The energy ray-curable adhesive layer is formed from the active energy ray, and after the flaky member is irradiated with activity, the other flaky structure is completed. Flaky Du - ",, Cloth or active energy ray to form a protective sheet. s The date of manufacture (4) Solar energy _ back liquid retention, other vinyl-like resin used for forming other sheet-like members, polyester resin solution for forming plastic film Wind:; = fine eucalyptus 曰 曰 洛 洛 洛 洛 洛 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Manuscript) propylene (10) transfer parts secretive Wei line hardening joint d layer of "Lai County active energy line, the hardening adhesive is free radical polymerizable" b, = 7 is not susceptible to (four) public opinion heart (four) H in hardening In the meantime, there is a pair of members r to correct the defect. However, the 'other aspect' is due to the passage of the sheet, so that the energy line is hardenable and then the active energy line is irradiated, and the emphasis is on whether or not the line-curable adhesive is radical polymerizable. It is possible to make it impossible to attenuate the active energy ray and it is easy to [m do have the opposite feature to the method of []], that is, to illuminate the active energy ray under conditions of easy fork to milk barrier, However, it has the advantage of having a wide selection of flaky members that can be used. The JTi3 system is read under the condition that the initial step is easily hindered by oxygen, and the other side is smeared in the formed layer. 53 201229177 The coating liquid for forming a sheet-like member forms another, and it is easy to ensure the adhesive layer and other sheet-like members =

Mo test = various types of manufacturing methods can be selected or further combined as j-meg, productivity, etc. required for the back protective sheet for solar cells. Further, in the case of [1] and [2], the other sheet-like members are superposed on the adhesive layer or the adhesive layer which is subjected to the curing treatment, and are superposed under heat and/or pressure. (3) The addition of the active energy ray (4) 丨 is applied to the thin layer to adjust the coating liquid to a moderate viscosity, and in the drying step, the solvent may be contained within a range that affects the flaky member. In the case where the curable adhesive contains a solvent, the active energy ray is irradiated to the active energy ray, and the active energy ray hardenability is then hereinafter = more = as a solvent, and acetone, ketone, etc. An acetal compound such as dimethyl ketone or methoxy acetoacetate, an ether compound such as bismuth acetonide or diol dimethyl ether, toluene, :: a compound of ethylene, a fresh fat (IV) a hydrocarbon compound, ethanol, isopropyl alcohol, n-butanol, water, etc., such as a compound or a dichloro fragrant gas. The scale solvent may be used alone or in combination of two or more. In the present invention, a device for using an active energy ray-curable sheet member may be a notch wheel coater, a dry layer knife coater, a die coater, a coater, a bar, and a pro. A coater, a reverse coater, a knife coater, a concave & gram plate gravure coater, and the like. The tamping machine and the smear-coated member are preferably used in an amount of about 26/53 201229177 0.1 〜50 g/m 2 活性 an active energy ray for curing the active energy ray-curable adhesive. For example, ultraviolet rays, electron lines, r lines, = outer lines, visible rays, and the like. '"<Embodiment> The following is a detailed description of the present invention by way of examples, but the present invention is not limited to the following examples. Further, parts and % in the examples show both parts by weight and % by weight. ～ Hereinafter, a combination of a urethane resin having a (meth) acrylonitrile group, an active energy ray-curable adhesive, and a method for producing a back sheet for a solar cell are shown.

Example 1 (manufacture of a urethane resin having a (fluorenyl) acrylonitrile group) D Polymerization tank of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction tube, and a dropping tank In the process, 8 parts of acetophenone (MEK), 857.4 parts of poly(butyl butyl ether glycol) pTMG 2 〇〇〇 (manufactured by Mitsubishi Chemical Corporation), and 31.2 parts of propylene glycol diglycidyl ether were added. Epoxy ester 7 〇pA (manufactured by Kyoeisha Chemical Co., Ltd.) having 2 mol of acrylic acid compound, 0.5 part of dibutyltin dilaurate (dbtdl) as a catalyst, and ο's part as radical polymerization Hydrogen hydrazine and hydrazine of the inhibitor were used as IRGANOX 1 〇 10 (manufactured by BASF Corporation) as an antioxidant, and the temperature in the polymerization tank was raised to 80 〇c while stirring under a nitrogen gas stream. At the time of ribbing, 111.4 parts of isophorone diisocyanate (a mixture formed by mixing with 2 parts of MEK) was dropped into the polymerization tank from the dropping tank for 2 hours. Then, at 8 Torr, it continued to react for 4 hours. It was confirmed by an infrared spectrophotometer that the absorption peak of the isocyanate group completely disappeared, and the reaction was terminated to obtain an amino phthalate resin D1 having a solid content of 5% by mass and having 27/53 201229177 (fluorenyl) acrylonitrile group. The properties of 1 are shown in Table 1A. Examples 2 to 10, and Examples 101 to 103 The reaction was carried out in the same manner as in Synthesis Example 1 in accordance with the composition of Table 1A or Table 1B to obtain an amine having a (fluorenyl) acrylonitrile group. Base phthalate resin D-2~ΕΜ0' and amino phthalate resin D-14~D-16. Amino phthalic acid resin D-2~D-10, and amino phthalate resin D- The properties of 14 to D-16 are shown in Table 1A or Table 1B. Comparative Example 1 800.0 parts of the polymerization tank in a polymerization tank equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction tube, and a dropping tank Ethyl ketone (MEK), 907.2 parts of polybutylene glycol PTMG_2000 (manufactured by Mitsubishi Chemical Corporation), 0. 5 parts of dibutyltin dilaurate (DBTDL) as catalyst, 0.3 parts of hydroquinone as a radical polymerization inhibitor, and IRj part of IRGANOX 1〇l〇 (made by BASF) ), the temperature in the polymerization tank was raised to 8 yc while stirring under a nitrogen gas flow. When it reached 80 ° C, 92.8 parts of isophorone diisocyanate (IPDI) and 200.0 were taken from the dropping tank for 2 hours. The mixture of MEK was dropped into a polymerization tank, and then the reaction was continued at 80 ° C for 4 hours, and it was confirmed by an infrared spectrophotometer that the absorption peak of the isocyanate group completely disappeared, and the reaction was terminated. Next, 3.6 parts of acrylic acid was placed in the reaction tank. 1.0 part of the catalyst is odorized tetrabutylammonium, the temperature in the polymerization tank is raised to 1 〇〇. The reaction is continued, and the reaction is continued until the acid value is 〇mgK〇H/g or less. When the ratio is 1.0 mgKOH/g or less, the crucible reaction is carried out to obtain an amino phthalate resin D_n having a (fluorenyl) acrylonitrile group having a solid content of 5 Å/Å. Properties of the amino phthalate resin D-11 Expressed in Table B. 28/53 201229177 Comparative Example 2 Composition of 1B 'Compared and compared i, the reaction was carried out in the same manner, and the amino phthalic acid vinegar resin (IV) having a (meth) propylene saponin was added. The properties of the urethane resin D-12 are shown in Table 1B. Comparative Example 3 According to Table 1B The composition was reacted in the same manner as in the case of the mixture 1 and was added to the amino carboxylic acid vinegar having a (meth)propyl group. D_13. The properties of the urethane resin D-13 are shown in Table 1B. The details of each component in Table 1A and Table 1B are as follows: PTMG-3_: Mitsubishi Chemical Corporation, polybutylene ketone diol, number average molecular weight 3,000 PTMG_2_ •• Mitsubishi Chemical Corporation Molecular weight: 2,000 PTMG-HKK) : I., Ltd., I., 细EXCENOL.2G2G: Polypropylene glycol 2,000 by Asahi Glass Co., Ltd.; C-1090: K_ay Co., Ltd. Amount of alcohol = 1,000 MPD : 3-methyl-1,5-pentanediol 1,9-ND : 1,9-nonanediol CHDM: cyclohexanedimethanol epoxy vinegar 70AP: manufactured by Kyoeisha Chemical Co., Ltd. , propylene glycol diglycidyl bond is added to the compound of 2 moles of acrylic acid DBTD.L. Dibutyltin dilaurate is intended for IRGANOX1 010 : manufactured by BASF Corporation and 29/53 201229177 IPDI: Isophorone diisocyanate AA: Acrylic acid TBAB: Tetrabutylammonium bromide MEK: Ethyl ketone <Mn ' Mw> Μη, Mw is determined by Tosoh Corporation GPC (gel permeation chromatography) "HPC-8020", and the solvent used tetrahydrofuran. Μη and Mw are converted to polystyrene. 30/53 201229177 宵例8 CO Q 800.0 1 745.3 1 53.7 s' uo o CO o τ- Ο CO 00 200.0 80100 144000 7062 CSJ CSJ CO Example 7 Q 800.0 I—736J...........I Ύ—CO LO inch T·* CO LO o CO o ο ◦ 00 200.0 32000 56400 5026 CSI CVI 1 H Example 6 CO Ο 800.0 00 i CO <0 oo to ή uo o CO o ο 281.0 200.0 26400 49000 5013 CO σ> co Example 5 ir> ο 800.0 s CO og csi CO CO LO 〇co d τ- Ο 卜 CsJ σ> 200.0 29000 52200 2501 卜 r-LO Example Ί T ο 800.0 呀LO CO 1 312 1 LO o CO o ο » —— 200.0 43000 78000 5071 Γ-» σ>σ> 哲例例3 cp ο 800.0 CO LO od LO CO ή LO o cr> o ο 178.8 | 200.0 36200 65100 5064 CNJ ς〇Example 2 CNJ ο 800.0 742.8 L43: 8 〇〇LO o CO o' ο ς〇200.0 29700 53500 4986 CM CO Example 1 Λ- Ο ο οο 卜 LO CO 卜 o CO LO to T—* CO LO 〇CO 6 ο σ> 03⁄4 200.0 30800 54500 5034 ΟΟ s Amine carbamate resin number PTMG-3000 PTMG-2000 PTMG-1000 EXCEN0 L-2020 C-1090 I 1.9-ND 1 Cyclodecyl ester 70PA DBTDL a醌IRGAN0X 1010 IPDI S ΤΒΑΒ f number fff average molecular weight ffifi average molecular weight (methyl) acrylonitrile equivalent amine " phthalate linkage when s solvent y —v < s_^ (A 2) y—s. ffl Nw^ Catalyst, etc. (C) Solvent catalyst, etc., polymerization tank, drop tank addition-/ie s 201229177 32/53 1 urethane bond when fi I (甲κ·) propylene 醯 当 fi fi fi fi fi fi fi fi fi fi fi fi fi ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff ff A 1 ) Solvent TBAB ΓΠ IPDI IRGAN0X 1010 mm DBTDL Epoxy ester 70PA CHDM 1,9-ND C-1090 EXCEN0L-2020 PTMG-1000 PTMG-2000 PTMG-3000 sm 2 σ> 7006 37000 20400 200.0 I 172.0 pp CO p ΟΊ H〇r° σ> 54.2 ^I CJ1 OJ OD oo ο CO 宵Example 9 1205 7020 148000 80200 200.0 92.2 oo OJ o cn 丨22_5 I •CO ro 876.0 800.0 D-10 贲例1() σ> r〇 1004 78500 41300 200.0 179.0 pp CO •O CJ1 | 157.3 663.7 800. 0 D-14 哲例101 σ> CO σ> 12220 153000 82500 200.0 CO powp cn I 12·9 | 54.6 cn cn 00 oo D-15 B Example 102 σ> 21780 162000 87100 200.0 5 CD op CO p ΟΊ CO Cn on ro 765.0 800.0 D-16 ff Example 103 1198 20000 68000 40000 〇•CO CD Ο ο 92.8 oo CO p ΟΊ CO o ro 00 oo D-11 Comparative Example 1 1198 5100 21000 10300 〇200.0 CO oo p •o CO p cn CO g ro 800.0 D-12 Comparative Example 2 cn 00 00 6250 I 74000 I 41000 189.0 1 189.0 1 oo CO o cn 25.3 1 785.7 CO o D-13 1 Comparative Example 3 201229177 Examples 11 to 20, Example 104 ～106, Comparative Examples 4 to 6 (Production of Active Energy Curing Adhesive) Having a (meth)acryl oxime group obtained from the above-mentioned households in accordance with the parts by weight shown in Table 2A or Table 2B Resin of urethane resin (D) = liquid, epoxy resin (6), carbamic acid with (meth) propyl group, active energy ray-curable compound other than the purpose of wax: Agent and its components to obtain active energy ray-curable adhesive 丨~7, 12~ Example 11~20, Example 1〇4~106), an active energy ray curable 8~10 (Comparative Example 4 ~ 6). Know 33/53 201229177 34/53 Tg of cured product (°c) Solvent photopolymerization initiator mm crS 漭 sweet ErWl 卟 difficult epoxy resin (E) mm 菏 w w active energy M line hardening splicing agent composition number Ethyl acetate IRGACURE 184 M2 1 0 M3 0 5 EPIKOTE 10 0 9 EPIKOTE 8 3 4 EPIKOTE 10 0 1 (D-16) solution (D-15) solution (D-14) solution (D_(3) solution (D-12) solution (D-11) solution (D-10) solution (D-9) solution (D_8) solution (D_7) solution (D-6) solution (D_5) solution (D_4) solution (D_3) solution (D_2) solution (D —1) Solution 1 g CO g CJl οι I on N3 CJl j : ih〇〇一θ Example 11 do o CO g tn cn cn ro cn go N3 Β Example 12 cL ro CO s cn CJl CJl ro un 1 1 o CO Example 13 <L· PO GO S cn cn rva tn ΓΟ o Office Μ COcn CO S CJl cn CJl J CJl 1 〇ΟΊ 宵 Example 15 CO h〇o cn j ; 〇σ> ΪΓ Example 16 1 CJl CO s Ol cn cn J CJl j : ; ί i Μ Ϊ i hO 〇宵 丨 7 ΓΟ OO CO g cn CJl cn ro ΟΊ ΐ ΐ I IS ; ro trade Example 18

> 2A

201229177 Comparative Example 6 〇Ο Ο CNJ S uo u> LO S CO ΙΛ s σ> 1 LO CNJ in uo UO s CO Another 1 1 CO 1 ir> C\J ΙΛ LO LO a CO Art 1 Responsible for example 106 I Lf> CNJ LO LO in s ΓΟ τ η Example i〇5 CO S CNl Lf> CSJ UO UO uo s CO Another 1 Example 1ϋ4 LO 1 am LO LD sc〇s 1 Example 20 nr 1 LO CNJ LO LO LO s CO 1 Η 9 CO 1 LO eg ΙΛ lO un s CO LO CSJ 1 composition number (D-1) solution (D-2) solution (D-3) solution (D-4) solution (D-5) solution (D-6) solution (D_7) solution (D-8) solution (D-9) solution (D_10) solution (D-11) solution (D-12) solution (D-13) solution (D-14) solution (D-15) solution (D-16) solution EPIKOTE10 0 1 EPIKOTE 8 3 4 EPIKOTE 10 0 9 M2 1 0 lM3 0 5 IRGACURE 184 Tg (°C) of ethyl acetate hardened 1 Activity Can S line hard ib il K /-"N paste Vw / shout me seat, view m - / mii epoxy (E) 骧 _ hardening compound Photopolymerization Photopolymer Starter Solvent 201229177 Table 2A' The details of each component in Table 2B are as follows: EPIKOTE 834 · Epoxy Resin (Japan Epoxy Resin Co., Ltd.)

Average molecular weight ship 〇 TE coffee: epoxy resin (Japan epoxy = system) number average molecular weight 900 A 〇J EPIKOTE 1009: epoxy resin (Japanese epoxy average molecular weight 3,800 number 1 M210. EO modified double A A propylene Acid § (East Asia Synthetic M305: pentaerythritol triacrylate vinegar (manufactured by Toagosei Co., Ltd.) IRGACURE 184: 1-carbyl-cyclohexyl phenyl group (manufactured by Wasabi) ~ each of the adhesives shown in Table 2A and Table 2B The glass transition severity (Tg) of the cured product was determined as follows. An adhesive bismuth sheet having a thickness of about _ was prepared and measured using a dynamic viscoelasticity measuring apparatus DVA_2 (manufactured by IT Measurement Co., Ltd.). , the temperature of the peak of tanS 値.

In addition, the adhesive hardener sheet is obtained by applying an adhesive to a polyester film having Wei Mlin by a knife coater, and after drying the solvent, irradiating ultraviolet rays (12 〇w metal halide lamp, UV_A field) The cumulative light t 5 〇 _7em 2 ) forms an active energy sclerosing adhesive layer ' and then peels off the polyester film. (Too% of the battery back protective sheet manufacturing method 1 to 6) Production method 1

The active energy ray-curable adhesive is applied to the sheet-like member, and after the solvent is volatilized, the other sheet-like member (s2) is placed while passing through two rolls set to 60 ° C. between. After laminating, ultraviolet rays are irradiated from the side of the other sheet-like member (S1) (120 W metal-based lamp, cumulative light amount in the field of UV/A 201229177 is 500 mJ/cm 2 ), and an adhesive layer formed by active energy ray hardening treatment is formed to produce solar energy. Battery back protection sheet. Further, the amount of the subsequent agent layer was 8 to 10 g/m2. Production method 2 The active energy ray-curable adhesive is applied to the sheet-like member (S2), and after the solvent is volatilized, ultraviolet rays (120 W high-pressure mercury lamp, cumulative light amount in the UV-A field: 200 mJ/cm 2 ) are irradiated from the coated surface side to form The active energy line hardens the finished adhesive layer. Then, while laminating the other sheet-like members (S1), they were passed through two rolls between 60 °C to form a laminate, whereby a laminate was produced. Next, an active energy ray-curable adhesive is applied to the S2 side of the laminate to volatilize the solvent, and then ultraviolet rays are applied from the coated surface side (12 〇w high-pressure mercury lamp, cumulative light amount in the UV-A field: 200 mJ/cm 2 ) to form The active energy line hardens the finished adhesive layer. Then, while laminating another sheet-like member (S3), the film was passed through two rolls of 6 Å, and after lamination, a back protective sheet for a solar cell was produced. Further, the amount of the two layers of the adhesive layer was 8 to 1 〇g/m2. Production Method 3 The active energy ray-curable adhesive is applied onto the sheet-like member (s4). After the solvent is volatilized, ultraviolet rays (120 W high-pressure mercury lamp, cumulative light amount in the UV_A field of 200 mJ/cm 2 ) are irradiated from the coated surface side to form active energy. A wire hardening finish of the adhesive layer. Then, while laminating the other sheet-like members (S3), the two rolls were set to 603⁄4, and after lamination, a laminate was produced. Next, an active energy ray-curable adhesive is applied to the S3 side of the laminate to evaporate the solvent, and then ultraviolet rays are irradiated from the coated surface side (12 〇 w height 37/53 201229177 pressure mercury lamp, cumulative light amount in the UV-Α field 200 mJ) /cm2) to form an adhesive layer that is completed by active energy ray hardening. Then, the other sheet-like member (S2) was superposed while being set to 6 通过. After the two rolls were rolled, a laminate was produced after lamination. Next, an active energy ray-curable adhesive is applied to the S2 side of the laminate to volatilize the solvent, and then ultraviolet rays are applied from the coated surface side (12 〇w high-pressure mercury lamp, cumulative light amount in the UV-A field: 200 mJ/cm 2 ) to form The adhesive layer which has been subjected to the active energy ray hardening treatment is then laminated while passing through the other sheet-like member (S1) while passing through two bonding rolls set to 6 〇 ° c. Then, a back protective sheet for a solar cell was produced. Further, the amount of the two-layer adhesive layer was 8 to 10 g/m2. Production Method 4 A thermosetting amino phthalate-based adhesive is applied onto a sheet-like member (si), and after volatilization of the solvent, the other sheet-like members (s2) are overlapped and the surface is set to 60 ° C. The two rolls are rolled to form a layer. After that, it was aged in a 60° (10) environment to obtain a back protective sheet for a solar cell. Further, the amount of the adhesive layer was 8 to 7. Production Method 5 A thermosetting amino phthalate-based adhesive is applied onto the sheet-like member (52), and after the solvent is volatilized, 'the other sheet-like member (8) is superposed on one side, and the surface is set to be 6 01 2 After the rolling, the hot-hardening base is applied to the S2 side of the (4) slab, and after the solvent is volatilized, the two (53) and - faces are overlapped and set to (4). 2 of the pro-sitting, make. Then, it is aged in 6 (TC environment), and the battery back protective sheet is used for the winter. In addition, the amount of the two-layer adhesive layer is J8~l〇g/m 〇 38/53

201229177 Production method 6 A thermosetting amino phthalate-based adhesive is applied onto a sheet-like member (S4). After the solvent is volatilized, the other sheet-like members are superposed on each other (S3), and the passage is set to 60. Two rolls of °C were used to make a laminate. Next, 'the thermosetting amino phthalate-based adhesive is applied to the S3 side of the laminate, and after the solvent is volatilized, the other sheet-like member (S2) is superposed and the passage is set to 60 ° C. In the case of rolling, a thermosetting amino phthalate-based adhesive is applied to the S2 side of the laminate to volatilize the solvent, and the other sheet-like structure is superposed; (S1) This was set to 6 (the two rolls of TC were laminated to form a layer. Then, it was aged in a paper environment for 1 week to obtain a back surface protective sheet for a solar cell. Further, a 'two-layer adhesive layer' The amount is 8 to 1 〇g/m2^ (Examples 21 to 33, 107 to 109, and Comparative Examples 7 to 15) The active energy ray-curable adhesives shown in Table 3A and Table 4, The method for producing a back surface protective sheet for a solar cell, and a combination of a sheet-like structure to obtain a surface protective sheet for a solar cell, according to the method described later, 'read adhesion, heat and humidity, productivity, and presence or absence of bubbles. In Table 3A, Table 3B, and Table 4. In addition, Example 2, Comparative Example / 12, 16 is shown in Figure 2C. Examples of the laminated structure, the examples, the ratios 8, 13, and 17 are examples of the laminated structure shown in Fig. 2D, and the examples 23, 25 to 33, 107 to 109, and the comparative examples 9, 1 and 14, 18, _ 2E Examples of the laminated structure shown in the 'Example 24, Comparative Example 1G, 15 and 19 examples of the structure of the stalks. 曰39/53 201229177 δ/53 The presence or absence of foaming or bubbling 1 Thermally active 1000-hour flaky member for backing sheet for solar cell. Active IS adhesive S 3 / S 4 S 2 / S 3 S 1 / S 2 S 3 / S 4 S 2 / S 3 Between S 1 / S 2 cn C /) C0 CO N) U) Judgment of the force determination, the force determination, the force determination, the force determination, the force determination, the force -4ir m, then the force 〇〇 \ \ \ \ ◎ \ \ \ \ ◎ CO \ \ |al (white = 1 - Bu) | 1 PET (250) I - a case of 21 〇〇 \ \ ◎ ◎ \ \ ◎ -P». ◎ cn \ PVF (30) PET (250 ) PVF(30) | ro Η 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 23 〇〇◎ Bu ◎ cn ◎ CO CO ◎ CO ◎ Bu Σ〇ϋΐ ΡΕΤ(50) _ΡΕΤ(12) PET(188) LLDPE(50) CO Example 2Ί 〇〇◎ σ> ro ◎ σ> ◎ 〇> ◎ —I ◎ Bu ND ◎ cn ΡΕΤ(50) AL (20) I PET(125)| I EVA(100) 1 CO N3 ΗExample 25 〇〇◎ σ> CO ◎ 〇> ◎ 03⁄4 ΓΌ ◎ 03⁄4 ◎ ◎ σ> ΡΕΤ(50) AL(20) | PET (125) 1 1 EVA(100) I CO CO ®Example 26 〇〇〇cn CO 〇cn 〇cn ro ◎ CO ◎ σ) ◎ CO 1 ΡΕΤ(50) 1 AL(20) PET(125) EVA (100 CO ®Example 27 〇〇◎ CO ◎ —J ◎ rvj ◎ 03⁄4 ◎ σ> rsa ◎ 03⁄4 ΡΕΤ(50) AL(20) PET(125) | EVA (100) CO ΟΊ Surprise Example 28

^3A 201229177 Example 1()9 Divination EVA (100) PET(125) AL(20) PET(50) CO ◎ CO ◎ r-^ ◎ CO CNJ < CO Csj <1 CO <3 〇〇 Example 108 CO CO EVA(100) | PET(125) I AL(20) | PET(50) I LO ◎ CO ◎ 卜 ◎ 〇 〇 CNJ — 〇〇〇 Example 1 () 7 LO cr> EVA (100) | PET(125) | AL(20) | PET(50) I CO CO <l c6 < 〇CO n· 〇in nf 〇〇〇〇ΪΤExample 33 inch 〇〇EVA (100) PET(125) | AL(20) | PET(50) | cb ◎ CO C£) ◎ inch to ◎ CO LT> 〇LO 〇LO LO 〇〇〇宵Example 32 CO CO EVA(1QQ) I PET( 125) AL(20) | PET(50) | CVI od ◎ CO ◎ CO ◎ ◎ LO 〇OO LO 〇〇〇哲例31 CNJ CO I EVA(100)1 PET(125)J AL(20) | PET(50) | lo p-»· ◎ CO 卜-· ◎ ^r ◎ 卜 · ◎ CNJ 卜 ◎ OO (£> ◎ 〇〇 Example 3 () 卜 CO I EVA (100) I PET (125) AL(20) | PET(50) I CO ◎ 〇> r-^ ◎ LO ◎ LO 〇LO LT> 〇CSJ LO 〇〇〇R Example 29 CO Ieva(ioo) I PET(125) AL(20) | PET(50) I cd ◎ CO ◎ m to ◎ I-: ◎ 〇 〇〇 〇〇 〇〇 〇〇 〇〇 线 线 线 | | | 池 池 池 池 池 rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn rn Judgment I Next force determination 1 Productivity 1 Bubble, presence or absence of bubbling S 1 / S 2 S 2 / S 3 S 3 / S 4 S 1 / S 2 S 2 / S 3 S 3 / S 4 Interlamellar-like member is difficult to withstand heat and humidity for 1000 hours 201229177 42/53 1 Bubbles and bubbling | | 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 生产 麟 麟 麟 麟 麟 麟3/S 4 S 1 / S 2 S 3 / S 4 S 2 / S 3 S 1 / S 2 CO w CO w ω | Judgment | Next Force | Judgment | | Next Force | | Judgment | Then force||judgment||continuation force||judgment|bubble force I|judgment|then force 〇〇\ \ \ X 〇cn \ \ \ \ ◎ —J \ |al (white=i-b)|PET( 250) | A CO Comparative Example 7 〇〇\ \ X ·〇CO X 〇\ ◎ tn ◎ CO \ PVFC30) | PET(250) | PVF(30) oo Comparative Example 8 〇〇X 〇X 〇X 〇 -J ◎ CO ◎ | PET(50) I AL(20) | | PET(125) | EVA (100) Ca) 09 Comparative Example 9 〇〇XPX ·〇CO X 〇cn ◎ ◎ -^j ◎ CO — JI PET(50) I Evaporation PETU2) PET(188) | LLDPE(50)| CO 03 Comparative Example 1() 〇〇XX h〇X ◎ ◎ σ> ◎ ro PET(50)| AL(20) I PET( 125)] [EVA(100)| CO CO Comparative Example 11 〇〇\ \ \ \ > CO CJ1 \ \ \ \ > CO CO \ \ AL (white smear) PET(250) | o Comparative Example 12 〇 〇\ \ > •ΓΝ3 CO > CO CO \ \ > CO ro > CO cn \ PVF(30) | PET(250) 1 PVF(30) | ro o Comparative Example 13 〇〇> CJ > Γ° > CO ho > CO > CO D> CO CO | PET(50) AL(20) PET(125) EVA(100)| CO o Comparative Example 〇〇> [S3 〇〇> CO > CO > CO ΟΊ t> CO ΟΊ > CJ 03⁄4 PET(50) Evaporation ΡΕΤΠ 2) PET(188) LLDPE(50) CO o Comparative Example 15 201229177 (Comparative Examples 16 to 19) P-3010 (manufactured by Kuraray Co., Ltd.) reacted with isophorone diisocyanate to form a polyamino phthalic acid ester having a hydroxyl group having a number average molecular weight of 15,000 and having a solid content ratio of 10:1. A biuret body of hexyl diisocyanate was blended, and 30% by weight of EPIKOTE 1001 was blended at a solid content ratio to prepare a thermosetting amino phthalate-based adhesive 11. Using the thermosetting amino phthalate-based adhesive agent shown in Table 5, the method for producing a back surface protective sheet for a solar cell, and the combination of the sheet-like members, a back protective sheet for a solar cell was produced. According to the method described later, the adhesion, the moist heat, the productivity, and the presence or absence of bubbles were evaluated. The results are shown in Table 5. 43/53 201229177 44/53 The presence or absence of foaming and bubbling, heat and humidity resistance, and the formation of a back sheet protective sheet for a solar cell, a sheet-like member, a thermosetting hard ester ester-based adhesive, S 3 / S 4 S 2 / S 3 between S 1 / S 2 S 3 / S 4 between S 2 / S 3 U) — I \ (Ω N) ϋ ω ω (Ω ro (Ω judgment adhesion force determination adhesion force determination Then, the force determination and the force determination are followed by the force determination 1 and then the force XX \ \ \ \ ◎ σ> h〇\ \ \ \ ◎ CT) CO \ \ AL (臼 color coating) ΡΕΤ (250) I 4^ Comparative Example 16 &gt X \ 〇CJ1 〇σ> \ 〇ΟΊ ΟΊ 〇C71 OO PVF(30) PET(250) PVF(30) ΟΊ Comparative Example 17 XX ◎ 〇<y> ◎ σ> CJ1 ◎ Οϊ CO 〇CJ1 〇〇◎ <Ti OO ΡΕΤ(50) AL(20) PET(125) EVA (100) Comparative Example 18 XX ◎ σϊ 〇σ> ◎ CO ro ◎ CO ◎ <y> ro ◎ CO ΡΕΤ (50) 蒸 蒸12) PET (188) LLDPE (50) σ > Comparative Example 19 201229177 The flaky members (S1 to S4) in Tables 3A to 5 are abbreviated as follows. "'' • PET (250): transparent poly Ethylene phthalate film (25 〇μηι) · ΡΕΤ (188): transparent polyethylene terephthalate film Ι88μιη), 又子·ΡΕΤ(125 wide transparent poly(p-phenylene terephthalate) Ethylene glycol film (thickness Ι25μιη) ·ΡΕΤ(50 wide transparent polyethylene terephthalate film (thickness 5〇μηι) • evaporated rhodium (12): in polyethylene terephthalate film (Thickness such as (7)), a film of a mixture of 5 (9) people (50 nm) of a mixture of the thickness of the cerium oxide and magnesium fluoride (% by mole) of 90/10. • AL (white coating) "Layer" is provided on one side of an aluminum foil (thickness 3 〇μηι) with a valence resin layer* from m. Weather resistant resin layer*·· OBBLIGATO PS2012 (white) main agent: hardener (13: 1) (AGC COAT-TECH company) • AL (20): Aluminum pig (thickness 20// m) • PVF (30) · Polydurized acetonitrile film (thickness 30 pm) • LLDPE (50). Polyethylene film ( Thickness (10) is called: • EVA: Ethylene/Ethyl Acetate Copolymerized Resin Film (Thickness: 1 〇〇 (4) The evaluation criteria of each of the evaluation methods in Tables 3A to 5 are as follows. (1) Adhesiveness The solar cell back protective sheet was cut into a size of 2QG_xl5 mm, and subjected to a tensile tester at a loading speed of 3 GG_/min according to the test method of ASTM D1876-61. The average enthalpy of the five test pieces 45/53 201229177 indicates the detachment strength (Ν/15_width) between the respective sheet-like members. ◎ · · · 6Ν or more 〇···4Ν or more~ less than 6Ν △ •••2Ν or more~ less than 4Ν χ··· Below 2Ν (2) Moisture and heat resistance The back surface protection sheet for solar cells is 85.保, 85% RH atmosphere for 1000 hours. The preserved solar cell back protective sheet was cut into a size of 200 mm x 15 mm and tested in accordance with ASTM D1876 61 using a tensile tester and a tau type peel test at a loading speed of 300 mm/min. The strength (N/15 mm width) between the respective sheet members was expressed by the average 値 of the five test pieces. ◎ · · · 6N or more

〇···4Ν or more~ less than 6N △ · · ·2Ν or more~ less than 4Ν χ· · · Less than 2Ν (3) Producing a roll of a back surface protective sheet for a solar cell of 50cm width and 500m length, The core is erected in an up and down direction, and the outer edge is picked up. α 〇··· does not deform in the subsequent sheet, and the shape of the drum can be maintained. 5 χ··· The deformation occurred in the succeeding sheet, and the shape of the drum could not be maintained. 3 (4) The presence or absence of bubbles and buoys is made of a 50cm wide, 5〇〇m long solar cell back protective sheet 46/53 201229177 Roller's erecting the core in the up and down direction, and at 6 (rc The environment was stored for one week. The state of the adhesive layer was observed through a transparent sheet-like member, and the sheet-like member was observed for the presence or absence of bubbling. 〇···No abnormality △ • • • Small bubbles were generated or small bubbles were generated. Or generate large buoys. Further, 'disclose the following remarks. [Remark 1] 胺 A urethane resin (D) having a (meth) acrylonitrile group, which is caused by the necessary number average molecular weight of $(8) a polyether polyol of ～5,_ (VIII) has a polyol component (Α) having no (fluorenyl) acrylonitrile group, a octylene group having a (meth) acrylonitrile group and having 1 2 3 4 or more hydroxyl groups. The polyol is obtained by the reaction of a knives (Β) and a polyisocyanate component (C). [Remark 2] As Remark 1 or Note 2, the acid ester resin (D), where the number [Remark 4] 47/53 1 5 A urethane tree having a (fluorenyl) acrylonitrile group: wherein the aforementioned number average molecular weight is 5 〇〇 5 , 〇〇〇 Polyether polyol 2) based the following - represented by general formula (1) by: 3

General formula (1): H〇(-R_0)n_H 4 (wherein R may have a hydrocarbon group having 3 to 8 carbon atoms of a side chain substituent, and η represents an arbitrary integer). 5 [Remark 3] The amine group having a (meth) acrylonitrile group has an average molecular weight of 5, 〇〇〇 150, 〇〇〇. 201229177 Amino methacrylate resin (D) having a (meth) acrylonitrile group as claimed in any one of claims 1 to 3 wherein the urethane bond equivalent is 2 〇〇 3 , 〇〇〇. [Remark 5] The amino phthalic acid vinegar resin (D) having a (fluorenyl) acrylonitrile group according to any one of the above items 1 to 4, wherein the aforementioned (mercapto) acrylonitrile group has an equivalent weight of 5 〇〇 to 4 〇. , hehe. [Remark 6] The amino decanoic acid having a (meth) acrylonitrile group as the one of the above-mentioned items 1 to 5 is a resin (D) 'wherein the aforementioned (mercapto) acrylonitrile equivalent is 1,200 to 20,000 Å [ Remark 7] For example, any of the terminal storage groups, saturated hydrocarbon groups, and unsaturated tobacco groups may be used as the resin (D) of the (mercapto) acrylonitrile group. By. [Remark 8] The amine group HfefKD having a (meth) acryl fluorenyl group as in any one of the following 5 main groups 1 to 7: wherein 'the number of atoms of the main chain skeleton between the bonds of the amino phthalic acid 0 is 3 the above. [Remark 9] The amine group having a (meth) propyl group based on any one of the main items 1 to 8 is known (9) wherein the polyol component (9) has two or more groups of acrylonitrile. [Remark 10] For the urethane resin (D) having a (meth) propylene ion group, the arrow, +, eve _ ># , 〒 The melamine component (Β) is a compound obtained by adding (meth)acrylic acid to an &oxy group having two or more ring-shaped latexes. This application is based on the Japanese application 48/53 201229177, which is based on December 15th, 2nd year, and the Japanese application for the purpose of applying for the Japanese application. Priority is based on -235723, the entire disclosure of which is incorporated herein. [Industrial Applicability] The active energy ray-curable adhesive containing the (fluorenyl) acrylonitrile-based urethane resin (D) of the present invention is a substrate for a plastic film or a metal film. The adhesion is excellent, and j_ is excellent in high temperature and humidity conditions. Therefore, it is suitable for use in the manufacture of a back surface protective sheet for solar cells. Moreover, it is also applicable to a surface protection sheet for solar cells. In addition, in other fields, it can be widely used as an electric and electronic component such as a plastic lens, a solder resist for an optical member replaceable printed wiring board, and an interlayer insulating film for a multilayer printed wiring board. , thin packaging of lithium-ion battery packs, coating agents for other papers or all plastic films, and additives for food packaging. Further, the aminodecyl phthalate (D) having a (meth) acrylonitrile group of the present invention can be used in the field of inks, paints, and the like in addition to the use of the above-mentioned adhesive. [Simple description of the map]

Surface map. A schematic cross-sectional view of a solar cell module according to the present invention is a schematic cross-sectional view showing an example of a back surface protective sheet for a solar cell of the present invention. Fig. 2B is a schematic cross-sectional view showing an example of a back protective sheet for a solar cell of the present invention. Fig. 2C is a schematic cross-sectional view showing an example of a back protective sheet for a solar cell of the present invention. Fig. 2D is a schematic cross-sectional view showing an example of a back protective sheet for a solar cell of the present invention 49/53 201229177. Fig. 2 is a schematic cross-sectional view showing an example of a back protective sheet for a solar cell of the present invention. Fig. 2F is a schematic cross-sectional view showing a back surface protective sheet for a solar cell of the present invention. [Explanation of main component symbols] 1 Solar cell slot 2 Surface sealing sheet for solar cell 3 Light-receiving side sealing material layer 4 Non-light-receiving side sealing material layer protective sheet 5, 53, 5 Bu 5 5 太阳能 5^ Solar battery back 11th sheet member 12 second sheet member 13 third sheet member 14 fourth sheet member 21 plastic film 22 vapor deposition layer 23 metal foil 24 coating layer non-metal oxide layer 51 first adhesive layer & 2 adhesive layer 3 third adhesive layer 〇〇 too ^ energy battery module 50 / 53

Claims (1)

201229177 VII. Patent application scope: An active energy ray-curable adhesive comprising a urethane resin (D) having a (meth) acrylonitrile group and an epoxy resin (E); The methyl methacrylate urethane resin (D) is composed of a necessary number average molecular weight of 500 〜5, and the ruthenium polyether polyol (A1) does not have (mercapto) propylene sulfhydryl group. A polyol component (A), a polyol component (B) having a (meth)acrylonium group and having two or more hydroxyl groups, and a reaction with a polyisocyanate component. 2. The active energy ray-curable adhesive according to claim 1, wherein the polyether polyol (A1) having a number average molecular weight of 500 to 5,000 is represented by the following general formula (1): 1) : H0(-R-0)nH (wherein R may have a hydrocarbon group having 3 to 8 carbon atoms of a side chain substituent, and n represents an arbitrary integer). ^ 3. The active energy ray-curable adhesive of claim 2 or 2, wherein the aforementioned amino phthalate resin (the number average molecular weight of ruthenium 5, 0 〇 0 to 150, 〇〇〇. The active energy ray-curable adhesive according to claim 1 or 2, wherein the amino phthalate bond of the aforementioned urethane resin (D) is two 200 to 3, 〇〇〇. The active energy ray-curable adhesive according to claim 1 or 2, wherein the aforementioned (meth) propylene in the urethane resin is 5.0 to 40, 〇〇 W二. 6. The active energy ray-curable adhesive according to claim 1 or 2, wherein the epoxy resin (E) has a number average molecular weight of 45 〇 5 5, 〇〇〇: as claimed Active energy ray-curable adhesive of the range i or 2, 51/53 7. 201229177 wherein the above epoxy resin (E) has a number average molecular weight of 5 〇〇 5, 〇〇 (). The active energy ray-curable adhesive of the first or second aspect, wherein the solid content of the active energy ray-curable adhesive is based The above-mentioned urethane resin (D) and 5 to 40% by weight of the above epoxy resin (E) are contained in an amount of from 5 to 85% by weight. 9. The active energy of the first or second aspect of the patent application The linear curable adhesive, wherein the polyol component (B) has two or more (fluorenyl) acrylonitrile groups. The active energy ray-curable adhesive according to claim 1 or 2, wherein The polyol component (B) is a compound obtained by adding a (meth)acrylic acid to an epoxy group of a compound having two or more epoxy groups. 11. A back protective sheet for a solar cell, which is protected by A solar cell back surface protective sheet having a surface on a side opposite to a sunlight incident surface of a solar cell element of a solar cell, comprising a laminate of two or more sheet-like members, and at least a part of the sheet-like member of the laminate Then, an adhesive layer which is completed by an active energy ray hardening method according to any one of the claims of the above-mentioned patents to the above-mentioned items, and then a sizing treatment is carried out. Sun of the item a back protective sheet for a battery, wherein at least one of the sheet-like members constituting the laminate has a water vapor barrier layer, and the water vapor barrier layer is selected from a metal film, a plastic film with a metal oxide layer, and A group consisting of a plastic film with a non-metal oxide layer. 13. A backsheet 52/53 201229177 for a solar cell according to claim u or 12, wherein the aforementioned active energy ray hardening process is completed. The glass transition temperature of the agent layer is -50 to 30 ° C. 53/53