TW201239057A - Adhesive composition for laminating sheet and back protective sheet for solar cell - Google Patents

Abstract

An adhesive composition for fabricating a back protective sheet of solar cell is provided. The adhesive composition provides high adhesion between various sheet-like portions, especially between layers including surface treatment layer of plastic film, and the high adhesion can be maintained even when the adhesive composition is exposed to an environment of high temperature and high humidity. The adhesive composition for a laminating sheet of this invention includes an acrylic polyol (A) and a polyisocyanate (B), wherein a number average molecular weight of the acrylic polyol (A) is 10, 000 to 100, 000m, a hydroxyl value is 1 to 100 mgKOH/g, and a glass transition temperature (Tg) is more than 10 DEG C and no more than 50 DEG C. Further, an equivalent ratio NCO/OH of a hydroxyl group from the acrylic polyol (A) and an isocyanate group from the polyisocyanate (B) is 0.1 to 10.

Description

[Technical Field] The present invention relates to an adhesive composition for a laminated sheet and a back protective sheet for a solar battery. [Prior Art] In recent years, multi-layer (composite) used in outdoor industry applications such as barrier materials, roofing materials, solar panel materials, window materials, outdoor flooring materials, lighting protection materials, automobile parts, signs, labels, etc. A multilayer (composite) laminate body such as a film is put into practical use. The multilayered laminate can be obtained by laminating (laminating) a metal-based raw material or a plastic-based raw material. Examples of the metal-based raw material include metal foils such as aluminum, copper, and steel sheets, metal plates, and metal deposition films. Plastic materials include polypropylene, polyethylene, polyester, fluororesin, acrylic resin, plastic film, plastic sheet, and plastic sheet. A binder used in the joining of a metal-based raw material or a plastic-based raw material is known as a polyepoxy-rotating agent and a polyaminophthalate-based adhesive. In Patent Document 1, a sheet for sealing a back surface of a solar cell is described, and at least two or more base layers are provided with a polyurethane-based adhesive. More specifically, a polyamine phthalic acid®-based adhesive which satisfies the following conditions and an adhesive for the following properties is described: a promotion evaluation for the completion of production; a high acceleration temperature of 1 it % stress test ( Hast) In the chamber, it is said that (10) the laminate strength after 168 hours of storage is at least 1Ν/Ι5_ to 20123903⁄4; Condition 2: in the hast chamber used as the evaluation of the use of pressurized steam, at 105 C, 1.05 After 168 hours at atm, no ridges between the substrates accompanying delamination were produced. Specifically, it has been proposed to combine the types of polyhydric alcohols of the polyols A to the polyols F in combination with the polyhydric alcohols of the polyols A to the polyhydric alcohol F. _ 彡 彡 ( (refer to Patent Application No. 2 to Item n of Patent Document 1). Patent Document 2 describes a rear sheet for a solar cell module comprising a laminate in which at least two substrates are bonded together by an acrylic adhesive. More specifically, an acrylic-based adhesive is proposed as an acrylic adhesive having hydrolysis resistance, insulation resistance, and moisture barrier property, and the acrylic adhesive contains a compound of the formula (I). An acrylic polymer obtained by polymerizing a monomer component of a monomer (refer to Patent Application No. 2 of Patent Document 2). CH2=C(R1)-C〇.〇z (I) In the formula, R1 represents a hydrogen atom or a fluorenyl group, and Z represents a hydrocarbon group having a carbon number of 4 to 25. Further, in the patent documents disclosed in the prior application, which is the basis of the priority, Patent Document 3 and Patent Document 4 describe an adhesive composition suitable for the following applications: on the untreated side of the plastic film. Other substrates are used in the subsequent sheets. [Prior Art Document] [Patent Document] 201239057r [Patent Document 1] International Publication No. 2007 148754 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei 2 No. Hei. In order to stably maintain the adhesive agent for a long period of time under severe conditions outdoors, it is important that the subsequent strength is stabilized even with the passage of time. Recently, as disclosed in Patent Document 3 or Patent Document 4, an adhesive which does not perform the surface of the unreacted surface of the surface or the substrate is preferably adhered to the other substrate. *There is no surface treatment* to shorten the manufacturing steps, thus reducing costs. (4) In other aspects, the surface treatment technology applied from the wire is also used, and the adhesive composition which improves the original performance of the adhesive composition and synergistically has superior adhesive properties is also used. The demand is also getting higher. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a backing sheet for a laminated sheet and a back protective sheet for a solar cell, wherein the laminated sheet is used to listen to the object between the carved members. The system shows a high adhesion between the layers of the f film treatment layer, even if it is exposed to another dish, the humidity can be _ high.

The back of the pool is protected. In order to solve the above problems, the Ulxe Tai I Co., Ltd. has made an intensive study, and the present invention can be completed by the above-mentioned composition "I". That is, the laminate for the laminated sheet of the present invention includes acrylic acid! 6 -r 1. 201239057t

a polyol (Α) and a polyisocyanate (A) having a number average molecular weight of 10,000 to a value of ImgKOH/g to 100 mgKOH/g and a glass transition temperature (Tg) exceeding 10 ° C. And 50 ° C or less, in addition, the ratio of the rhodium to the isocyanate group derived from the polyacrylic acid (A) and the isocyanate group derived from the polyisocyanate (B) is 0.1% NCO/OH. ~10. Preferable examples of the polyisocyanate (B) include an example of a polyisocyanate derived from an alicyclic diisocyanate or an aliphatic diisocyanate. The laminated sheet adhesive composition of the above aspect is used in the manufacture of a back protective sheet for solar cells comprising two or more sheet members, and is suitable for use in the following applications: forming the sheet members to be joined to each other At least a portion of the layer of the agent. Further, the back surface protective sheet for a solar cell of the present invention comprises: an adhesive layer formed of the adhesive composition for a laminated sheet of the above aspect; and two or more sheet members laminated with the adhesive layer described above. [Effects of the Invention] For the use of a sheet, the composition of the second layer of the composition of the layer of the film, the layer of the layer of the film, the layer of the film, the layer of the film, and the layer of the film, In the high-filled environment of the plastic, the high-pressure adhesive can be turned on the high-temperature back protective sheet. [Embodiment] The embodiment of the present invention will be described in detail below. Further, other embodiments may also fall within the scope of the present invention as long as it conforms to the gist of the present invention. Further, in the present specification, "arbitrary number A to any number B" = δ is a range indicating the number a and the number A, and is a range of the number B and less than the number B. Further, the description of "(meth)" "acrylonitrile" as described in the specification and the patent application includes any compound which is referred to as "acrylofluorene" and a compound which is referred to as "methacryl". Further, it is similarly defined in "(meth)acrylyl" and "(T-based) acrylate". As the acrylic polyol (A), a monoacetic acid acrylate monomer having a hydroxyl group and a mono(meth)acrylate monomer having no warp group can be preferably used. The mono(meth)acrylate monomer containing a trans group is a human ^=(methyl) propyl sulfhydryl group in the i molecule! More than one monomer. A preferred example is a monomethyl acetonitrile monomer, an ε-caprolactam modified (meth)acrylic monomer, etc. obtained by the reaction of 3 inventories of I 2 decyl alcohol and (meth)acrylic acid. The number average molecular weight of the acid polyol (Α) is, in terms of 'the double bond with the mono(meth)acrylic acid acrylate monomer and the (meth) group = 〜3. The side chain portion is ugly Delaid $AM progress is better 1

In the case of 丨, left and right, if the propylene chain element = number: the average molecular weight is equivalent, the side bond portion 2 = a large amount of I 8 201239057 The more positive the chain of the alcohol (A) becomes longer. As a result, the mechanical properties (specifically, the elongation) of the adhesive layer after curing are improved, and the force is increased. The mono(indenyl) acrylate monomer obtained from 2,700 alcohol can be exemplified by (methane), dilute -2- mercaptopurine, (mercapto) acrylic acid by propyl vinegar, 1,4- Butanediol mono(indenyl)acrylic acid brewing, (poly)ethylene glycol mono(indenyl)acrylic acid vinegar, and the like. In addition, a mono(meth)acrylate monomer obtained from 3 ^ or more of an alcohol such as 2,3-dihydroxypropyl (meth)acrylate may also be used as a monomethyl group having a hydroxyl group. ) acrylate monomer. The mono(meth)acrylate monomer having no hydroxyl group can be suitably used by selecting a radical polymerizable monomer known from the prior art. Suitable examples are, for example, (meth)acrylic acid, (meth)acrylic acid, vinegar, (meth)propionic acid, third vinegar, (methyl)propionic acid, 2_ Ethyl hexanoic acid, (meth) propyl, acid octyl vinegar, (meth) acrylic acid lauryl vinegar, (meth) propionic acid tridecyl: (meth) benzoic acid stearyl ester, etc. A long-chain (meth)acrylic monomer represented by a (meth)acrylic acid alkyl ester monomer, and acrylonitrile or the like. In addition to the above-mentioned hydroxyl group-containing (meth) acrylate monomer and non- 3 hydroxy mono(meth) acrylate monomer, it is also possible to copolymerize other monomers such as (meth) acrylic acid, A monomer such as maleic acid or maleic anhydride containing a ring-based monomer or a sour liver or a vinyl monomer such as styrene. Further, the (meth)acrylic acid vinegar monomer and the radical-free monomer may each independently use a β compound, or two of them may be used in combination. The same applies to the case of using other monomers. In the present invention, the acrylic polyol (Α) must have a number average molecular weight of 10,000 to 100,000. Further, it is preferably 1〇(4) 201239057τ~70,000, more preferably 25, 〇〇〇~5〇, 〇〇〇. A laminated sheet obtained by laminating two or more sheet-like members, for example, a back protective sheet for a solar cell, which can be laminated with an adhesive composition for laminated sheets of the present invention (hereinafter also referred to as "adhesive" and "object"). Obtained through the following steps. = The joint faces of the - sheet members are coated with the adhesive composition to be dried. ^次', the other #-shaped parts are superimposed on the adhesive layer, and the layer is called "aging" in the environment of 4 01 to 60 C for 2 days to 丨 weeks, and the adhesive layer is hardened to obtain a laminate. sheet. When the number average molecular weight of the acrylic polyol is less than 1 Å, the cohesive force of the adhesive layer before the aging step tends to be insufficient, and the adhesive force before the aging step becomes small. In the case of jade production, the shape of the peach is entangled. The general condition T causes the core to age in the vertical direction. If the force before the aging step is small, the winding is easily spread when the aging is performed, and it is not suitable for industrial production. Further, if it is less than 1 Torr, there is a problem that the cohesive force after the aging step is insufficient, and the heat and humidity resistance is lowered, and delamination occurs. Further, if the number average molecular weight of the acrylic polyol exceeds 100,000 ', there is a tendency that the reduction of the adhesive is higher than the coating property, and the manufacturing property of the component is lowered. As a result, there is a subsequent change in the aging step f. Small 虞. Although the residual force is larger than that of the old one due to aging, it is gradually lowered by the subsequent heat and humidity resistance test after 3,000 hours and below the lower limit of use. Further, the number average molecular weight in the present invention is determined by a gel permeation layer (C) and is converted to a value in terms of polystyrene. More specifically, 201239057, the number average molecular weight in the present invention is a value obtained by a measurement method described in the examples described later. Further, the glass transition temperature and the NCO/OH equivalent ratio are similarly expressed as values obtained by the method described in the example described later. The hydroxyl value of the acrylic polyol (A) is determined by the content of the mono(meth)acrylate monomer having a hydroxyl group. In the present invention, the hydroxyl value must be from 丄 mgKOH/g to 100 mgKOH/g. Further, more preferably, it is 4 mgKOH/g to 40 mgKOH/g. If it is less than 1 mgK0H/g, the crosslinking with the isocyanate curing agent tends to decrease, and the heat and humidity resistance is lowered. In addition, when it exceeds 100 mgKOH/g, although the adhesive force before aging may be exhibited, the crosslinking density tends to become high after aging, and it may not be able to exhibit sufficient adhesive force, and thereafter it is resistant to moist heat. In the test, the force was further reduced. Further, in the present invention, the glass transition point (Tg) of the acrylic polyol must exceed 10 ° C and be 50 ° C or less for the reason described later. Further, it is more preferably more than 10 ° C and not more than 30 ° C. <Polyisocyanate (B) > The polyisosorbate (B) is, for example, a compound derived from a well-known diisocyanate, and a known compound can be used without limitation. For example, it can be exemplified by: 2,4-nonylbenzene diisocyanate (alias: 2,4-TDI), 2,6-nonylbenzene diiso-acid ester. (alias: 2,6-TDI), diterpene diisocyanate (alias: XDI), phenyl pyridinium diisocyanate (alias: MDI), isophorol homodiisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate (alias: HDI), double (4 - isocyanate cyclohexyl) decane, or hydrogenated diphenyl decane diisocyanate 201239057,

The compound of the same day, which is the compound of the sulphuric acid and vinegar, which is the pre-polymer of the sulphate, the trimethoprim, the biuret, and the ester residue. a mixture of a diisocyanate and a polyhydric alcohol, a uretdione having an isocyanate residue, a compound of a ureido citric acid, and a blocked isocyanuric acid. Polyisomeric; 7 may be a single compound or a combination of two or more. From the viewpoint of the viscoelasticity of the cured coating film after self-crosslinking, it is preferred to use a polyisocyanate derived from an alicyclic diisocyanate or a monthly Hr isocyanate. More specifically, the lipid = phthalate ester may, for example, be isophorone diisocyanate, methyl-2,6-ring 'di,:, acid ester or the like. Further, examples of the aliphatic diisocyanate include hexa-acidic acid, pentamethylene diisocyanate, and the like. Moreover, the alicyclic, trimethylolpropane adduct, and biuret type of the isocyanate of the alicyclic ring, the diisocyanate, and the two of the Liner's two different grades of the compound are mentioned. a prepolymer having an isocyanate residue (a diisocyanate derived from a polyalcohol = a low polymer), a urea di-salt having an isocyanate residue, a glyphosate body, or the like Complex, etc. Moreover, in the case of paying attention to the speed of hardening, it is preferred to use isocyanate having an aromatic content of 'xylene diisocyanate _ (alias: XDI) but having an elongation between the NCO and the aromatic ring. vinegar. If the hardening speed is fast, it is preferable in terms of shortening the aging time. Further, the isocyanic acid in the polyisocyanate (B) is preferably from 5 wt% to 30 wt%. Further, the isocyanate concentration in the polyisocyanate (b) can be determined by a drum method by titration with n-t-ylamine/hydrochloric acid 12 201239057

*Τ X is evaluated for evaluation. Specifically, after dissolving the sample in a dry state, an excess of dibutylamine solution is added and reacted, and the remaining di-n-butylamine is back-titrated by hydrochloric acid, and the titration curve is The inflection point is used as the end point 'the isocyanate group content rate is calculated based on the titration to the end point. The amount of the polyisocyanate (B) used can be determined by the ratio of the hydroxyl group derived from the acrylic polyol (A) to the nc〇/〇h equivalent ratio of the isocyanate group derived from the polyisocyanate (B), and the NCO/OH equivalent ratio is set to 〇. 1~1〇. More preferably, the NCO/OH equivalent ratio is from 0.5 to 6. If it is less than ai, there is a tendency for the force to decrease after exposure to the inside and the outside. Further, if it exceeds, there is a tendency that the adhesion force after the initial aging is lowered. The NC〇/〇H equivalent ratio can be obtained by the following mathematical formula (1). Tian x (561/OH (solid matter weight NCO/OH ratio = polyisophthalate required amount (parts by weight) value) X (NCO% / (42x100)) X (1 〇〇 / polyol amount)) Mathematical formula (1) :: It is clear that the person has found that the following conditions satisfy the following conditions, and it is possible to obtain an adhesive composition for a laminated sheet having excellent characteristics. That is, it is possible to provide an adhesive composition which exhibits a high adhesion between the sheet members, particularly the layers comprising plastic, yttrium, and yttrium:::: even if exposed (2) The specific description has a (1) specific range of translational temperature (Tg) of the glass transition, A;), and further (iv) derived from 201239057 acrylic polyol (A) reading base and derived from polyiso ^ The equivalent ratio of the acid vinegar group NCO / OH is set to the above-mentioned special two isocyanine for reasons. Dry lotus. In the following, the plastic film processing step with the surface of the untreated plastic film is added to add value. Compared with the case of the film in the middle of the force = the right Tg of the propylene S-70 alcohol is too low, the hardening before aging is not sufficient 'so the process of forming the composition of the adhesive is soft. There is some kind of connection between the parts of the film. "After aging, even if the adhesive layer is sufficiently cured, the Tg of the acrylic polyol as a raw material is low, and the cohesive force of the adhesive layer is insufficient, and it becomes difficult to ensure a large adhesion force: When the laminated body is placed under high temperature and high humidity for a long period of time, there is a tendency that the adhesion force is gradually lowered due to insufficient cohesive force of the adhesive layer. On the other hand, if the Tg of the acrylic polyol is too high, There is a tendency for the wettability of the substrate to be insufficient. Although the adhesion force after aging is somewhat larger than before aging, the hardened adhesive layer after crosslinking is too hard 'therefore there is an aging step In the present invention, the reason for obtaining the above excellent effect is that the Tg of the acrylic polyol is set to a temperature range which is not too low and not too high (specifically, more than 10 〇). C is 50 ° C or less), and further based on the specific hydroxyl value, specific NCO / OH equivalent ratio, 201239057.

~r I The range of molecular weights, thereby synergistically exciting the activity of the movement of the c-polyol at the molecular level of the molecule, so that the docking hoof is known as the range of αΐ~1〇 In particular, 0.5 i shows the balance: the balance of ^ and after the aging step -, a. ^ ^ and surprisingly found that even before aging, the force. It has also been found that after the aging step, a high adhesion can be maintained after being placed under two humidity conditions. When a metal poise, a metal plate, or a metal film is used as the substrate, it is preferable that the adhesive composition for a laminated sheet of the present invention contains an anti-sintering coupling agent from the viewpoint of improving the adhesion strength. The oxime coupling agent is not limited to the following ones, and examples thereof include ethylene tris(Ρ-曱-milyl ethoxy) Wei, ethylene ethoxy wei, and ethylene trimethoxy wei and the like. Xenon (meth)propoxy-trimethoxy oxime, hydrazine methyl) propylene methoxy propyl triethoxy wei, and γ (meth) propylene methoxy propyl dimethyl Oxymethyl (10) and the like (methyl) propylene oxime iso; Ν 3,4-epoxycyclohexyl)ethyltrimethoxy zephyr, β-(3,4-epoxy% <hexyl)methyl three? Oxygen-sinter, β_(3,4-epoxycyclohexyl)ethyltriethoxydecane, Η3,4-epoxycyclohexyl)methyltriethoxydecane, γ-glycidoxypropyltriazine Epoxy decanes such as oxydecane and γ glycidoxypropyl triethoxy decane; Νββ(aminoethyl)γ-aminopropyltrimethoxydecane, Ν-β (aminoethyl) γ_Aminopropyltriethoxydecane, Ν-Ρ(aminoethyl)γ-aminopropylmethyldiethoxydecane, guanylpropyltriethoxydecane, γ- Aminopropyltrimethoxydecane, hydrazine-phenyl-7-amine 15 201239057, propyltrimethoxy sulphur, and N_styl _γ-aminopropyltriethoxy sulphur , class; and γ· County propyl trimethoxy Wei, and thiopropyl triethoxy Wei and other sulfur-containing Wei fresh. These compounds may be used singly or in combination of two or more kinds. The amount of the granules added in an amount of from 5 parts by weight to 3% by weight is preferably from 5 parts by weight to about 3 parts by weight per part by weight of the acrylic acid polyol (a). When the amount is from W by weight, the effect of improving the strength of the gold shot by the coupling agent is inferior; even if it is added in an amount of more than 5 parts by weight, the performance of the conversion to the above is improved. The adhesive composition for a laminated sheet of the present invention may be a so-called two-liquid mixed type adhesive in which a main component and a curing agent are mixed at the time of use, or a one-liquid type adhesive in which a main component and a curing agent are mixed in advance. . Further, the acrylic acid polyol (A) or the polyisocyanate g (B) of the present invention may be used alone or in combination. Further, other main agents or curing agents other than the present invention may be used singly or in combination. In general, τ, the main agent includes a C-racing: το alcohol (Α), a decane coupling agent, an organic solvent, and other additives, and the hardener includes a polyisocyanate (Β), an organic solvent, and other additives. As other additives, an adhesion promoter, a reaction accelerator, a leveling agent, a phosphorus-based or phenol-based antioxidant, and an ultraviolet ray may be formulated in the adhesive for laminating sheets of the present invention within the range not departing from the gist of the present invention. Stabilizers, metal deactivators, flame retardants, plasticizers, organic pigments, inorganic pigment additives. In the case of using a metal layer (metal foil, metal plate, etc.) as a sheet member, in the case of 201239057, in order to make the metal of the adhesive composition of the laminate of the present invention close to the south, a samaric acid compound such as a dish acid may be added. , partial linonic acid, pyrophyllin, phosphorous acid or esters of these acids. Further, the adhesive composition for a laminated sheet of the present invention can be used as a solar cell laminate in addition to being used as a surface protective sheet for producing a solar cell, and as a thickening agent (4). In this case, it is preferable to put an anti-caking agent. Further, an additive which is known as a follow-up can be disposed without limitation without departing from the gist of the present invention. For example, the limbs should be promoted, and specific examples thereof include metal catalysts such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dimaleate; Soil (5,4,0) deca-carbene-7, anthraquinone, 5-diazabicyclo(4 3 〇) daughter-in-5,6-di-ylamino],8-diazabicyclo(5) , 4, 〇) a tertiary amine such as eleven carbon thinner _7, such as a reactive tertiary amine such as diethanolamine. One or two or more kinds of reaction accelerators can be used as the reaction accelerator. Further, in order to improve the appearance of the laminate, a known leveling agent or antifoaming agent may be formulated in the main component. ° ^ homogenizing agent can be exemplified by polyether modified polydimethyl methoxy oxane, polyester modified polydimethyl wei yun, Qianji modified polymethyl silk Wei burning, ^ 妒 modified hydroxy containing poly Methyl decane, polyether ester modified hydroxy-containing polydimethyl hydride = decane, acrylic copolymer, methacryl oxime copolymer, di-modified polymethyl alkyl decane, alkyl acrylate Ester copolymers, alkyl methyl ether copolymers, lecithins, or mixtures thereof, etc. | 〇3 "ί匕17 20123903⁄4 Defoaming agents include anthrone resin, anthrone solution, and alkane A vinyl group is exemplified by a copolymer of a decyl acrylate and an alkyl methacrylate, or a mixture of such a defoaming agent. When a leveling agent or an antifoaming agent is added, one type of compound may be used independently, and two or more types of compounds may be used arbitrarily in combination. Further, 'as a known additive used in the present invention, in order to suppress the vaporization of the adhesive which is caused by the ultraviolet rays of the sun or the like over time, the adhesion of the adhesive due to heat such as solar heat over time is yellow A well-known phosphorus- or phenol-based antioxidant, ultraviolet ray, and metal deactivator are blended in the main agent. These additives may be used singly or in any combination of two. The phosphorus-based or phenol-based oxidizing agent, ultraviolet stabilizer, and metal deactivator used in the present invention are preferably 〇〇5 parts by weight based on 100 parts by weight of the solid content of the acrylic polyol (A). The range of parts by weight is more preferably 1 part by weight of hydrazine. If the amount is less than 0.05 by weight, a sufficient yellowing suppressing effect cannot be obtained. If the amount is 5 parts by weight, the adhesive strength of the adhesive is greatly deteriorated. As the curing agent, in addition to the above polyisocyanuric acid (B), a well-known sputum (for example, 2,5-dimethyl-2- oxone) may be optionally contained within a range that does not inhibit the effects of the present invention. Carbendene, or 2 2 —(1,4—butylene)·oxazoline) or anthraquinone compounds (eg, diammonium dibenzoate, diterpene sebacate, or diammonium adipate)肼) and so on. The solvent to be used in the present invention may, for example, be vinegar such as ethyl acetate, dibutyl citrate or celecoxib acetate; propylene, butyl hydrazine, isobutyl ketone, methyl

201239057 ~T ketones such as isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; aromatic tobaccos such as toluene and monoxylene; and toothed hydrocarbons such as dioxin and H gas , dimethyl hydrazine, dimethyl sulfonamide, and the like. These solvents may be used singly or in combination of two or more kinds. The non-volatile component (solids) of the adhesive of the present invention is preferably in the range of from 0% by weight to 50% by weight. The present adhesive can be adjusted by using a solvent as exemplified above. Next, a method of producing a back protective sheet for a solar cell using the adhesive composition for a laminated sheet of the present invention, and an example of a back protective sheet for a solar cell will be described. The manufacturing method or configuration of the back surface protective sheet for a solar cell is not limited to the following examples, and various manufacturing methods or configurations can be employed depending on the purpose or needs. As a solar cell module, a simple solar cell module has a configuration in which a filler or a glass plate is sequentially laminated on both surfaces of a solar cell unit as a solar cell element. Since the glass plate is excellent in transparency, weather resistance, and scratch resistance, it is now generally used as a dense sheet on the light receiving side of the sun. However, in terms of cost, safety, and workability, the company has developed a back surface protection sheet for solar cells other than glass sheets, which are replacing the glass. board. For the solar cell back protective sheet, there is a back surface protective sheet for solar cells, such as a plastic film such as a polyester film, a metal oxide on a polyester film, or the like, and a vapor deposition layer for producing a non-metal oxide. Metal layer = metal foil such as plastic film or aluminum foil, plastic film with a tantalum nitride layer, and the like. The layered 201239057 can be joined between the sheet members by using the laminate composition of the present invention. The back surface protective sheet for a solar cell composed of a plurality of layers can impart various properties by the multilayer structure. For example, by imparting insulation by using a polyester film, weather resistance can be imparted by using a fluorine-based film, and aluminum foil is used to impart water vapor barrier properties. As for the solar cell back protection sheet, it can be selected according to the product and use of the solar cell module. A vinyl fluoride perfluoroalkyl vinyl ether copolymer or a tetrafluoroethylene-specific resin film. Examples of the plastic film include a polyester resin film such as polyethylene terephthalate or polybutylene terephthalate, a polyethylene resin film, a polypropylene resin, and a t-chloroacetic resin. Membrane, polycarbonate resin film, polycrystalline resin film, poly(meth)acrylic resin film, polyvinyl fluoride, polyvinylidene difluoride, polytrifluoroethylene, polyethylene tetrafluoroethylene, Polytetrafluoroethylene, tetrafluoropropene copolymer

κ a is not in the raw materials. Month'j 20 201239057 • a. v ^ a L· Metal case can be listed as (4) or copper box. As a metal oxide or a non-metal inorganic oxide to be steamed, for example, an oxide such as a metal, a tin, a tin, or a sodium borax can be used as a solar cell module. Weather resistance, water vapor transmission, electrical insulation, mechanical properties, and packaging work during use. 4 j^b 'Laminated polybutylene terephthalate with a temperature-dependent property. A back protective sheet for a solar cell made of a vinegar-like resin film such as a vinegar, a polycarbonate, or a lipid film; in order to prevent a decrease in output of the solar cell due to the influence of water, it is preferable to have a layer of water a back protective sheet for a solar cell formed by vapor-transforming a plastic film of a vaporized metal oxide or a non-metallic inorganic oxide or a metal H such as n; in order to prevent appearance defects due to photodegradation; A back surface protective sheet for solar cells made of a fluorine-based resin film having good weather resistance. ◊In addition, in order to protect the solar cell module from damage, the solar cell rear protection sheet is damaged by voltage application. According to the power generation capacity of the solar cell unit, an electrical circuit requiring a partial discharge voltage of 700 ¥ or looov is used. Insulation or a structure including a foamed layer to increase a partial discharge voltage. As the electrical insulation property of the method of increasing the partial discharge voltage depends on the thickness of the film or the foamed layer, there is a tendency that the film or the foamed layer becomes a film. Recently, a composition using 1 〇〇 μιη to 300 μηι has been used. The formation of the agent layer is, for example, applying an adhesive composition on one side of a sheet member such as a plastic film, and volatilizing the solvent, and bonding it to another 5 21 201239057 laminated substrate at room temperature or It is made to be hardened by warming and is obtained by coating on any one of the sheet members: followed by coating the composition with heat and hardening, forming a subsequent layer, forming an adhesive layer w, coating other > The coating liquid for forming a component is formed by a heat or active energy sheet member. Examples of the apparatus for applying the adhesive composition to the sheet member include a knurling wheel coater (c〇_c boring machine, die coater, machine, bar coater, ===) :, reverse roll coater, knive coater (_ecoater), concave, micro gravure coater, etc. For the drying conversion meter on the surface of the layer, it is preferable that αι coffee 2~5〇 For roots, use ~Hg/m2~5Gg/m2. As a laminate substrate, select any substrate, and set it to 3 or more layers and then apply all or part of the layers. The composition of the hair styling agent is used in the middle. The bismuth bismuth: the coating liquid for yak formation can be exemplified by the formation of a resin film, a liquid Α resin surface, a polyethylene compound solution, a polypropylene system. Poly; system (4) ^ B_ resin solution, polycarbonate resin solution, solution + as a preferred example ' - ' " grid, lit for the solar cell back protection sheet required performance, price group A., choose a variety The manufacturing method or the method of the present invention will be described in more detail by way of example, but the following 22 201239057 I The examples of XV/- do not impose any limitation on the scope of the present invention. In addition, the evaluation of the examples f is carried out according to the following method. In addition, in the examples, the parts are not seriously injured, and the % is not wt〇/〇. The hydroxyl value represents mgK〇H/g. The number average fraction. The amount of the glass, the glass transition temperature, and the hydroxyl value can be determined by the following method: <Quantum average molecular weight> The measurement of the number average molecular weight is made by Tosoh Corporation. GpC (gel permeation chromatography) "HPC-8020" 'solvent uses tetrahydrofuran. The number average molecular weight can be obtained by standard polystyrene conversion. <glass transition temperature (Tg) > glass transition temperature (Tg) The measurement can be carried out by using DSC "RDC220" manufactured by Seiko Instruments Inc., and about 1 〇mg of the polycarbonate amino phthalate polyol synthesized by the following method is used in the measurement. A sample obtained by drying a solution of a carbonate amine phthalate polyol A_14 was placed in a DSC apparatus and cooled to 〇〇 by liquid nitrogen. After that, Dsc was obtained by heating at 10 ° C/min. Figure to find the glass transition temperature. t; hydroxyl value> The hydroxyl value can be determined by dissolving about 2 g of the sample in about 10 ml of pyridine, and adding a pre-adjusted acetic anhydride/pyridine volume ratio of 15/85. The mixed solution was allowed to stand for 5 hours at 5 m. Thereafter, 1 ml of water and 1 ml of ethanol were added, and the solution was titrated by 氢氧化.1 n of potassium hydroxide (ethanol solution). The indicator was phenolphthalein. (Production of Acrylic Polyol (A)> (Synthesis Example A-1) 100 parts by weight of ethyl acetate was placed in a 4-necked flask equipped with a condenser, a nitrogen gas introduction tube, a dropping funnel, and a thermometer, and was raised 23 201239057x - · 1" After warming to 8 ° °c, add 4 7 parts by weight of buprenorphate vinegar by a dropping funnel for 2 hours, 55.5 parts by weight of base (10) acid vinegar, and acrylic acid-domain vinegar 1.8 parts by weight & azobisisobutyl butyl nitrile 2. 〇 by weight of a monomer liquid previously pre-mixed. Thereafter, the reaction was allowed to proceed for 1 hour, and then 2 parts by weight of azobisisobutylonitrile was added to carry out a reaction for 1 hour, and the above steps were carried out until the conversion of the monomer became 98% or more', followed by cooling. Then, ethyl acetate was added to obtain a 50% solid solution. (Synthesis Example A-2 to Synthesis Example A-18) The same procedure as in Synthesis Example i was carried out except that the molecular weight was adjusted by the addition amount of the polymerization initiator azobisisobutyl nitrile, and the results shown in Table 1 were obtained. The acrylic acid polyol of Synthesis Example A-2 to Synthesis Example a-18. In addition, the synthesis example A-15 is an acrylic polyol which is represented by the synthesis example 1 in the patent document 2. In addition, the cleverness in Table 1 is as follows. ΒΑ: butyl acrylate, hydrazine: ethyl methacrylate, Εα: ethyl acrylate, St: styrene, CHMA: cyclohexyl methacrylate, 2Εηα: 2-ethylhexyl acrylate, hydrazine: acrylic acid-2 -hydroxyethyl ester, 4-hydroxybutyl acrylate 24 201239057 [Table 1] Monomer composition number average molecular weight Tg (°C) Mean value (mgKOH/g) BA EMA EA St CHMA 2EHA HEA 4HBA A-1 42.7 55.5 1.8 —10000 15 8.6 A-2 42.7 55.5 1.8 35000 15 8.6 A-3 42.7 55.5 1.8 _ 60000 15 8.6 A-4 31.2 67.0 1.8 35000 30 8.6 A-5 20.2 78.0 1.8 35000 45 8.6 A-6 43.0 56.1 0.9 —35000 15 4.3 Α·7 41.4 55.0 3.6 ___ 35000 15 17 2 Α·8 39.5 53.3 7.2 35000 15 34.4 Α-9 42.7 55.5 1.8 _35000 15 8.6 Α-10 42.7 55.5 1.8 35000 15 8 6 Α·11 42.7 55.5 1.8 35000 15 8 6 A-12 42.3 45.5 10.0 2.2 35000 15 8.6 A-13 48.0 50.2 1.8 35000 15 8 6 A-14 68.0 20.0 10.0 2.0 50000 -20 9.6 A-15 70.0 10.0 10.0 10.0 25000 55 — A-16 42.7 55.5 1.8 6000 15 0.0 — A-17 42.7 55.5 1.8 J20000 15 - rnZ^ A-18 19.5 63.5 23.0 35000 <Example of formulation of adhesive composition> (Examples 1 to 13 and Comparative Examples 1 to 6) are 100 with respect to solid content In parts by weight of the acrylic acid poly-alcohol (A), the polyisocyanate (B) as a curing agent is formulated in the compounding ratio shown in Table 2, and the glycidyl group-containing compound as an additive is formulated. Mixture ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.) 3.0 parts by weight, & 0.01 parts by weight of dioctyltin dilaurate ("NEOSTANNU-810", 曰东化成八制造), further solidified with ethyl acetate The content is 30%. 25 201239057^ propylated acid polyol (A) polyisocyanate 数 数 number t average molecular s Tg (° 〇 value (mgKOH / g) type NCO / OH ratio ratio ratio example 1 Α-1 10000 15 8.6 Hardener A 2.0 10.2 Example 2 Α-2 35000 15 8.6 Hardener A 2.0 10.2 Example 3 Α-3 60000 15 8.6 Hardener A 2.0 10.2 Example 4 Α-4 35000 30 8.6 Hardener A 2.0 10.2 Example 5 Α-5 35000 45 8.6 Hardener A 2.0 10.2 Example 6 Α-6 35000 15 4.3 Hardener B 2.0 3.4 Example 7 Α-7 35000 15 17.2 Hardener B 2.0 13.4 Example 8 Α-8 35000 15 34.4 Hardener B” 2.0 26.8 Example 9 Α-9 35000 15 8.6 Hardener B 1.2 4.0 Example 10 Α-10 35000 15 8.6 Hardener B 4.0 13.4 Example 11 Α-11 35000 15 8.6 Hardener C 2.0 10.7 Example 12 Α-12 35000 15 8.6 Hardener C 2.0 10.7 Example 13 Α-13 35000 15 8.6 Hardener A 2.0 10.2 Comparative Example 1 Α-14 50000 -20 9.6 Hardener D 4.5 15.0 Comparative Example 2 Α-15 25000 55 48.3 Hardener E 0.5 8.0 Comparative Example 3 Α-16 6000 15 8.6 Hardener A 2.0 10.2 Comparative Example 4 Α-17 120000 15 8.6 Hardener A 2.0 10.2 Comparative Example 5 Α-18 35000 15 110. 0 Hardener A 0.5 32.7 Comparative Example 6 Α-2 35000 15 8.6 Hardener A 12.0 61.3 *ι ratio = main agent: hardener (solid ratio) [Table 2] *2 Relative to (A) 100 parts ( For the non-volatile component, 3.0 parts by weight of KBM-403 (矽炫 coupling agent) is formulated. *3 Relative to (A) 100 parts by weight (non-volatile content), U-8100.01 heavy loan is formulated as a reaction promotion *4 Hardener A: TakenateD-160N (manufactured by Mitsui Chemicals Co., Ltd., modified T1^p adduct of hexamethylene diisocyanate) Hardener B: TakenateD_178N (manufactured by Mitsui Chemicals, Inc. Amidoisoformate-based allophanate modification) Hardener C: isophorone diisocyanate isocyanurate modification) Hardener D: Sumidur N3300 (manufactured by Sumika Bayer Urethane, Liu Yajia Equivalent urethane modified product of bis-isodecanoate) Hardener E: Sumidur N3200 (semi-urea modified product of succinyl diisocyanate manufactured by Sumika Bayer Urethane Co., Ltd.) <Production Example of laminated film 1 Using each of the adhesive compositions of Examples 1 to 13 and Comparative Examples 1 to 6 to dry coat The amount is 4 g/m 2 to 5 g/m 2 , and the adhesive composition is applied to a polyester film [made by Toray Industries, Lumirror X-10S, thickness 50 μπι] by a dry laminator. Processing surface. Then, 26 201239057κ ~τ χ ντ^·ν/ι/ιΓ After the solvent is volatilized, it is laminated on another poly-[[Dongli company,

Lumlr: or x-los, thickness 50 handsome] on the corona treatment surface. Thereafter, the adhesive film is hardened by a hardening treatment (aging) for 3 days to form a laminated film 1. Further, the production example of the laminated film 2 was produced by using the laminated film 1 according to the production method of the laminated film 1 described above, and using the laminated composition of the laminated film 1 to produce a [corona" polyester film. The laminated film 2 of the /layer layer / aluminum case]. &lt;Production Example of Laminated Film 3&gt; Using the adhesive compositions of Examples 1 to 4 and Comparative Example 2 and Comparative Example 3, steaming with SiO2 (4) (4) was prepared in accordance with the method for producing the laminated film 1 The laminated film in which the plating layer and the adhesive layer are in contact with each other to form a structure of [corona treated poly S film/sequence/dioxygen (4)] is shown in Table 2 and Table 3, and Examples 1 to 13 are shown. Comparing m to the combination of the main agent and the hardener in Comparative Example 6, and the initial adhesion of the laminated film crucible to 1000 hours, 2 hours, and 3000 hours after exposure to an environment of 85 C and 85% humidity. Then force. Further, Tables 1 and 5 show the use examples 1 to 4 and comparative examples. 2. The initial adhesion of the laminated film 2 and the laminated film 3 of Comparative Example 3 was exposed to an adhesion of 1 hr, 2 hr, and 3000 Å in an environment of 85 C and 85% humidity. The specific reading method will be described below. <Adhesion test before aging and after aging> The laminated film 丨, the laminated film 2, and the laminated film 27 201239057r 3 before and after aging were cut into 200 mm &gt;&lt; 15 mm, respectively, at 25 After standing for 6 hours in an environment of °C and a humidity of 65%, a tensile tester was used according to the test method of ASTM-D1876-61 at a load speed of 300 mm at 25 ° C and a humidity of 65%. The T-peel test was performed at min. The peeling strength (N/15 mm width) between the PET film/PET film, the PET film/aluminum foil, and the PET film/cerium oxide vapor-deposited polyester film was indicated by the average value of the five test pieces. &lt;Adhesion test after moisture heat resistance test&gt; The laminate after aging was cut to a size of 200 mm to 85. (:, 1000 hours, 2000 hours, 3000 hours in an environment of 85% humidity. Thereafter, after standing for 6 hours in an environment of 6: humidity, 65%, according to the test method of ASTM-D1876-61 The T-peel test was carried out using a tensile tester 'at 25 ° C and a humidity of 65%' at a load speed of 3 〇〇 mm/min. The PET film/PET film was represented by the average of five test pieces. Peel strength (ΝΠ5 mm width) between PET film/interior box, PET film/cerium oxide vaporized polyester film. &lt;Evaluation Criteria&gt; [Aging just test] ◎Excellent in practical use :3 N/15 mm or more 〇 Practical area: 2 N/15 mm~3 ΝΠ5 mm △ Practical lower limit: 1 N/15 mm ~2 N/15 mm X is not practical: less than 1 N/15 mm [After the test , adhesion test after heat and humidity resistance test] ◎ excellent in practical use: 5 N / 15 mm or more. Practical area: 4 N / 15 mm ~ 5 N / 15 mm 28 201239057 ^ ~ riv / ^ v / l / α Γ △ Practical lower limit: 2N/15mm~4N/15mm x not practical: less than 2N/15 mm [Table 3] Next, the strength of the heat and humidity resistance test before and after aging (N/15 mm) 85 ° C, 85% RH After the passage of time Strength (N/15mm) Old w: before aging at 4〇°C 3夭 1000 hours after 2000 hours 3000 hours after example 1 2.4 〇4.6 〇4.7 〇4.4 〇4.0 △ Example 2 3.3 © 6.2 ◎ 6.3 ◎ 6.1 ◎ 6.0 ◎ Example 3 2.2 〇5.6 ◎ 5.4 ◎ 5.5 ◎ 5.3 ◎ Example 4 2.8 〇 6.1 ◎ 6.3 ◎ 6.2 ◎ 6.0 ◎ Example 5 1.8 △ 4.7 0 4.9 〇 4.9 0 4.6 〇 Example 6 3.1 ◎ 5.2 ◎ 5.4 ◎ 4.6 0 4.2 0 Example 7 3.4 © 5.5 ◎ 5.1 ◎ 4.5 0 4.1 〇 Example 8 3.2 ◎ 4.7 〇 4.7 〇 4.2 0 3.7 Δ Example 9 3.5 ◎ 4.5 〇 4.6 〇 4.2 〇 3.8 Δ Example 10 3.3 ◎ 5.9 ◎ 6.0 ◎ 4.9 〇 4.7 〇 Example 11 3.1 4,2 〇4,3 〇4.1 〇3.4 Δ Example 12 3.1 4.6 0 4.6 〇4.3 〇3.2 △ Example 13 2.8 ◎ 6.3 ◎ 6.3 ◎ 6.0 ◎ 5.9 ◎ Comparative Example 1 3.2 ◎ 3.9 Δ 3.4 Δ 3.1 △ 2.9 △ Comparative Example 2 0.1 X 1.2 X 0.9 X 0.7 X 0.3 X Comparative Example 3 0.3 X 3.1 Δ 2.8 Δ 2.2 X 1.4 X Comparative Example 4 0.5 X 3.7 Δ 3.8 Δ 3.2 Δ 3.1 Δ Comparative Example 5 4.5 ◎ 1.9 X 1.5 X 0.5 X 0.1 X Comparative Example 6 Produces 4 suspected gels when preparing the adhesive, because This is not applied to the coating [Table 4]

Aluminum foil / treated polyester film adhesion strength and heat resistance test before and after aging strength (Ν / 15 mm) 85 ° C, 85% RH after the passage of time after the strength (N / 15mm) before aging at 40 ° After aging for 3 days, after 1000 days, after 1000 hours, after 2000 hours, after 3000 hours, Example 1 2.1 〇 4.4 〇 4.8 〇 3.9 △ 3.7 △ Example 2 3.2 ◎ 5,7 ◎ 5.4 ◎ 5.1 ◎ 4.6 0 Example 3 2.3 〇 4.7 〇 4.3 〇 4.2 0 4.1 〇Example 4 2.5 〇4.5 〇5.1 ◎ 4.7 〇4.2 〇Comparative Example 2 0.6 X 2.5 Δ 2.7 Δ 2.3 X 1.4 X Comparative Example 3 0.8 X 2.8 Δ 2.9 △ 2.3 △ 1.5 X 29 20123905^ [Table 5]

矽Evaporation of polyester film/treated polyester film and subsequent strength before and after aging of the source heat test 85 Ϊ, 85% RH a a# P3 level after the bonding strength (N / 丨 5 mm) old - 匕Before 4 (3 days after TC to 1000 hours after 2000 hours and 2000 hours after 3000 hours) Example 1 2.6 〇 4.8 〇 4.8 〇 3.5 Δ 3.1 △ Example 2 3.8 0 5.2 ◎ 4.9 〇 4.7 0 3.9 Δ Example 3 2.4 0 5.5 ◎ 4.8 〇4.3 0 3.6 Δ Example 4 2.7 0 5.2 ◎ 4.5 〇4.3 〇4.1 0 Comparative Example 2 0.6 X 3.1 △ 2.5 Δ 1.9 X 0.9 X Comparative Example 3 U.3 X 2.5 △ 2.3 Δ 2.1 △ 1.9 X As shown in Table 3 It can be seen that the following results are obtained: the adhesive composition of the example is excellent in adhesion force both before aging and after aging. Moreover, it is known that an excellent adhesion force is obtained after the resistance/heat resistance test. The adhesive strength is maintained, so the example of the adhesive composition is particularly suitable for long-term heat and humidity resistance for outdoor use. JIS C 8917 (Environmental test method and endurance test method for crystalline solar cell module) will be 85t: The humidity is 85%. ^ Mosquito is _ sex test B · 2, it is known that the test of riding harshness in this example, the performance is more than _ hours, after the long time of the time can be transferred to the next time, the composition of the next The material has sufficient long-term heat and humidity resistance. ° &quot; The back protective sheet for solar cells has such a long enough interlayer adhesion strength (laminate strength) to maintain the layer during the test, so it can be used in the solar cell component. There is no decoupling-step to help maintain the longevity efficiency of solar cells. 'Long is related to the popularity of solar cells. It is also helpful for environmental protection from the perspective of the longevity of solar cells.' Other than stone fuel 201239057 The composition of the medicinal agent can be used as a laminate material for outdoor industrial layers such as buildings (barrier (4), outer lining material, barrier agent 2 material, solar cell panel material (back protection sheet for solar cells, too = pool surface) Protective sheet), window material, outdoor flooring materials, materials, automotive parts, etc.) provide strong bonding strength with an adhesive. 2) The strength of the subsequent strength due to water content during outdoor exposure over time 'Li is lower, and can maintain strong bonding strength over a long period of time. Example 1 is a case where the glass transition temperature of the bupropion acid polyol (A) is j〇c 'lower than urc. It is the result of obtaining a left-handed force of 'only 3 (10) 5 mm) even in the case of surface treatment. . In contrast, the glass transition temperature of the case 2 (B) is higher than 55 〇C, which is higher than the case of thieves. As a result of the evaluation, there was no wettability to the substrate in the county, so the initial adhesion was extremely small, and (4) the heat-heat test was further lowered. Comparative Example 3 is an example in which the number average molecular weight of the acrylic polyol (A) is 6,000 K 10,000. It can be seen that the result of the evaluation is that the cohesive force of the adhesive before the aging step is insufficient, and the adhesion force before the aging step is extremely small. In the case of industrial production, the laminated body in a state of being wound into a roll shape ages the winding core in the vertical direction. If the adhesion force before the aging step is extremely small, the winding is easily spread at the time of aging, and is not suitable for industrial production. Comparative Example 4 is an example in which the number average molecular weight of the acrylic polyol (a) is 12 Å, and 〇〇〇 ' is larger than ιοο, οοο. It can be seen that the result of the evaluation is that the wet/wideness of the pet film is insufficient, and sufficient adhesion cannot be obtained before aging. Compared with the ratio of 31 201239057 • · W w γ J t , the winding is easy to disperse during aging, which is not suitable for industrial production. Moreover, after the heat and humidity resistance test, no heat and humidity resistance test was found. The force is reduced, but since the force is originally low, it is known to be worse than the example. Comparative Example 5 is an example in which the OH value of the acrylic polyol (A) was 110.0 and more than 100. As a result of the evaluation, it was found that the crosslinking became excessive and it became a very hard cured coating film, which was inferior in adhesion. Comparative Example 6 is that the compounding amount of the polyisocyanate (B) is NC〇/〇H=12^. It is understood that the result of the 5-flat mussel is that the reaction with the acrylic polyol (A) is carried out before the coating to produce a gel. Therefore, it is impossible to apply. This application claims the priority of this patent application No. 2011-030369 filed on February 16, 2011 with the Japan Intellectual Property Office. The contents disclosed in the special injection request are fully integrated into this statement [ Industrial Applicability] The adhesive composition for laminated sheets of the present invention is a bonded object for joining the same or different raw materials, for example, in the joining of a multi-layered laminate of a plastic-based raw material and a metal-based raw material. Use as appropriate. Of course, it is also suitable for the joining of plastic raw materials and metal-based raw materials. The composition of the present invention can maintain a high adhesion even when exposed to a high-temperature and high-humidity environment. Therefore, it is a multi-layer laminate material (barrier material, exterior wall material, roofing material, sun) for outdoor industrial applications such as buildings. ▲, pool panel materials (solar battery surface protection sheet, solar cell surface protection ^), window * materials, outdoor flooring materials, lighting protection materials, automotive parts, etc. are suitable for the adhesive. Can be used for a long time Since the time passes through the dimension 32 201239057, it is particularly suitable for applications requiring strong environmental resistance, such as the formation of a back protective sheet for solar cells. Moreover, it is also suitable for the formation of a surface protective sheet for solar cells. The laminated sheet adhesive composition of the invention exhibits a high adhesion between the layers especially for the surface treatment layer containing the plastic film, and can also be suitably applied to the surface untreated raw material (including the untreated plastic surface). In the film) [Simplified description of the diagram] [Explanation of main component symbols] No 0 33

Claims (1)

201239057, VII. Patent application scope: 1. A laminated tablet connector composition comprising an acrylic polyol (A) and a polyisocyanate (B), the acrylic polyol (A) having a number average molecular weight of 1 〇, 〇〇〇~100,000, and the pass value is 1 mgK〇H/g~1〇〇mgKOH/g, and the glass transition temperature (Tg) exceeds i〇°c and is less than 5〇°c, derived from the above The equivalent ratio of the hydroxyl group of the acrylic polyol (A) to the isocyanate group derived from the polyisocyanate (B) is 〇~1〇2. The laminated sheet according to the above aspect, wherein the polyisocyanate (8) comprises a polyisocyanate derived from an alicyclic diisocyanate or an aliphatic diisocyanate. | If you apply for a patent range! The composition for a laminated sheet according to the above aspect, wherein the back sheet of the sheet-like member is formed by a back surface protective sheet for connecting the sheet members to each other. The back surface protective sheet for a solar cell, which is laminated by at least two or more layers of a thin layer formed by a smear of a smear of a smear of a smear of a smear of a smear, and a smear of a smear of a smear. ~Γ Λ. IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None. 201239057ί -γ χ \j^\j^riL 1 is the Chinese manual of No. 101104898. There is no slash correction. This is the date of the invention: 1st, 1st, June 15th, invention patent specification 2 (this manual format 'order, please do not change ※Please do not fill in the ※) ※Application number: ※Application曰: ※^(:Classification·· ! I. Invention name: (Chinese/English) Adhesive composition for laminated sheets and back protection sheet for solar cells ADHESIVE COMPOSITION FOR LAMINATING SHEET AND BACK PROTECTIVE SHEET FOR SOLAR CELL II. SUMMARY OF THE INVENTION: An adhesive composition is provided which exhibits a high adhesion between various sheet members, particularly between layers comprising a plastic film surface treatment layer. It is suitable for wearing a back protective sheet for solar cells even when exposed to a high temperature and high humidity environment, and is suitable for wearing a back protective sheet for a solar cell. The adhesive sheet for a laminated sheet of the present invention includes an acrylic polyol (A) and a polyisocyanate ( b), the number average molecular weight of the propanol polyhydric alcohol (Α) is 10,000 〜 〇〇, 〇〇〇, and the value of lmg KOH / g ~ 100 mg KOH / g 'Additional glass transfer The degree is more than 10 ° C and 50 ° C or less, and the equivalent ratio NCO / OH of the light base derived from the acrylic polyol to the isocyanate group derived from polyisocyanate (B) is 〇·1 to 10. Abstract: An adhesive composition f〇r fabricating a back 201239057 Hiozopm is No. 101104898 Chinese manual without picture correction period: June 15, 101, invention: [Technical field of invention] The present invention is About the use of the technology + the back protection sheet for the pool. The composition of the carrier for the laminated sheet and the solar power [Prior Art] Near the 'materials for the outdoor production, solar panel materials, windows Material J: The protective material, the automobile parts, and the late (four) smear to the material of the slab material 'day' only) the film f is a hundred layer (composite) layered body is put into practical use. More than two ί" raw materials or _ _ original (four), etc. ϋ two? evaporation 臈 。. Plastic raw materials can be cited polypropylene umbrella chaos, gas resin, acrylic resin plastic ^, _ plate 'in the table (four) into There are dioxide (four) Na, a plastic film of the organic layer, etc. Metal enamel... and film 4..., the adhesive used in the machine is first; =:== carbazate-based adhesive. In the case of the above-mentioned conditions, the above-mentioned conditions are satisfied, and the above-mentioned conditions are satisfied. Condition 1: In the room after storage for 16 Μ, at a high acceleration temperature atm measured by an unsaturated vapor stress of a pressurized sputum: at a temperature of at least 1.05 1 N/15 mm to 201239057 Revised date: June 1st, 1st, June 15th is the Chinese manual of No. 101104898. There is no slash correction; Condition 2: In the same room as the evaluation device using pressurized steam, After 168 hours at 105 ° C and 1.05 atm, there is no delamination associated with it. In particular, a plurality of polyurethane-based adhesives in which a crosslinking agent is added to each of the six types of polyols of polyol A to polyol F (refer to Patent Document 1 is a second to a second item of the patent application. Patent Document 2 describes a rear film for a solar battery module. ·,. -------V ^ iitL nj 1^/η , its . A laminate comprising at least two substrates bonded together by an acrylic transfer agent. More specifically, an acrylic primer is proposed as a C-catalyst having hydrolysis resistance, insulation resistance, and moisture transmissibility, and the acrylic acid receptor contains a compound represented by the general formula (I). A propylene-based polymer obtained by polymerizing a monomer component of a monomer (refer to Patent Application No. 2 of Patent Document 2). CH^C^R^CO-OZ (I) In the formula, R1 represents a hydrogen atom or a fluorenyl group, and z represents a hydrocarbon group having a carbon number of 4 to 25. In addition, as disclosed in Patent Document 3 and Patent Document 4, Patent Document 3 and Patent Document 4 disclose an adhesive composition suitable for use under the mouth: untreated plastic film. The surface is used in the next sheet with other substrates. [Prior Art Document] [Patent Document] 201239057 ΗΙΌΖΟρίΐί For the Chinese manual of No. 101104898, there is no slash correction. This α w is fixed for a period of time: 1 6 1 June 15 曰 [Patent Document 1] International Publication No. 2007-148754 [Patent [Patent Document 2] Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. Under the severe conditions, the adhesion is stably maintained over a long period of time, and it is important that the strength is stable even after passage of time. Recently, as disclosed in Patent Document 3 or Patent Document 4, the untreated surface of a plastic such as a film which has not been subjected to surface treatment can be closely adhered to another substrate. (4) The nuclear spine is light and the manufacturing process can be shortened, so the cost can be reduced. However, on the other hand, it has also been applied to the adhesive composition which has been subjected to the (4) surface treatment technique from the prior art, and which has an excellent adhesion property to the adhesive composition and (4). The demand is also getting higher. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a laminated sheet female composition and a solar cell surface protection sheet, wherein the laminated sheet is composed of an adhesive composition between various #-shaped members, The system exhibits a high adhesion force in the phase of the surface layer of the plastic film, and can be turned into a high-side environment to expose the solar cell back protective sheet. ^Wei Qiao et al. have made intensive studies to solve the above problems, and: f Ϊ 解决 can solve the above-mentioned lessons by using the adhesive composition for laminated sheets shown below! Thus, the present invention has been completed. Also in the laminate of the present invention, the use of the subsequent stilettos includes the inclusion of propyl benzoate 201239057 ~ Τ X is the Chinese manual of No. 101104898 without a slash correction. Amendment date: June 15, 2011, alcohol (Α) and polyisocyanate (Β), the acrylic polyol (Α) has a number average molecular weight of 10, 〇〇〇~100,000, a hydroxyl value of ImgKOH/g to 100 mgKOH/g, and a glass transition temperature (Tg) exceeding l〇°c and In addition, the equivalent ratio NCO/OH of the radical derived from the acrylic polyol (A) to the isocyanate group derived from the polyisocyanate (B) is 0.1 to 10. Preferred examples of the polyisocyanate (B) include alicyclic groups Example of Polyisocyanate Derived from Diisocyanate or Aliphatic Diisocyanate The laminate of the above-mentioned laminated sheet is used in the manufacture of a back protective sheet for solar cells comprising two or more sheet members, and is suitable for use in the production of a back protective sheet for solar cells comprising two or more sheet members. At least a portion of an adhesive layer for joining the sheet members to each other is formed for use in the following applications. In addition, the back surface protective sheet for a solar cell of the present invention comprises: two or more sheet-like members laminated by the above-mentioned adhesive layer by the laminate #4 secret agent shim (4) of the above aspect. [Effects of the Invention] According to the present invention, it is possible to obtain an excellent effect that a laminate composition and a back surface protective sheet for a solar cell, which are interposed between various sheet members, can be provided. It is a back-side protective sheet which exhibits a high adhesion force between the layers including the plastic layer and the high-temperature humidity. [Embodiment] 7 201239057 Η-ιυζ, υριιΙ Correction period: June 15th of the following year No. 101104898 Chinese manual without slash correction This embodiment of the present invention will be described in detail below. Further, other embodiments may be included in the scope of the present invention as long as they conform to the gist of the present invention. Further, in the present specification, the description of "arbitrary number Α to arbitrary number Β" means a range of the number A and the number A, and is a range of the number B and the number 6. Further, the description of "(meth)acrylonitrile" as described in the specification and the patent application includes any compound which is referred to as "acrylofluorene" and a compound which is referred to as "mercaptopropene". Further, it is similarly defined in "(indenyl) propylene group" and "(meth) acrylate". &lt;Protonic acid polyol (A) &gt; The acrylic polyol (A) can preferably be a mono(meth)acrylate monomer having a hydroxyl group and a mono(indenyl)acrylate monomer having no hydroxyl group. Copolymer. The mono(meth)acrylate monomer having a hydroxyl group is a monomer having a fluorene (fluorenyl) acrylonitrile group and one or more hydroxyl groups in the ruthenium molecule. Preferable examples thereof include a mono(meth) acrylate monomer obtained by a reaction of a divalent alcohol with (meth)acrylic acid, and an ε-caprolactone modified (meth)acrylic monomer. If the number average molecular weight of the acrylic polyol (Α) is the same degree, the part irrelevant to the copolymerization of the mono(meth)acrylate monomer, that is, via the ester bond, is considered from the viewpoint of the adhesion. The carbon number of the partially bonded portion (alkyl or alkenyl group, hereinafter referred to as "side chain portion") is preferably from 1 to 17, more preferably from 1 to 9, more preferably丄~3. The side chain portion forms a side chain of an acrylic polyol (Α) after copolymerization. The carbon number of the side chain portion of the mono (meth) acrylate monomer is generally about 1 to 30, but if the amount of the acryl polyol (Α) is equal to the molecular weight, the side chain portion The shorter, the acrylic plural 201239057 Ί i. is the first 〇11 〇 side correction date: June 15, 101, the more positive the main chain of alcohol (A) becomes longer. The mechanical properties of the crucible (and the body of the mountain ^ ..., the fruit of the hardened joint layer is increased by 7 is the elongation) and the force is increased. For example, 幻===_, (methyl)-propane _, _ ding: § 夂酉曰, (poly) 乙二Alcohol mono (meth) acrylate vinegar, etc. Yuan 卜 ( (five) (A f) C, m propyl vinegar, etc. by the 3 〇〇 and its eve "and the single (meth) acrylate passed § The body can also be used as an early (meth) acrylate monomer containing a thiol group. The mono(methyl) propyl acetoate s monomer can be suitably selected from the radically polymerizable monomer of the prior ring 丨舆 a And suitable examples are as follows: linoleum (meth) propyl acetonate n-butyl vinegar, (meth) acrylic acid isobutyl vinegar ^ propyl glycerol third vinegar, (mercapto) acrylic acid _2 _ B Hexyl vinegar, (meth) propyl, n-octyl ruthenium, (meth)acrylic acid lauryl vinegar, (meth)acrylic acid tridecane =, (methyl acid hard fat Gu et al (methyl) _ Weiji § A long-chain (meth)acrylic monomer represented by a monomer, acrylonitrile, etc. / In addition to the above-mentioned hydroxyl group-containing (meth) acrylate monomer and non-3 carboxylic acid (f-based) acrylic acid In addition to the ester monomer, it can also be copolymerized with other singles. For example, a carboxyl group-containing monomer such as (meth)acrylic acid, maleic acid or maleic anhydride or an anhydride thereof, or a vinyl monomer such as styrene, etc. Further, a group-containing (meth) acrylate monomer The single (meth)acrylic acid® fluorene monomer having no hydroxyl group may be used alone or in combination of two or more compounds. The same applies to the case of using other monomers. The number average molecular weight of the acrylic polyol (A) must be 1 〇, 〇〇〇~1 〇〇, 〇〇〇. Further, preferably 1 〇〇〇〇 9 201239057 ^ιυζυριχΐ is the 101 HM898 Chinese The specification has no slash correction. The revision period is: June 15th to 70,000, more preferably 25,000 to 50,000. The adhesive composition for laminated sheets of the present invention (hereinafter also referred to as "adhesive composition" A laminated sheet obtained by laminating two or more sheet-like members, for example, a back protective sheet for a solar cell, can be obtained, for example, by the following steps: Applying an adhesive composition to a joint surface of one of the sheet-like members It is dry. Its Then, the other sheet-like members are superposed on the adhesive layer, and are obtained by hardening the adhesive layer by a step called "aging" which is stored for 2 曰 to 1 week in an environment of 4 〇t to 60 c. In the case where the number average molecular weight of the acrylic polyol is less than 10,000, there is a tendency that the cohesive force of the adhesive layer before the aging step is insufficient, and the adhesive force before the aging step becomes small. In the case of industrial production When the state of winding is to_ the layer body is subjected to aging in the vertical direction of the winding core under the reading condition. If the force before the aging step is small, the greening is performed when the aging is progressing, which is not suitable for In addition, if the production is less than 1 〇, the cohesive force after the aging step tends to be insufficient, and as a result, the refractory property is lowered and delamination occurs. Further, if the number average molecular weight of the acrylic polyol exceeds _, 〇〇〇, the viscosity of the adhesive becomes high, and the wettability of the sheet member tends to decrease, and as a result, the force becomes small. The initial force of the shaft is increased due to aging. U'j is larger than I', but there is a gradual decrease in the enthalpy of the shaft. After 3000 hours, it is lower than the lower limit of use: 'And the analyzer (G) ί里均分子# is obtained by gel permeation chromatography (GPC) and is converted to polyphenylene (10). More ^ 10 201239057 -rlx 1 is the third line of the Chinese manual. In the first half of the year, the numerical average molecular weight in the present invention is a value obtained by the measurement method described in the examples described later, and the same applies to the glass transition temperature production and the NCO/OH equivalent ratio. The value obtained by the method of the ten households ^^ described later is shown. ° The hydroxyl value of the acrylic polyol (A) is determined by the content of the mono(methyl)propane S monomer containing a hydroxyl group. In the invention, the hydroxyl value must be 1 mgKOH/g~1〇〇mgK〇H/g. Further, more preferably 4 〇mgK〇H/g~40 mgKOH/g. If less than 1 mgKOH/g, then it is stored. 2 The tendency to crosslink with the isocyanate hardener is lowered, and there is a tendency to reduce the heat and humidity resistance. Moreover, if it exceeds l 〇mgK〇H/g, although it may exhibit an adhesive force before aging, but the crosslinking density tends to be high after aging, and there is no possibility of exhibiting sufficient adhesion force, and further resistance to moist heat is further enhanced. Further, in the present invention, the glass transition point (Tg) of the acrylic polyol (A) must exceed 1 (rc and 5 〇. 匸 or less for the reason described later. Further, more preferably It is more than 1 (rc and is 3 (rc or less. ^ &lt; polyisocyanate (B) &gt; Polyisocyanate (B) is, for example, a compound derived from a well-known diacetoic acid vinegar, without limitation Known compounds are used, for example, from 2,4-toluene diisocyanate (alias: 2,4_TDI), 2,6-toluene diisocyanate ^ (alias: 2,6_TDI), xylene diisocyanate Purpose (alias: xm), diphenylmethane diisocyanate (alias: MDI), isophora diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate (alias: Η〇ι), bis(4_isocyanate Cyclohexyl)methyst, or hydrogenated diphenyl carbaryl diisocyanate 201239057 _June 15 曰Hiozupul is No. 101104898 Chinese specification without a slash correction of a compound derived from a diisocyanate such as an ester, that is, the diisocyanate, the tri-methyl propyl sulphide adduct, a biuret type, a prepolymer having an isocyanate residue (a low compound obtained from a diisocyanate and a polyhydric alcohol), a uretdione having an isocyanate residue, and a urea ruthenic acid dimer: The compound and the block isocyanate. The polyiso-acid acid (^) may be used alone or in combination of two or more. From the viewpoint of the viscoelasticity of the cured coating film after self-crosslinking, the polyisocyanuric acid (B) is preferably a polyisocyanate derived from an alicyclic diisocyanate or a fatty bis-isocyanate. More specifically, examples of the alicyclic monoisocyanate include isophorone diisocyanate, methyl-2,6-cyclohexanedicarboxylate, and the like. Further, examples of the aliphatic diisocyanate include hexamethylene di- and penta-indenyl diisocyanate. Further, as the derivative of the above-mentioned sulfonium ring diisocyanate and the aliphatic diisocyanate compound, it is an isocyanate, a methyl methyl ester adduct, a monourea type, and an isocyanate residue. Prepolymer (from II, = low polymer), with an isothermal acid residue =; carboxylic acid vinegar, or a composite of these. Gland such as two === hard money degree of love, it is better to use a book - heterozygous self-intention (alias: xm), although: between the two and the aromatic ring with a tender base, cool, Faster, it is better in terms of shortening the aging time. It is 5^=isocyano-(8), and the isocyanate group concentration is preferably t/ί)~30 wt%. In addition, in the festival, the concentration of D, the ester group is obtained in (8), and the isocyanate is obtained by the method. The titration is made by n-butylamine/hydrochloric acid. 12 201239057 Revision date: June 15, 2011 It is evaluated by the Chinese manual No. 101104898 without the slash correction method. Specifically, after dissolving the sample in dry toluene, an excess of dibutylamine solution is added and reacted by hydrochloric acid. The remaining di-n-butylamine was back-titrated, and the inflection point on the titration curve was used as the end point. The isocyanate group content was calculated based on the titration to the end point. The polyisocyanate (B) can be used in an amount equivalent to the nc〇/〇h equivalent ratio of the acrylic acid polyol (a) = hydroxyl group to the isocyanate group derived from the polyisocyanate (B), and the NC 〇 / 〇 H equivalent The ratio is set to 〇丨~1〇. More preferably, the two CO/OH equivalent ratios are 〇.5 to 6. If it is insufficient, there is a tendency for the force to decrease after exposure to indoors and outdoors. Further, when it exceeds 10, there is a tendency that the adhesion force after the initial aging is lowered. The NC0/0H equivalent ratio can be obtained by the following mathematical formula (1). NCO/OH ratio, isocyanic acid _ required amount (parts by weight) χ (56i / 〇hx (NCO% / (42xl00)) x (1, polyol $)) Mathematical formula (1), mouth ~ Liu Lide order The composition of the agent by filling up == 2 can be ascertained by satisfying all of the following conditions. That is, the glue 2: === r is in the plastic =:; environment can also maintain high == system =: average molecular weight, (ϋ) specific range of / · · < special range of the number of translation temperature (For example, the glass of the C. serrata range is used to ride CA), and further (iv) is derived from 13 201239057 Ηΐυζ, υριιι is the Chinese manual of No. 101104898. There is no slash correction. This revision date: 1〇1年六月15曰The reason for the isocyanation of the base group of the acrylic polyol (4) and the equivalent ratio NCO/〇H derived from the polyacetate group is described. K special "complement. In the following, the untreated plastic film layer with the laminated surface is added to the surface by the corona discharge, etc., and the additional value is partially added. In the case of the force, it is necessary to have a two-two surface untreated plastic film compared to the laminate of the acrylic polyol m. The hardening is not too low, and the adhesive layer is before the aging. IB !, therefore, the adhesive composition of the adhesive is a layer of adhesive. The adhesive force is soft and can be expressed between the sheet members. 亦 2 = bucket, after aging, even if the adhesive layer is sufficiently hardened, The cohesive force; the Tg of the foot reading is low and there is a layer of the adhesive layer. In addition, if the lyrics are inclined to be mixed with A_. The tendency is: the ground is placed under high temperature and high humidity, and the force is gradually lowered. If the cohesive strength of the layer of the agent is insufficient, the Tg of the acid of the binder is too high, and there is a certain amount of the base ratio. Although the adhesion after aging is harder than the pre-aging phase, there is an old Γί, but The hardened adhesive layer after crosslinking is too much changed to the tendency of the adhesive force to deteriorate after the localization step. It is because the temperature range in which the above-mentioned excellent effects are obtained is known from the postal study (the Tg of the Xia 义 polyol) It is set to be not too low, but it is more than 10 °c and is less than 50% in terms of body, and it has a specific hydroxyl value and a specific NCO/OH equivalent ratio in its soil V °. , 14 201239057 为 for the Chinese manual No. 101104898, no picture dirty The original revision period: June 15, 101 and a specific range of the average molecular weight, thereby synergistically exciting the activity of the molecular motion level of the C-polyol, so that the wettability of the subsequent object and In particular, it has been found that by controlling the NCO/OH equivalent ratio to a range of ο·!, particularly in the range of 〇5 to 6, a moderate degree of crosslinking can be achieved and after the aging step It shows a high adhesion. Moreover, it is surprisingly found that f exhibits a high adhesion even before aging. It is also found that after the aging step, it can be maintained after being placed in a high temperature and humidity. In the case where a metal case, a metal plate, or a metal deposition film is used as the substrate, it is preferable that the adhesive composition for a laminated sheet of the present invention contains a brothel from the viewpoint of improving the adhesion strength. The decane coupling agent is not limited to the following, and examples thereof include vinyl tris(β-methoxyethoxy) sinter, vinyl ethoxylate, and ethylene trioxy oxane. Base decanes; Methyl) propylene methoxy propyl trimethoxy oxysulfide, γ-(meth) propylene methoxy propyl triethoxy oxime, and γ (methyl decyl) propylene methoxy propyl dimethyl (meth) propylene oxime such as oxydecyl decane, alkane; β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, ρ_(3,4_cyclo,cyclohexyl)methyltrimethyl Oxylate, β_(3+epoxycyclohexyl)ethyltriethoxydecane, Ρ·(3,4-epoxycyclohexyl)methyltriethoxydecane, γ-shrinkage, oleyloxypropane Ethylene methoxy decane, and γ-glycidoxypropyl tris oxide, decane and other epoxy decanes; Ν-β-(aminoethylaminopropyldimethoxydecane, Ν-β- (aminoethyl)_γ-aminopropyltriethoxydecane, Ν-β-(aminoethyl)aminopropylmethyldiethoxydecylaminopropyldiethoxydecane, γ-Aminopropyltrimethoxydecane, Ν-phenyl-γ- 15 201239057 Hiozopill Modified 曰期:1〇1月615曰为101104898号 Chinese manual no slash correction of the aminopropyl propyl trimethoxy Base decane, and N_phenyl_γ_aminopropyltriethoxy oxime Xi amine stone burning the like; and Ya _ mercaptopropyl trimethoxy Silane, and Yu Ah _ propyl triethoxy silane-sulfur-containing Silane like. These compounds may be used singly or in combination of two or more kinds. The addition amount of the Shi Xiyuan coupling agent is preferably 0 丨 part by weight to 5 parts by weight, more preferably ≤ 3 weight loss, relative to the acrylic polyol (Α). If it is less than 〇丨 by weight, the effect of improving the adhesion strength of the gold material due to the addition of the Shi Xi Xuan coupling agent is inferior; even if it is added in excess of 5 parts by weight, the above reading energy is not found to be improved. The adhesive composition for a laminated sheet of the present invention may be a two-liquid mixed type adhesive in which a main agent is mixed at the time of use, or may be a one-liquid type in which a pre-agent and a hardening agent are combined (four). Further, the acid polyol (4) or the polyisophthalic acid vinegar (8) of the present invention may be used for each other, and the other main agent or curing agent of the present invention may be used in plural or plural kinds. In general, the main agent includes an acrylate package = a coupling agent, an organic (four), other additives, a hardened poly phthalate (B), an organic solvent, and other additives. In addition, the additive can be used in the range of the present invention, and the adhesive for the layered sheet of the homogenized layer can be formulated with an adhesion promoter, a reaction promoting agent, a dish or a series of antioxidants, and a UV stabilizer. , gold additive (four), resistance _, plasticizer, organic pigment, inorganic pigment, etc. in the use of metal layers (metal town, metal plate, etc.) as a sheet-like component 16 201239057 ~Γ 1 vy^.v/l^xx' l is the first G-side Chinese saying that the duck has no scribing correction. When the date of the correction is June 15th, the phosphoric acid-based compound can be added to improve the metal adhesion of the adhesive composition for a laminated sheet of the present invention. For example, phosphoric acid, sulphur, sulphuric acid, sulphuric acid or esters of such acids. ',, and, 'The adhesive composition for laminated sheets of the present invention is preferably used as an adhesive for forming a back protective sheet for a solar cell, and can also be used as a tackifying coating for a solar cell laminated sheet. Used as a dose. In this case, it is preferable to put an anti-caking agent. The adhesive of the month 7 can be unrestrictedly formulated as an adhesive agent without departing from the gist of the present invention. For example, a reaction accelerator can be used. Specific examples thereof include metal catalysts such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dimaleate; 18-diaza-bicyclo[5.4.0]undec carbon Alkene-7,1,5-diazabicyclo[4 3 0]nonene_5,6-dibutylamino-1,8-diazabicyclo[5.4.0]undecene-7 A tertiary amine; a reactive tertiary amine such as triethanolamine. One or two or more kinds of reaction accelerators can be used as the reaction accelerator. Further, in order to improve the appearance of the laminate, a homogenizing agent or an antifoaming agent of a known U may be blended in the main component. Examples of the leveling agent include polyether modified polydimethyl siloxane, polyester modified polydimethyl siloxane, aralkyl modified polymethyl alkyl siloxane, and polyester modified hydroxyl group. Polydidecyl fluorinated alkane, polyether ester modified hydroxy-containing polyfluorenyl oxalate, acrylic copolymer, mercapto acrylonitrile-based copolymer, polyether modified polydecylalkyl oxane, A known leveling agent such as an alkyl acrylate copolymer, an alkyl methacrylate copolymer, lecithin, or a mixture thereof. 17 Revision period: June 15, 2010, 201239057 Hiozopiii is No. 101104898 Chinese no-face correction. The defoaming agent can be listed as _resin, stone smoke solution, vinylidene (4) alkyl acrylate and methacrylic acid A known antifoaming agent such as a copolymer of an alkyl ester or such a cleansing compound. When a leveling agent or an antifoaming agent is added, one type of compound may be used independently, and two or more types of persons may be used: they may be used in combination. σ 〜 〜 ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ It is known that it is an anti-oxidation agent and a metal deactivator. These additives may be used singly or in combination of any combination. This financial office makes social meals, or (4), UV stabilizers, metal deactivation _ pairs: 5 «.:! Γ 1004 ^ 5 仏 仏 , , , , , , , , , , , , , , , , , , , , , , , 01 01 01 01 01 01 Crane (4) 接着 力 力 在 不 不 : : 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 m aeronautical - I oxazoline, or 2,2-d, M butyl) _ fork V Xin Shanglin)) or bismuth compound r / azelaic acid dioxime, or diammonium adipate). —醯肼, the solvent used in the present invention Ding 8-su (four) two 18 201239057 ~r i Revision date: 1〇1月15月15臼 For the 101st turn 98# Chinese manual no face correction ^ butyl _=+ ketones when ketones; tetrahydro-seven, two. Wei et al.; toluene: aromatic hydrocarbons such as diphenylbenzene; methylene chloride, 1,2-dichloroethane and other functional, meridian; dimercapto-hard, diterpene-xanthine and the like. These solvents may be used singly or in combination of two or more kinds. The non-volatile component (solids) of the adhesive of the present invention is preferably in the range of from 1% by weight to 50% by weight. The present adhesive can be adjusted by using a solvent as exemplified above. Further, a method of manufacturing an I-side protective sheet for a solar cell using the adhesive composition for a laminated sheet of the present invention, and a y example of a back protective sheet for a solar cell will be described. The manufacturing method of the back surface protective sheet for solar cells is not limited to the following examples, and various manufacturing methods or configurations can be employed depending on the purpose or needs. The solar cell module of the Shih 2 solar cell module has a configuration in which two _ sub-layers of the solar cell unit of the solar cell unit of the solar cell of 7% are installed. It is also commonly used as the light-receiving side of solar cell modules. However, in terms of non-light-receiving side without transparency, from the perspective of cost or property f, each company develops (4) protective sheets other than glass plates, and these solar cell back protective sheets are being used in the pool == back == product; : The plastic film of the financial metal layer of the solar oxide of the following is the metal layer of the metal layer of the oxide, the metal box of the know-how, and the plastic enamel with the nitride layer. 19 201239057 Hiozopni is the Chinese version of the 1011048^ without a slash correction. The revised period: June 15, 101. The laminated sheet adhesive composition of the present invention can be joined between the sheet members. The multi-layered back surface protective sheet for a solar cell can impart various properties by the multilayer structure. For example, by using a polyester film, the film can be imparted with a fluorine-based film by using a fluorine-based film to impart a water-based gas barrier property. As for the back protection sheet for solar cells, the root 2 can be selected by using the product and use of the solar cell module. "Plastic film, for example, polyacetal resin film such as polyparaphenylene m, polypyrene naphthalene vinegar, polyethylene resin film, polypropylene resin film, polystyrene resin film, poly carbon J: Membrane, bismuth film, polygas bake polycondensation: ΐ &quot;t虱fluoroethylene, polyethylene tetrafluoroethylene, polytetrafluoroethylene, j ethylene: fluoroalkyl vinyl ether copolymer, tetrafluoroethylene _妓 妓 : 等 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠 鼠A multilayer film or the like is formed, and a plurality of sheets of the above-mentioned film formed by laminating a plurality of the above-mentioned film can be suitably used by a plastic film which is easy to pick up by a surface: corona, thunder, thunder The treatment is carried out under the treatment of ★, the water treatment, the flame treatment, etc., and the surface of the film is attached with fine embossing, the fading process of the chemical portion of the shell, etc. Of course, the stomach of the present invention can also be used. The pleated state is suitable for use in raw materials with untreated surfaces. Adhesive layer for laminated sheets 20 201239057 Revision date: June 15, 2011 The Japanese manual No. 101104898 has no underline correction. The metal tour can be cited as Shaozhen or copper box. As the metal oxide or non-metal inorganic oxide of the distilled ore, for example, _, m can be discharged, tin, sodium, boron, An oxide such as titanium, lead, bismuth or antimony. Among these, it is preferable to satisfy the properties such as weatherability, water vapor permeability, electrical insulation, mechanical properties, and packaging operation when used as a solar cell module. a backing protective sheet for a solar cell formed by laminating a temperature-resistant polyethylene terephthalate film such as lanthanum phthalate, a polyester resin film such as naphthalene dicarboxylate or polycarbonate; In order to prevent a decrease in output due to solar electric noise, it is preferable to laminate a back surface of a solar cell made of a gold alloy, in order to prevent appearance defects due to photodegradation; preferably = good financial property (4) The solar cell made of a resin film protects the solar cell from the back side. _ Back_Picture to protect the solar cell module from the second to the second. The damage caused by the domain cell::: Sex 2: Partial discharge voltage is 700 V Or the electrical electricity or the foaming layer. The electrical method for improving the partial surface area: = direction. Recently, the formation of the d layer is, for example, the application of an adhesive composition on the early surface of a piece of plastic film or the like, so that the solvent is volatilized, and the other 21 201239057 410Ζ〇ρΐΐί is corrected. Period: June 15th, 2011 is the Chinese manual No. 101104898. The laminated substrate is bonded without being scribed, and it is obtained by hardening it at normal temperature or under heating. Alternatively, it may be produced by applying an adhesive composition to any one of the sheet members and heat-hardening to form an adhesive layer, and then coating other sheet-like member-forming coating liquids by heat or activity. The energy lines form other sheet members. An example of a notched wheel coater (e_a(10) te〇, dry laminator: knife-coating machine, plate coater, pro-coater, bar coater, and the like) is applied to a sheet member. Gravure pro-coater, reverse roll coater, knife coater (blade (10) e〇, ton printing coater, cloth, etc.. The subsequent dose applied to the surface of the laminated substrate is changed by = Preferably, it is about Q lg / m2 〜 5 () g / m 2 or so. More preferably t ir $ 〜 5 G g / m 2 or so. As a laminate substrate, it can be used according to the use: In the case of the above-mentioned multilayer structure, the θ, ° all or part of the towel is used in the adhesive group of the present invention: the coating liquid can be used to form a resin solution for the plastic film: polyethylene resin Solution, polypropylene-based poly-paste; == polycarbonate, fat solution, solution, etc., as a case of the case of the (meth) propylene late-caffeine solution, the fluorine-based resin cell, and the performance of the back protective sheet for the pool, The price is combined. (4) The method or the surface method is used to describe the method. The following is a more detailed description of the present invention. 22 201239057 The Chinese manual No. 101104898 is not slashed. The example of the revised date is not limited to the scope of the present invention. The evaluations in the examples are carried out according to the following methods. In the examples, parts represent parts by weight, % means wt%, and hydroxyl value means mgK〇H/g. The number average molecular weight, glass transition temperature, and hydroxyl value can be determined by the following method: &lt;Quantum average molecular weight&gt; The average molecular weight of the crucible was measured by Gpc (gel permeation chromatography) "HPC-8020" manufactured by Tosoh Corporation, and the solvent was tetrahydrofuran. The average molecular weight of the crucible was determined by standard polystyrene conversion. <Glass transfer temperature (Tg) &gt; The measurement of the glass transition temperature (Tg) can be carried out using DSC "RDC220" manufactured by Seiko Instruments Inc. The amount measured in an aluminum pan is about 1 藉 by the following method. A sample obtained by drying a synthetic acrylic polyol Ad~acrylic polyol A-18 solution, which is installed in a Dsc apparatus and cooled by a liquid nitrogen to -We's according to a temperature of 1 G ° C/min. The glass transition temperature was determined by the DSC chart. 〇 <Hydroxyl value> The impurity can be obtained by dissolving about 2 g of the sample in about 10 ml of pyridine, and then adding the previously prepared acetic anhydride/pyridine. 5 nU of a mixed solution of 15/85 by volume was allowed to stand for 20 hours. Thereafter, 1 ml of water and 10 ml of ethanol were added to determine by titration of 1N potassium hydroxide (ethanol solution). The indicator used phenolphthalein. &lt;Production of Acrylic Polyol (A)&gt;, (Synthesis &lt;Column A.1), in a 4-necked flask equipped with a condenser, a gas introduction tube, a drip hopper, and a thermometer, 1〇〇重量份,升23 201239057 HlOZOpili Corrected flood season: June 15th, 2011 is the 101104898 Chinese manual without a slash correction to 80 C, then drip the butyl acrylate by a dropping funnel for 2 hours | s 42 7 weight 5: part, 55.5 parts by weight of methyl propyl methacrylate, 1.8 parts by weight of acrylic acid 2-hydroxyethyl vinegar, and 2.0 parts by weight of azobisisobutyl nitrite pre-mixed Body fluid. Thereafter, the reaction was allowed to proceed for 1 hour, and then 0.2 Torr of azobisisobutylcarbonitrile was added thereto to cause a reaction for 1 hour, and the above steps were carried out until the conversion of the monomer became 98% or more, followed by cooling. Then, ethyl acetate was added to obtain a solution in which the solid content was 50%. (Synthesis Example A-2 to Synthesis Example A_18) The synthesis examples shown in Table 1 were obtained by the same procedure as in the case of the addition of the polymerization initiator dioxin diisobutyl nitrile to (4) the molecular weight 'other than the combination'. A_2~Acid acid polyol of the synthesis example. Further, an acrylic polyol having a composition represented by the example A-1 is known as 兮 π π 疋 寻 寻 利 驮 驮 T T 。 。. In addition, it is said as follows. Between: BA: butyl acrylate, ethyl methacrylate, ea ethyl vinegar, St: styrene, C_A: mercapto acrylate, coffee a: 2-ethylhexyl acrylate, HEA :Acrylic acid 2-hydroxyethyl ester, Apropylidene-4-butylbutyl ester · 24 201239057, • Μ. X is No. 101104898 Chinese manual without slash correction This amendment 曰 - 101年ό月15日[表1] Monomer composition Number average molecular weight Tg (°c) Hydroxyl value (mgKOH/g) BA EMA EA St CHMA 2EHA HEA 4HBA A-1 42.7 55.5 1.8 loooo 15 8.6 A-2 42.7 55.5 1.8 35000 15 8.6 A-3 42.7 55.5 1.8 60000 15 8.6 A-4 31.2 67.0 1.8 35000 30 8.6 A-5 20.2 78.0 1.8 35000 45 8.6 A-6 43.0 56.1 0.9 35000 15 4.3 A-7 41.4 55.0 3.6 35000 15 17.2 A-8 39.5 53.3 7.2 35000 15 34.4 A-9 42.7 55.5 1.8 35000 15 8.6 A-10 42.7 55.5 1.8 35000 15 8.6 ' A-11 42.7 55.5 1.8 35000 15 8.6~~ A-12 42.3 45.5 10.0 2.2 35000 15 8.6~~ A-13 48.0 50.2 1.8 35000 15 8.6 A-14 68.0 20.0 10.0 2.0 50000 -20 9.6 A-15 70.0 10.0 10,0 10.0 25000 55 8.6~^ A-16 42.7 55.5 1.8 6000 15 8, factory ^ A-17 42.7 55.5 1.8 120000 15 8^6 ~~ A-18 19.5 63.5 23.0 35000 15 ιϊ〇(Γ^ &lt;Example of Formulation of Adhesive Composition&gt; (Examples 1 to 13 and Comparative Examples 1 to 6) The acrylic polyol as a main component is 1 part by weight in terms of solid content ( Α) 'Polyisophthalic acid vinegar (Β) as a hardener is formulated with the blending ratio shown in Table 2, and a glycidyl group-containing hair transfer coupler ("ΚΒΜ-403" Shin-Etsu Chemical Co., Ltd.) is formulated as an additive. Manufactured by the company, 3.0 parts by weight of dioctyltin dilaurate ("NE〇STANNU_81〇", manufactured by Nitto Kasei Co., Ltd.) 0.01 parts by weight, and further adjusted the solid content to 25 201239057 H-lOZOpiTl as the third 01104898 Chinese manual without slash correction This revision period: ;! ο 1 June 丨 5 曰 [Table 2] 知 食 酸 酸 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( mgKOH/g) Type NCO/OH ratio formulation ratio Example 1 A-1 10000 15 8.6 Hardener A 2.0 ” 10.2 Example 2 A-2 35000 8.6 Hardener A 2.0 10,2 Example 3 A-3 60000 15 8.6 Hardener A 2.0 10.2 Example 4 A-4 35000 30 8.6 Hardener A 2.0 10.2 Example 5 A-5 35 000 45 8.6 Hardener A 2.0 10.2 Example 6 A-6 35000 15 4.3 Hardener B 2.0 3.4 Example 7 A-7 35000 15 17.2 Hardener B 2.0 13.4 Example 8 A-8 35000 15 34.4 Hardener B 2.0 26.8 Example 9 A -9 35000 15 8.6 Hardener B 1.2 4.0 Example 10 A-10 35000 15 8.6 Hardener B 4.0 13.4 Example 11 A-11 35000 15 8.6 Hardener C 2.0 10.7 Example 12 A-12 35000 15 8.6 Hardener C 2.0 10.7 Example 13 A-13 35000 15 8.6 Hardener A 2.0 10.2 Comparative Example 1 A-14 50000 -20 9.6 Hardener D 4.5 15.0 Comparative Example 2 A-15 25000 55 48.3 Hardener E 0.5 8.0 Comparative Example 3 A-16 6000 15 8.6 Hardener A 2.0 10.2 Comparative Example 4 A-17 120000 15 8.6 Hardener A 2.0 102 Comparative Example 5 A-18 35000 15 110.0 Hardener A 0.5 — 32 7 Comparative Example 6 Enterprise 1 ^GQ Krr . L. A-2 35000 15 8.6 Hardener A 12.0 ~~ 61.3 *1 Blending ratio = main Qi: hardener (solid ratio) *2 Relative to (A) 100 parts by weight (non-volatile content), blending KBM403 (decane coupling agent) 3 _〇 by weight. *3 With respect to (A) ] 00 parts by weight (nonvolatile matter), υ-8100.01 parts by weight was formulated as a reaction accelerator. *4 Hardener A : TakenateD-160N (manufactured by Mitsui Chemicals, TMP plus hexamethylene diisocyanate) 1:1 Hardener B : TakenateD-178N (manufactured by Mitsui Chemicals, hexamethylene II) Isocyanate ureido oxime ester modification) Hardener C ··Ivorofer diisocyanate isoindole urate modified hardener D : Sumidur N3300 (Sumika Bayer Urethane company, hexamethylene diisocyanate Cooling agent acid S|modified substance) Hardener E: Sumidur N3200 (manufactured by Sumika Bayer Urethane, hexamethylene diisocyanate condensed product) '- &lt;Production example of laminated film 1 &gt; Using each of the adhesive compositions of Examples 1 to 13 and Comparative Examples 1 to 6 to a dry coating amount of 4 g/m 2 to 5 g/m 2 , followed by a dry laminator The composition was applied to a corona-treated surface of a polyester film [manufactured by Toray Industries, Lumirror X-10S, thickness 50 μm]. Then, 26 201239057 is the 10110 side Chinese manual without a slash correction. The date of this revision: June 1st, 1st, 2011, after the volatilization of the granules, it is laminated on another polyester film [made by Toray Industries, Lmniiror X_10s Corona treatment surface with a thickness of 5 〇 μηη]. Thereafter, curing treatment (aging) was carried out for 3 days at 40 C, whereby the adhesive was hardened to form a laminated film 1. &lt;Production Example of Laminated Film 2&gt; Using the adhesive compositions of Examples 1 to 4 and Comparative Example 2 and Comparative Example 3, the method of producing the laminated film 1 was carried out to prepare [corona treatment 0 polyester film] The laminated film 2 of the /layer layer / aluminum foil]. &lt;Production Example of Laminated Layer 3&gt; Using the adhesive compositions of Examples 1 to 4 and Comparative Example 2 and Comparative Example 3, a polyester film was deposited by ruthenium dioxide according to the method for producing the laminated film 1 The vapor deposited layer and the adhesive layer are in contact with each other to form a laminated film 3 of a structure of a corona-treated polyester film/adhesive layer/cerium oxide-deposited polyester film. Table 2 and Table 3 show examples. }~Example 13, Comparative Example}~Combination of the main agent and the hardener in Comparative Example 6, and the initial adhesion force of the laminated film 1 and exposure to an environment of 85 ° C and a humidity of 85% for 1000 hours, 200 () Time, and the force after 3_ hours. &quot; Moreover, in Tables 4 and 5, the initial adhesion force of the laminated film 2 and the laminated film 3 using the examples 1 to 4, the comparative example 2, and the comparative example 3 is shown in an environment of 85 ° C and a humidity of 85%. Exposure to exposure for 1 hour, 2 hours/, and 3000 hours. The specific evaluation method will be described below. &lt;Adhesion test before aging and after aging> The laminated film 2, laminated film before and after aging 27 201239057 lozopul Corrected period: 1 June 1st, the first 101KM898 Chinese The instructions are not slashed. The 3 is cut to a size of 200 mm x 1.5 mm, and allowed to stand for 6 hours in an environment of 25 ° C and a humidity of 65 〇 / '. 'Through the tensile test according to the test method of ASTM-D1876-61. Machine, at 25. (:, in a humidity of 65%, the τ-type peeling test was carried out at a load speed of 300 mm/min. The average value of the five test pieces indicates the PET film/PET film, the ρΕΤ film/aluminum foil, the enamel film/ Peel strength between the ruthenium dioxide vapor-deposited polyester film (N/15 mm width). &lt;Adhesion test after moisture heat resistance test&gt; The laminate after aging was cut into 2 〇〇 claws The size is at 85. (:, humidity is 85%, the environment is allowed to stand for 1 hour, 2 hours, 3000 hours. Thereafter, at 25: (:, humidity 65% environment is allowed to stand 6 After the hour, the tensile tester was used according to the test method of ASTM_D1876_61, and the τ-type peeling test was carried out at a load speed of 3 〇〇mm/min in an environment of 25: (6°, humidity: 65%). The average value indicates the peel strength (N/15 mm width) between the PET film/PET film, the ruthenium film/aluminum foil, and the ΕΤ film/ruthenium dioxide shovel polyester film. Further, &lt;Evaluation Criteria&gt; [Aging Front force test] ◎ Excellent in practical use: 3 N/15 mm or more 0 Practical area: 2 N/15 mm~3 N/15 mm △ Practical lower limit: 1 N/15 mm~ 2 N/15 mm x is not practical: less than 1 N/15 mm [test after aging, adhesion test after heat and humidity resistance test] ◎ excellent in practical use: 5 N/15 mm or more 〇 用 区域 area: 4 N /15 mm~5 N/15 mm 28 201239057 τ 1 yj^Kj^fLX 1 Revision date: June 1st, 1st, June 15th, No. 101104898 Chinese manual No picture 丨 Line correction △ Practical lower limit: 2N/15 Mm ~4 N/15 mm x not practical: less than 2N/15 mm 〇〇[Table 3] k-stress heat and humidity resistance test before and after aging (NA5 mm) 85 ° C, 85% RH after the passage of time Then intensity (N/15mm) aging at 40 °c before aging for 3 days, 1000 hours after 2000 hours, after 3000 hours, after example 1 2.4 〇4.6 0 4.7 〇4.4 〇4.0 Δ3.3 ◎ 6.2 ◎ 6.3 ◎ 6.1 ◎ 6.0 ◎ Example 3 2.2 〇5.6 ◎ 5.4 ◎ 5.5 ◎ 5.3 ◎ Example 4 2.8 〇 6.1 ◎ 6.3 ◎ 6.2 ◎ 6.0 ◎ Example 5 1.8 Δ 4.7 〇 4.9 〇 4.9 〇 4.6 〇 Example 6 3.1 ◎ 5.2 ◎ 5.4 ◎ 4.6 〇 4.2 〇 Example 7 3.4 ◎ 5.5 ◎ 5.1 ◎ 4.5 〇 4.1 〇 _ Λ ^ [8 3.2 ◎ 4.7 〇 4.7 〇 4.2 〇 3.7 △ Poor 9 3.5 ◎ 4.5 〇 4.6 〇 4.2 〇 3.8 △ Example 10 3.3 ◎ 5.9 ◎ 6.0 ◎ 4.9 〇 4.7 〇 3.1 ◎ 4.2 〇 4.3 〇 4.1 〇 3.4 △ Example 12 3.1 ◎ 4.6 〇 4.6 0 4.3 〇 3.2 △ Example 13 2.8 ◎ 6.3 ◎ 6.3 ◎ 6.0 ◎ 5.9 ◎ Comparative Example 1 3.2 ◎ 3.9 Δ 3.4 Δ 3.1 Δ 2.9 Δ Comparative Example 2 0.1 X 1.2 X 0.9 X 0.7 X 0.3 X 0.3 X 3.1 △ 2.8 Δ 2.2 X 1.4 X t匕 Comparative Example 4 0.5 X 3.7 Δ 3.8 Δ 3.2 Δ 3.1 Δ Comparative Example S 4.5 ◎ 1.9 X 1.5 X 0.5 X 0.1 X Comparative Example 6 4 t gel was produced in the preparation of the adhesive, so that the coated aluminum foil/treated polyester was not applied. Film _ Next strength and heat resistance test before and after aging (N / 15 mm) 85 ° C, 85% RH after the passage of time after the strength (N / 15mm) before aging at 40 ° c after 3 days After 1000 hours 2000 hours after 3000 hours 3 hours Example 4 2.1 0 4.4 〇 4.8 〇 3.9 △ 3.7 △ 3.2 ◎ 5.7 ◎ 5.4 ◎ 5.1 ◎ 4.6 〇 23 〇 4.7 〇 4.3 〇 4.2 〇 4.1 〇 2.5 〇 4.5 〇 5.1 ◎ 4.7 〇 4.2 〇Comparative Example 2 0.6 X 2.5 Δ 2.7 Δ 2.3 X 1.4 X 0.8 X 2.8 △ 2. 9 Δ 2.3 Δ 1.5 X 29 201239057 ^tiozopiri is the Chinese manual of No. 101104898 without a slash correction. The revised period: June 15, 101 [Table 5] As shown in Table 3, it was found that the following examples of the adhesive composition of the examples were superior in both the pre-aging and post-aging conditions. Further, it is known that the force is excellent after the heat and humidity resistance test. The adhesive strength can be maintained over a long period of time. Thus, the example of the adhesive composition is particularly suitable in terms of long-term heat and humidity resistance for outdoor use. In JIS C 8917 (Crystalline Solar Cell Module and Endurance Test Method), it will be known as a particularly harsh tester for a long-term == temple-like test B_2 under pits and humidity of 85%. In the actual wealth, the performance is more than _hour, and after the small size = the strength of the subsequent strength can be maintained for a long time, it can be said that the composition of the present invention has sufficient long-term heat and humidity resistance. The solar cell back protection sheet is used to maintain the sheet phase in such a long-term moisture resistance test. The 相 is related to the popularity of the solar cell system, and it is considered from the viewpoint of ensuring == It also contributes to environmental protection. 30, Λ[ 201239057 Revision date: June 15, 101 for the 101st chest 98th Chinese ___ repair! £ This use, Li's adhesive composition can be used as a building for buildings and other outdoor filial = multi = 峨 barrier Materials, exterior wall materials, barriers,: Field battery panel materials (back protection sheets for solar cells, Tai* household materials, outdoor flooring materials, lighting protection t-adhesives provide strong bonding strength. Moreover, 妳,: and ~ At the end of the turbulent road, the subsequent strength due to hydrolysis, etc., decreases with time, and work, and can be returned to the next strength. ❹ ◎ iron ratio =: is the glass transition temperature of the (tetra) acid polyol (A) It is an example of Lu Liping π-amine main C. The result of the evaluation is the result of obtaining a joint force of 'only _5 mm when it is on the surface W'. ^ 55. (: The ratio of the glass transition temperature of the acrylic polyol (A) is the example of the C. The evaluation of the silk is obtained substantially without the result of further reduction in the test, and the force is extremely small, and The heat and humidity resistance of 6000 to 3 is an example in which the number average molecular weight of the acrylic polyol (4) is m. It is understood that the result of the evaluation is that the aging step 刖 = the cohesive force of the carrier is insufficient, and the adhesion force before the aging step is extremely small. The roll-shaped read state _ layer body is aged in the direction of the core L. If the force before the aging step is extremely ', the winding is easy to spread when aging, it is not suitable for industrial production. ηοοΓΓ is acrylic acid The number average molecular weight of the alcohol (A) is 12 _ 'more than the weight, _. The result of the evaluation is that the wetness of the PET film is sufficient for the aging secret. With the ratio 201239057 41626pitl Revision date: 101 years 6 The monthly 15曰 is the 1011G4898 Chinese saying _ no scribe correction. The same as in the third example, the winding is easy to spread during aging, which is not suitable for industrial production. Moreover, after the heat and humidity resistance test, no heat and humidity resistance is found. Sex test The subsequent force is lowered, but the adhesion is originally low, so it is known to be inferior to the example. Comparative Example 5 is an example in which the OH value of the acrylic polyol (A) is 110.0 and more than 100. It is known that the result of the evaluation is crosslinking. Excessively, it becomes a very hard hardened coating film, and the adhesion is poor. Comparative Example 6 is that the amount of polyisocyanate (B) is nc〇 / 〇h = 12, and the result is that it is applied before coating. The reaction of the acrylic polyol (A) produces a gel and is therefore incapable of coating. θ This application claims Japanese Patent Application No. 2011-030369, filed on Jan. 16, 2011, to the Japanese Intellectual Property Office. Priority, the content of S disclosed in the patent application is incorporated in the entire specification. [Industrial Applicability] The adhesive composition for laminated sheets of the present invention is an adherend for joining the same or different raw materials. For example, it can be suitably used for a bonding sheet of a multi-layer laminate of a plastic-based material and a metal-based material. It is also suitable for the bonding of the original (4) and the metal-ruthenium materials. The laminate of the present invention The composition is a high-temperature and high-humidity environment, and it can maintain a high adhesion. As a result, it is a multi-layer laminate material for outdoor industrial applications such as (four) materials (barrier materials, exterior wall materials, roofing materials, solar cell panel materials). (back protection sheet for solar cells, surface protection sheet for solar cells), window materials, outdoor flooring materials, lighting protection materials, automotive parts, etc. are suitable for adhesives. They can pass through the ground for a long time. 32 201239057 For the Chinese manual No. 101104898, there is no picture fj line correction. The date of this correction is: June 15th, 1st, and the subsequent strength, so it is especially suitable for strong use, for example, the back protection sheet for solar cells. ^ ^ = use of two sex, pool The formation of a surface protection sheet. Further, the product of the present invention = particularly for the surface treatment layer containing the plastic film ==, can also be suitably applied to the surface of the untreated 匕3 surface untreated transfer). Raw materials (also [Simple description], Ο No. [Description of main components] None. 33 201239057ί -γ χ \j^\j^riL 1 is the Chinese manual of No. 101104898. There is no slash correction. This is the date of the invention: 1st, 1st, June 15th invention patent specification 2 (this specification format 'order, please do not Change, please do not fill in ※ ※ ※ Application number: ※Application 曰: ※^(:Classification·· ! I. Invention name: (Chinese/English) Adhesive composition for laminated sheets and back protective sheet for solar cells ADHESIVE COMPOSITION FOR LAMINATING SHEET AND BACK PROTECTIVE SHEET FOR SOLAR CELL II. SUMMARY OF THE INVENTION: An adhesive composition is provided which exhibits high adhesion between various sheet members, particularly between layers comprising a plastic film surface treatment layer. i can maintain a high adhesion even when exposed to high temperature and high humidity, and is suitable for wearing a back protective sheet for solar cells. The adhesive sheet for laminated sheets of the present invention includes acrylic polyol (A) and polyisocyanate. (b) The number average molecular weight of the propanol polyhydric alcohol (Α) is 10,000 〜 〇〇, 〇〇〇, and the value of the process is from 1 mg KOH / g to 100 mg KOH / g ' The temperature exceeds 10 ° C and is 50 ° C or less, and the equivalent ratio NCO / OH of the light base derived from the acrylic polyol to the isocyanate group derived from polyisocyanate (B ) is 〇·1 to 10. Abstract: An adhesive composition f〇r fabricating a back 201239057 πιυζυριιΐ is No. 101104898 Chinese manual without scribe correction. Amendment date: June 1st, 1st, 2015, protective sheet of solar cell is provided. High adhesion between various sheet-like portions, especially between layers including surface treatment layer of plastic film, and the high adhesion can be maintained even when the adhesive composition is exposed to an environment of high temperature and high humidity. The adhesive composition for a laminating Sheet of the invention includes an acrylic polyol (A) and a polyisocyanate (B), wherein a number average molecular weight of the acrylic polyol (A) is 10,000 to 100,000 m, a hydroxyl value is 1 to 100 mgKOH/g, and a Glass transition temperat Ure (Tg) is more than 10°C and no more than 50°C. Further, an equivalent ratio NCO/OH of a hydroxyl group from the acrylic polyol (A) and an isocyanate group from the polyisocyanate (B) is 0.1 to 10. 201239057 丄1 is the Chinese manual No. 101104898. There is no slash correction. This revision date: June 15, 101 VII. Scope of application: 1. A laminate for the laminating sheet, including acrylic polyol (Α) and Polyisocyanate (Β), the acrylic polyol (Α) has a number average molecular weight of 1 〇, 〇〇〇~100,000, and a hydroxyl value of 1 mgKOH/g to 100 mgKOH/g, and the glass transition temperature (Tg) exceeds l 〇 ° C and 50 ° C or less, the equivalent ratio NCO / OH of the hydroxyl group derived from the acrylic polyol (A) to the isocyanate group derived from the polyisocyanate (B) is 0.1 to 1 Torr. 2. The adhesive composition for laminated sheets according to claim 1, wherein the polyisocyanate (B) comprises a polyisocyanate derived from an alicyclic diisocyanate or an aliphatic diisocyanate, ^ f as claimed The adhesive composition for a laminated sheet according to the above aspect of the invention, which is used in the manufacture of a back protective sheet for solar cells comprising two or more sheet members, and is used in the following applications. Forming at least a portion of an adhesive layer for joining the sheet members to each other. 4. A back protective sheet for a solar cell, comprising: ^ as described in the patent application of the above-mentioned items - Item 3: an adhesive layer formed by a tablet composition; At least two or more sheet-like members laminated in the layer. 34 201239057&gt;η ~r χ 1 is the Chinese manual of No. 101104898. There is no slash correction. The revision period is: 1 〇 1 year, 15th of the month. 4. Designation representative map (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 〇