WO2012057292A1 - Polyphenylene-ether layered film, solar-cell sheet, and solar-cell module - Google Patents

Abstract

A polyphenylene-ether layered film comprising a UV-absorbing coating film laminated onto at least one surface of a base film comprising a resin composition, said resin composition containing polyphenylene ether and a pigment.

Description

Polyphenylene ether-based laminated film, solar cell sheet and solar cell module

The present invention relates to a polyphenylene ether-based laminated film having excellent weather resistance, a solar cell sheet (including a laminated sheet for solar cell) used for protecting a solar cell module, and a solar cell comprising the same. Regarding modules.

In recent years, with increasing awareness of environmental issues such as global warming, solar power generation, in particular, has high expectations for its cleanliness and non-polluting properties. The solar cell constitutes the central part of a photovoltaic power generation system that directly converts sunlight energy into electricity. In general, a plurality of solar cell elements (cells) are wired in series and in parallel as the structure, and various packaging is performed to protect the cells, thereby forming a unit. A unit incorporated in this package is called a solar cell module, and the surface to which sunlight hits is generally covered with a transparent substrate (glass / translucent solar cell sheet; front sheet), and a thermoplastic (for example, ethylene- The gap is filled with a filler (sealing resin layer) made of a vinyl acetate copolymer), and the back surface is protected by a back surface sealing sheet (back sheet).

Since these solar cell modules are mainly used outdoors, various characteristics are required for their configuration and material structure. The backsheet is also required to have sufficient durability, flame retardancy, dimensional stability, high mechanical strength, etc. in consideration of outdoor use. In addition, from the viewpoint of cleanliness and non-pollution, it is also required to reduce the environmental load. Furthermore, adhesion with a sealing resin layer and a junction box is also an important required characteristic. In particular, in order to effectively protect the power generation element in the sealing resin layer, adhesion with the sealing resin layer is very important.

On the other hand, polyphenylene ether is known as engineering plastics with excellent heat resistance, flame retardancy, dimensional stability, non-hygroscopicity, electrical properties, etc., but has difficulty in moldability. Blended with polystyrene with excellent processability.
It is also known that polyphenylene ether is discolored (deteriorated) by ultraviolet rays. That is, polyphenylene ether is decomposed by ultraviolet rays, and in extreme cases, it becomes tattered and may not be practically used.

In order to suppress the deterioration of polyphenylene ether (hereinafter sometimes abbreviated as PPE) due to ultraviolet rays, Patent Document 1 discloses a flame-retardant resin sheet having a layer structure composed of two layers of a surface layer and a base layer. The relatively thin surface layer is impact-resistant polystyrene containing at least one of an ultraviolet absorber and a light stabilizer, and the relatively thick base layer is a non-halogen flame retardant. A flame retardant resin sheet having excellent weather resistance, which is a modified polyphenylene ether containing benzene, is disclosed.
According to this technique, an impact-resistant polystyrene layer containing an ultraviolet absorber or a light stabilizer and a modified PPE layer containing a non-halogen flame retardant are laminated by thermal fusion. In this case, it is considered that the extrusion temperature of the modified PPE as the base layer is relatively low at 210 to 240 ° C., and the content of the styrene resin contained in the modified PPE is considerably large. In a PPE system having a small content of styrene resin component (for example, PPE: styrene resin mass ratio 99: 1 to 60:40), the molding temperature is close to 300 ° C. It is conceivable that deterioration of the UV absorber and light stabilizer in the impact polystyrene is inevitable. Moreover, it is limited that the matrix resin of the layer containing an ultraviolet absorber or a light stabilizer is an impact-resistant polystyrene.
Although attempts have been made to improve the UV stability of the PPE sheet in this way, it can be said that the practical level has not been reached.

On the other hand, Patent Document 2 discloses that a fluorine-containing acrylic polymer (A) comprising a copolymer of an acrylic monomer and a perfluoroalkyl group-containing acrylic monomer and a fluoropolymer on at least one surface of a base resin film. A film of a composition mainly composed of two components of vinylidene fluoride resin (B) is formed, and an acrylic monomer and an ultraviolet absorbing monomer are provided between the film and the base resin film. And an agricultural resin film provided with an adhesive acrylic resin layer containing a polymer (C) obtained by polymerizing an acrylic monomer having a cycloalkyl group and a UV-stable monomer. Yes.
This technology relates to a weather-resistant agricultural resin film, and as a base resin film, a film usually used for an agricultural resin film is exemplified, and a PPE film is not exemplified.

JP 2001-113637 A JP 2009-296893 A

One of the properties required for the front sheet and the back sheet is weather resistance. In particular, in solar cell applications, attention is paid to hydrolysis resistance among weather resistance. This is because conventionally, a PET film that is easily hydrolyzed has been used, and its improvement has been a problem. Therefore, attention is hardly paid to the stability with respect to ultraviolet rays as the weather resistance of the solar cell sheet. However, since it is a major premise that the solar cell is used outdoors, it is also necessary to have excellent ultraviolet light stability. In this respect, when PPE is used, the solar cell sheet is decomposed by ultraviolet rays and becomes tattered, and therefore cannot be practically used.
The present invention has been made under such circumstances, and the first object is excellent in weather resistance (particularly, UV stability) and suitable as a solar cell sheet used for protecting a solar cell module. A second object is to provide a sheet for a solar cell. The second object is to provide a polyphenylene ether-based laminated film. A third object is to provide a solar cell module comprising the solar cell sheet.

As a result of intensive studies to achieve the above object, the present inventors have obtained the following knowledge.
Preferably, the base film is made of a specific composition by a polyphenylene ether-based laminated film in which an ultraviolet-absorbing coating film is laminated on at least one side of a base film composed of a resin composition containing polyphenylene ether and a pigment. It has been found that the first object can be achieved by using a laminated structure of two types and three layers, and the present invention has been completed. That is, the present invention is as follows.

[1] A polyphenylene ether-based laminated film obtained by laminating an ultraviolet-absorbing coating film on at least one side of a base film composed of a resin composition containing polyphenylene ether and a pigment.
[2] The polyphenylene ether-based laminated film according to [1], further including a styrene-based resin in the resin composition.
[3] The polyphenylene ether-based laminated film according to [1] or [2], wherein the ultraviolet-absorbing coating film is an acrylic ultraviolet-absorbing coating film.
[4] The polyphenylene ether-based laminated film according to [2] or [3], wherein the content ratio of the polyphenylene ether and the styrene resin in the resin composition is 99: 1 to 60:40 by mass ratio.
[5] The acrylic ultraviolet absorbing coating film is formed using a copolymer of an acrylic monomer having an ultraviolet absorbing group and other acrylic monomers [3] or The polyphenylene ether-based laminated film according to [4].
[6] The polyphenylene ether-based laminated film according to any one of [3] to [5], wherein the acrylic ultraviolet-absorbing coating film is formed by applying a solvent-based paint and drying.
[7] The polyphenylene ether-based laminated film according to any one of [1] to [6], wherein the pigment in the resin composition is a black pigment.
[8] The base film is a laminated film having at least an intermediate layer and surface layers on both sides thereof, and the intermediate layer is composed of a resin composition A containing polyphenylene ether and a pigment, and on both sides thereof. The polyphenylene ether-based laminated film according to any one of [1] to [7], wherein the provided surface layer is composed of the resin composition B that contains polyphenylene ether and substantially does not contain any pigment.
[9] The polyphenylene ether-based laminated film according to [8], wherein the resin composition A and / or the resin composition B further contains a styrene resin.
[10] A solar cell sheet using the polyphenylene ether-based laminated film according to any one of [1] to [9].
[11] A solar cell sheet obtained by further laminating a gas barrier layer on the solar cell sheet according to [10].
[12] A solar cell sheet obtained by laminating and integrating the solar cell sheet according to [10] or [11] and a sealing resin layer.
[13] A solar cell module provided with the solar cell sheet according to any one of [10] to [12].
[14] The solar cell module according to [13], wherein the solar cell sheet is used as a backsheet.

According to the present invention, a polyphenylene ether-based laminated film excellent in weather resistance (particularly UV stability) and suitable as a solar cell sheet used for protecting a solar cell module, the solar cell sheet, and the solar cell. The solar cell module which comprises the sheet | seat for operation can be provided.
Furthermore, a solar cell sheet obtained by laminating a gas barrier layer on the solar cell sheet and a solar cell sheet obtained by laminating and integrating the solar cell sheet and a sealing resin layer can be provided.

It is a schematic sectional drawing which shows an example of the solar cell module of this invention. It is a graph which shows the relationship between the exposure time and the residual rate (%) made into the breaking strength before exposure in the accelerated weather resistance test of each film obtained by the Example and the comparative example.

First of all, in this specification, “film” is generally a thin flat product whose thickness is extremely small compared to length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll. (JIS K6900). In general, a “sheet” is a product that is thin by definition in JIS, and whose thickness is small and flat for the length and width. However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.

[1] Polyphenylene ether-based laminated film The polyphenylene ether-based laminated film of the present invention (hereinafter sometimes simply referred to as “laminated film”) is a group composed of a resin composition containing polyphenylene ether, a styrene resin, and a pigment. An ultraviolet-absorbing coating film is laminated on at least one side of the material film.
Here, “the ultraviolet absorbing coating film is laminated on at least one side of the base film” means “an aspect in which the ultraviolet absorbing coating film is laminated directly on at least one side of the base film” and “A mode in which an ultraviolet-absorbing coating film is laminated on at least one surface of a base film with at least one layer, film, thin film-like member or the like interposed” is included.

(Polyphenylene ether)
In the present invention, polyphenylene ether is used as the main component of the resin composition constituting the base film.
Here, the “main component” represents occupying the largest proportion of the resin composition, and the lower limit is not particularly determined, but the polyphenylene ether is preferably 50% by mass or more, and 65% by mass or more. It is more preferable that it is 80 mass% or more. If it is this range, durability, a flame retardance, dimensional stability and high mechanical strength, high adhesiveness with a sealing resin layer, etc. can be achieved.

Specific examples of polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6- Ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-) 6-propyl-1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1,4-phenylene) ether, poly (2,6 -Dibromomethyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-ditolyl-1,4-phenyle) ) Ether, poly (2,6-dichloro-1,4-phenylene) ether, poly (2,6-dibenzyl-1,4-phenylene) ether, poly (2,5-dimethyl-1,4-phenylene) ether Etc. Of these, poly (2,6-dimethyl-1,4-phenylene) ether is preferably used.

Also, a copolymer obtained by grafting a styrene compound onto polyphenylene ether may be used. Examples of the polyphenylene ether grafted with a styrene compound include a copolymer obtained by graft polymerization of styrene, α-methylstyrene, vinyltoluene, chlorostyrene and the like as the styrene compound to the polyphenylene ether.

Furthermore, the polyphenylene ether may be modified with a modifying agent having a polar group. Examples of polar groups include acid halides, carbonyl groups, acid anhydrides, acid amides, carboxylic acid esters, acid azides, sulfone groups, nitrile groups, cyano groups, isocyanate esters, amino groups, imide groups, hydroxyl groups, and epoxy groups. , An oxazoline group, a thiol group, and the like.

In the laminated film of the present invention, the polyphenylene ether used for the base film is preferably such that the lower limit of the intrinsic viscosity obtained from the viscosity measured in chloroform at 30 ° C. is 0.2 dl / g or more. / G or more is more preferable, and 0.4 dl / g or more is more preferable. If the value of the intrinsic viscosity is within this range, problems such as inferior heat resistance, flame retardancy, and mechanical strength are unlikely to occur. The upper limit is preferably 0.8 dl / g or less, more preferably 0.7 dl / g or less, and further preferably 0.6 dl / g or less. When the value of the intrinsic viscosity is within this range, it is difficult to cause problems such as the shear viscosity becomes too high and the productivity is inferior.
Further, for the purpose of improving moldability, polyphenylene ethers having different intrinsic viscosities may be used in combination.

Commercially available polyphenylene ethers are sold under the trade names “PPO646”, “PPO640”, and “PPO630” by SABIC Innovation Plastics and under the tradenames “S201A” and “S202” from Asahi Kasei Chemicals, respectively. Is possible.

In the laminated film of the present invention, the resin composition constituting the base film is made of styrene for the purpose of improving the physical properties such as extrusion molding, impact resistance, flame retardancy, and adhesion to the polyphenylene ether described above. It is preferable to blend a resin.
(Styrenic resin)
Examples of this styrene resin include GPPS (general purpose polystyrene), HIPS (high impact polystyrene), ABS (acrylonitrile-butadiene-styrene), SEBS (hydrogenated styrene-butadiene-styrene block copolymer), SBS (styrene). -Butadiene-styrene block copolymer) and SEPS (hydrogenated styrene-isoprene-styrene block copolymer).
These styrenic resins may be used alone or in combination of two or more. The content ratio of the polyphenylene ether and the styrene resin in the resin composition is preferably 99: 1 to 60:40 by mass ratio, respectively. That is, the lower limit of the amount of the styrene resin to the total amount of the polyphenylene ether and the styrene resin is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. By mix | blending in this range, a moldability can be improved and impact resistance can be improved. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and still more preferably 20% by mass or less. If it is the blending within this range, the effect of improving the flame retardancy and heat resistance by the polyphenylene ether can be further utilized.

(Optional resin component)
In the laminated film of the present invention, the resin composition constituting the base film is made of the above-mentioned polyphenylene ether with the purpose of improving physical properties such as extrusion molding, impact resistance, flame retardancy, and adhesiveness. Other resin components can be appropriately blended as necessary within the range not impairing the effects of the invention.

Other resin components include, for example, ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / propylene / nonconjugated diene copolymers, ethylene / ethyl acrylate copolymers, ethylene / glycidyl methacrylate copolymers. Polymers, ethylene resins such as ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene / propylene-g-maleic anhydride copolymer, polyester resins such as polyester polyether elastomer and polyester polyester elastomer, polyamide resins And polyphenylene sulfide-based resin. These may be blended singly or in combination of two or more.

In the laminated film of the present invention, the resin composition constituting the base film needs to contain a pigment.
(Pigment)
As the pigment, a black pigment is preferably used from the viewpoint of improving weather resistance (particularly, UV stability). Although it does not specifically limit as a black pigment, Carbon black, black iron oxide, etc. are used, and carbon black is preferably used especially from a viewpoint of long-term stability. This black pigment is blended in the resin composition in an amount of usually 0.1 to 7% by mass, preferably 1 to 5% by mass, more preferably 2 to 4% by mass.
By blending this black pigment, the weather resistance (particularly UV stability) of the resulting laminated film becomes more excellent due to a synergistic effect with the UV-absorbing coating film provided on at least one side of the base film. .

The base film used in the laminated film of the present invention may be a single-layer film, or, as will be described later, at least an intermediate layer and a laminated film having a two-layer / three-layer structure having surface layers on both sides thereof. There may be.
When the base film is a film having a single layer structure, the thickness is usually about 10 to 1000 μm, preferably 10 to 300 μm, more preferably 20 to 120 μm, depending on the application.
In the case of a laminated film having two types and three layers, the composition of the intermediate layer and the surface layer will be described in detail later, but the total thickness is usually about 10 to 500 μm.
In the present invention, an ultraviolet-absorbing coating film is laminated on at least one side of the substrate film described above to obtain a polyphenylene ether-based laminated film having excellent weather resistance.

[UV absorbing film]
The UV-absorbing coating film is not particularly limited. For example, acrylic resin, alkyd resin, silicon resin, cellulose, phenol resin, melamine urea resin, chlorinated rubber resin, vinyl chloride resin, vinyl acetate resin, acrylic resin, An epoxy resin, urethane resin, polyester resin, fluorine resin, or the like is used.
Of these, acrylic polymers are preferred because they are excellent in light resistance and compatibility with ultraviolet absorbers.
In the laminated film of the present invention, as a method of forming an ultraviolet-absorbing coating film laminated on at least one side of the base film, a resin as described above, for example, an acrylic polymer, an ordinary ultraviolet absorber, Or there exists the method of forming using what added this ultraviolet absorber and the usual hindered amine light stabilizer.

On the other hand, an acrylic monomer having an ultraviolet absorbing group, or a combination of an acrylic monomer having an ultraviolet absorbing group and an acrylic monomer having a photostable group, and other acrylic monomers The method of forming an acrylic UV-absorbing coating film using a copolymer with a body is a preferable method because the active ingredient exhibits long-term weather resistance without bleeding out.
The ultraviolet absorbing group is a group that suppresses the generation of radicals by absorbing irradiated ultraviolet rays. From this point, a benzotriazole group and / or a benzophenone group are preferable. It is done.
Moreover, said light-stable group has the effect | action which capture | acquires the generated radical and inactivates, and a hindered amine group is mentioned preferably specifically from said point. That is, the stable nitroxy radical generated in the hindered amine group is combined with the active polymer radical, and returns to the original stable nitroxy radical, and this is repeated.

On the other hand, the acrylic monomer having an ultraviolet absorbing group, or a combination of an acrylic monomer having an ultraviolet absorbing group and a combination of an acrylic monomer having a photostable group and other copolymerized with the acrylic monomer. As the acrylic monomer, a cycloalkyl acrylate monomer having a cycloalkyl group in the ester portion is preferably used.
The cycloalkyl group has an action of imparting water resistance and water vapor permeability resistance to a resin such as an acrylic copolymer constituting the acrylic ultraviolet absorbing coating film.
Therefore, in the present invention, a synergistic effect can be obtained in terms of weather resistance by combining the acrylic copolymer with an ultraviolet absorbing group, a light-stable group introduced as required, and a cycloalkyl group. .
In the laminated film of the present invention, the acrylic copolymer constituting the acrylic ultraviolet absorbing coating film, which is an ultraviolet absorbing coating film, is an acrylic monomer having the above ultraviolet absorbing group (hereinafter referred to as acrylic ultraviolet radiation). An acrylic monomer having a light-stable group (hereinafter referred to as an acrylic light-stable monomer) and a cycloalkyl (meth) acrylate, which are optionally used. Can be obtained.
(Meth) acrylate refers to both acrylate and methacrylate. The same applies to similar terms below.

Below, although an ultraviolet absorptive coating film is explained in full detail by making the said acrylic type ultraviolet absorptive coating film into an example, this invention is not limited to this.
(Acrylic UV absorbing monomer)
Preferable examples of the acrylic ultraviolet absorbing monomer include acrylic benzotriazoles and acrylic benzophenones.

<Acrylic benzotriazoles>
In the present invention, the acrylic benzotriazoles are specifically preferably compounds represented by the following general formula (1) or (2).

（前記一般式（１）中、Ｒ⁵は水素原子または炭素数１～８の炭化水素基を表し、Ｒ⁶は低級アルキレン基を表し、Ｒ⁷は水素原子またはメチル基を表し、Ｙは水素原子、ハロゲン原子、炭素数１～８の炭化水素基、低級アルコキシ基、シアノ基またはニトロ基を表す。）

(In the general formula (1), R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ⁶ represents a lower alkylene group, R ⁷ represents a hydrogen atom or a methyl group, and Y represents a hydrogen atom. Represents an atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a lower alkoxy group, a cyano group or a nitro group.)

（前記一般式（２）中Ｒ⁸は炭素数２又は３のアルキレン基を表しＲ⁹は水素原子またはメチル基を表す。）

(In the general formula (2), R ⁸ represents an alkylene group having 2 or 3 carbon atoms, and R ⁹ represents a hydrogen atom or a methyl group.)

In the general formula (1), the hydrocarbon group having 1 to 8 carbon atoms represented by R ⁵ is specifically methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl. Chain, pentyl group, hexyl group, heptyl group, octyl group and other chain hydrocarbon groups; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and other alicyclic hydrocarbon groups; phenyl group, Aromatic hydrocarbon groups such as tolyl group, xylyl group, benzyl group and phenethyl group are enumerated. R ⁵ is preferably a hydrogen atom or a methyl group.

The lower alkylene group represented by R ⁶ is preferably an alkylene group having 1 to 6 carbon atoms. Specifically, a straight chain such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, or a hexylene group. Examples include chain alkylene groups and branched chain alkylene groups such as isopropylene group, isobutylene group, s-butylene, t-butylene group, isopentylene group, and neopentylene group, preferably methylene group, ethylene group, and propylene group. .
Examples of the substituent represented by Y include hydrogen; halogen such as fluorine, chlorine, sulfur, iodine, etc .; hydrocarbon group having 1 to 8 carbon atoms represented by R ⁵ ; methoxy group, ethoxy group, propoxy group, butoxy Groups, pentoxy groups, heptoxy groups and the like, lower alkoxy groups having 1 to 8 carbon atoms; cyano groups; nitro groups. From the viewpoint of reactivity, hydrogen atoms, chlorine atoms, methoxy groups, t-butyl groups, cyano groups are preferred. Group, a nitro group.

Specific examples of the acrylic ultraviolet absorbing monomer represented by the general formula (1) include 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2 -[2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5'-(methacryloyloxyethyl) phenyl] -2H -Benzotriazole, 2- [2'-hydroxy-5'-t-butyl-3 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) ) Phenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxy) Til) phenyl] -5-methoxy-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2′-hydroxy- 5 ′-(methacryloyloxyethyl) phenyl] -t-butyl-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole From the viewpoint of ultraviolet absorption, 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) is preferable. ) Phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-t- Til-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -t-butyl-2H-benzotriazole, more preferably Are 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole . Only one kind of these acrylic ultraviolet absorbing monomers represented by the general formula (1) may be used, or two or more kinds may be appropriately mixed and used.

In the acrylic ultraviolet absorbing monomer represented by the general formula (2), the alkylene group having 2 or 3 carbon atoms represented by R ⁸ is specifically an ethylene group or trimethylene. Group, propylene group and the like.
Examples of the acrylic ultraviolet absorbing monomer represented by the general formula (2) include 2- [2′-hydroxy-5 ′-(β-methacryloyloxyethoxy) -3′-t-butylphenyl]. -4-t-butyl-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(β-acryloyloxyethoxy) -3′-t-butylphenyl] -4-t-butyl-2H-benzotriazole 2- [2′-hydroxy-5 ′-(β-methacryloyloxy n-propoxy) -3′-t-butylphenyl] -4-t-butyl-2H-benzotriazole, 2- [2′-hydroxy- 5 ′-(β-methacryloyloxy i-propoxy) -3′-t-butylphenyl] -4-t-butyl-2H-benzotriazole is preferable, and 2- [ '- hydroxy-5' - is a (beta-methacryloyloxy ethoxy)-3'-t-butylphenyl] -4-t-butyl--2H- benzotriazole. These acrylic UV-absorbing monomers represented by the general formula (2) may be used alone or in combination of two or more.

<Acrylic benzophenones>
Examples of acrylic benzophenones used as acrylic ultraviolet absorbing monomers are obtained by reacting 2,4-dihydroxybenzophenone or 2,2 ′, 4-trihydroxybenzophenone with glycidyl acrylate or glycidyl methacrylate. 2-hydroxy-4- (3-methacryloyloxy-2-hydroxy-propoxy) benzophenone, 2-hydroxy-4- (3-acryloyloxy-2-hydroxy-propoxy) benzophenone, 2,2′-dihydroxy-4- ( And monomers such as 3-methacryloyloxy-2-hydroxypropoxy) benzophenone and 2,2′-dihydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone. From the viewpoint of versatility of the raw material, 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone is preferable.

The acrylic UV-absorbing monomer is used to further improve the weather resistance of the UV-absorbing coating film containing the resulting acrylic copolymer, and the content ratio in the total acrylic monomer component is as follows. It is as follows. In the case of acrylic benzotriazoles, preferably from 0.1 to 50% by mass, more preferably from 0.5 to 40% by mass, and still more preferably from 1 to 30 from the viewpoint of sufficient ultraviolet absorption performance and prevention of coloring by ultraviolet irradiation. % By mass. In the case of acrylic benzophenones, the amount is preferably from 0.1 to 10% by mass, more preferably from 0.2 to 5.0% by mass, from the viewpoint of sufficient ultraviolet absorption performance and compatibility.

<Acrylic light-stable monomer>
The acrylic light-stable monomer that is optionally used preferably has a hindered amine group, and more preferably has at least one hindered amine group and acryloyl group in the molecule.
The acrylic light-stable monomer is preferably a compound represented by the following general formula (3) or (4).

（前記一般式（３）中、Ｒ¹は水素原子またはシアノ基を表し、Ｒ²及びＲ³はそれぞれ独立して水素原子または炭素数１又は２の炭化水素基を表し、Ｒ⁴ は水素原子または炭素数１～１８の炭化水素基を表し、Ｘは酸素原子またはイミノ基を表す。）

(In the general formula (3), R ¹ represents a hydrogen atom or a cyano group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms, and R ⁴ represents a hydrogen atom. Or a hydrocarbon group having 1 to 18 carbon atoms, and X represents an oxygen atom or an imino group.)

（前記一般式（４）中、Ｒ¹は水素原子またはシアノ基を表し、Ｒ²及びＲ³はそれぞれ独立して水素原子または炭素数１又は２の炭化水素基を表し、Ｘは酸素原子またはイミノ基を表す。）

(In the general formula (4), R ¹ represents a hydrogen atom or a cyano group, R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms, and X represents an oxygen atom or Represents an imino group.)

In the acrylic light-stable monomer represented by the general formula (3) or (4), the hydrocarbon group having 1 to 18 carbon atoms represented by R ⁴ is specifically a methyl group or an ethyl group. Propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group Chain hydrocarbon groups such as hexadecyl group, heptadecyl group and octadecyl group; alicyclic hydrocarbon groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; phenyl group, tolyl group, xylyl Groups, aromatic hydrocarbon groups such as benzyl group and phenethyl group. Among these, in the present invention, R ⁴ is preferably a hydrogen atom or a methyl group from the viewpoint of light stabilization reactivity.
Examples of the hydrocarbon group having 1 or 2 carbon atoms represented by each of R ² and R ³ include a methyl group and an ethyl group, and a methyl group is preferable.

Specific examples of the acrylic light-stable monomer represented by the general formula (3) include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) Acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2 , 6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine , 4-crotonoylamino-2,2,6,6-tetramethylpiperidine and the like. Among these, in the present invention, 4- (meth) actyl is used from the viewpoint of light stabilization reactivity. Royloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6 6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine are preferred, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyl Oxy-1,2,2,6,6-pentamethylpiperidine is more preferred. These may be used alone or in a suitable mixture of two or more. Of course, the acrylic light-stable monomer of the general formula (3) is not limited to these compounds.

Specific examples of the acrylic light-stable monomer represented by the general formula (4) include 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetra Methylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotoyloxy-2,2,6 6-tetramethylpiperidine and the like. Among these, in the present invention, 1-acryloyl-4-acryloylamino-2,2,6,6-tetramethylpiperidine, 1-methacryloyl is used in the present invention from the viewpoint of versatility of raw materials. -4-Methacryloylamino-2,2,6,6-tetramethylpiperidine is preferred, 1-methacryloyl-4-methacryloylamino-2,2,6,6 Tetramethylpiperidine is more preferred. These may be used alone or in a suitable mixture of two or more. The acrylic light-stable monomer of the general formula (4) is not limited to these.

The acrylic light-stable monomer used as desired is contained in the total acrylic monomer component for obtaining an acrylic copolymer in an amount of 0.1 to 50% by mass from the viewpoint of light stabilization performance. It is preferably contained in a range of 0.2 to 10% by mass, more preferably 0.5 to 5% by mass. When the content is within the above range, the weather resistance is sufficiently exhibited.

(Cycloalkyl (meth) acrylate)
Cycloalkyl (meth) acrylate is a component used for improving the hardness, elasticity, solvent resistance, gasoline resistance, weather resistance, and the like of the resulting acrylic ultraviolet absorbing coating film. Preferred examples of the cycloalkyl (meth) acrylate include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, and cyclododecyl (meth) acrylate. These can be used alone or in combination of two or more. The cycloalkyl (meth) acrylate is preferably used in the range of 5 to 80% by mass, more preferably 10 to 70% by mass, and further preferably 15 to 50% by mass in the total acrylic monomer component. When the amount used is within the above range, performance such as hardness and weather resistance of the coating film is sufficiently exhibited, and it is preferable that both drying property and leveling property are obtained.

<Crosslinkable functional group>
In the acrylic ultraviolet absorbing coating film in the laminated film of the present invention, the acrylic copolymer preferably has a crosslinkable functional group and is formed by crosslinking with a crosslinking agent. Thereby, since the said acrylic copolymer has a crosslinked structure, the physical property and weather resistance of a coating film will improve, As a result, the outstanding weather resistance performance will be maintained over a long term.
Examples of the crosslinkable functional group possessed by the acrylic copolymer include a hydroxyl group, an amino group, a carboxyl group or an anhydride thereof, an epoxy group, and an amide group. One kind of these crosslinkable functional groups may be present in the acrylic copolymer, or two or more kinds thereof may be present. In the present invention, among these crosslinkable functional groups, groups having active hydrogen such as a hydroxyl group, an amino group, and a carboxyl group are preferable from the viewpoint of stability.

Examples of the acrylic monomer containing a hydroxyl group include, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate, and a polyester diol mono (from phthalic acid and propylene glycol) ( Examples include (meth) acrylic monomers having a hydroxyl group such as (meth) acrylate, and preferred are hydroxypropyl acrylate and hydroxyethyl methacrylate. These can be used alone or in combination of two or more.
Acrylic monomers containing a crosslinkable functional group are crosslinked when the resulting acrylic copolymer is blended with other crosslinkable compounds such as polyisocyanate to form a resin composition for thermosetting coatings. It is a component necessary for the reaction with the active compound, and is used in the range of 2 to 35% by mass, preferably 3.5 to 23% by mass in the total polymerizable monomer component. If the amount is within the above range, the amount of the crosslinkable functional group in the obtained acrylic copolymer is appropriate, the reactivity between the acrylic copolymer and the crosslinkable compound is maintained, and the crosslinking density is sufficient. Thus, the desired coating film performance is obtained. Also, the storage stability after blending the crosslinkable compound is good.

<Other polymerizable unsaturated monomers>
In the present invention, other polymerizable unsaturated monomers for forming an acrylic copolymer can be used.
Examples of other polymerizable unsaturated monomers used in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl. (Meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid alkyl esters such as stearyl (meth) acrylate; epoxy such as glycidyl (meth) acrylate Group-containing unsaturated monomers; nitrogen-containing unsaturated monomers such as (meth) acrylamide, N, N′-dimethylaminoethyl (meth) acrylate, vinylpyridine, and vinylimidazole; halogen-containing substances such as vinyl chloride and vinylidene chloride Unsaturated monomer; aromatic unsaturated monomer such as styrene, α-methylstyrene, vinyl toluene; vinyl ester such as vinyl acetate; vinyl ether; unsaturated cyanide compound such as (meth) acrylonitrile One or two or more selected from these groups can be used.

In addition, from the viewpoint of internal catalysis during the crosslinking reaction, a polymerizable unsaturated monomer containing an acidic functional group can also be used. For example, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and Carboxyl group-containing unsaturated monomers such as maleic anhydride; sulfonic acid group-containing unsaturated monomers such as vinyl sulfonic acid, styrene sulfonic acid and sulfoethyl (meth) acrylate; 2- (meth) acryloyloxyethyl acid Acid phosphate ester unsaturated monomers such as phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-2-chloropropyl acid phosphate, 2-methacryloyloxyethylphenyl phosphate, etc. One or two selected from these groups It is possible to use the above.

The other polymerizable monomers can be used as necessary within the range not impairing the action of the acrylic copolymer in the present invention, and the amount used is 0 to 92. It can be 9 mass%. Among the other polymerizable monomers, the polymerizable monomer containing an acidic functional group serves as an internal catalyst when the acrylic copolymer undergoes a crosslinking reaction with a crosslinking agent. May be 0 to 5% by mass, preferably 0.1 to 3% by mass in the polymerizable monomer component.

<Polymerization method of acrylic copolymer>
The method for obtaining an acrylic copolymer using the monomer is not particularly limited, and a conventionally known polymerization method can be used.
For example, when adopting the solution polymerization method, usable solvents include, for example, toluene, xylene and other high boiling aromatic solvents; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether acetate. Solvents; ketone solvents such as methyl ethyl ketone and methyl sobutyl ketone; aliphatic alcohols such as isopropanol, n-butanol and isobutanol; alkylene glycol monoalkyl such as propylene glycol monomethyl ether, propylene glycol monoethyl ether and diethylene glycol monoethyl ether Ethers etc. can be mentioned, These 1 type, or 2 or more types of mixtures can be used.

Examples of the polymerization initiator include 2,2′-azobis- (2-methylbutyronitrile), t-butylperoxy-2-ethylhexanoate, 2,2′-azobisisobutyronitrile, benzoyl Usable radical polymerization initiators such as peroxide and di-t-butyl peroxide can be listed. These may be used alone or in combination of two or more. The amount used is not particularly limited and can be appropriately set depending on the desired properties of the acrylic resin.
Reaction conditions such as reaction temperature and reaction time are not particularly limited. For example, the reaction temperature is in the range of room temperature to 200 ° C., preferably in the range of 40 to 140 ° C. The reaction time can be appropriately set so that the polymerization reaction is completed according to the composition of the monomer component and the type of the polymerization initiator.

(Crosslinking agent)
The crosslinking agent is not particularly limited as long as it is a compound or polymer containing two or more functional groups that crosslink and cure with the above-mentioned crosslinkable functional groups, and the type of functional group possessed by the acrylic copolymer. 1 type or 2 or more types can be appropriately selected and used according to the above.
For example, when the crosslinkable group possessed by the acrylic copolymer is a hydroxyl group, examples of the crosslinking agent include a compound or polymer having a phenol group, an epoxy group, a melamine group, an isocyanate group, or a dialdehyde group. A compound or a polymer containing an epoxy group, a melamine group or an isocyanate group is preferable from the viewpoint of crosslinking reactivity and pot life, and an isocyanate group is particularly preferable from the viewpoint of pot life control.

When the crosslinkable functional group of the acrylic copolymer is a carboxyl group or an anhydride thereof, examples include crosslinkable compounds such as polyisocyanate compounds or modified products thereof, aminoplast resins, and epoxy resins. When the group is an epoxy group, examples include a crosslinking agent containing a compound such as an amine, carboxylic acid, amide, N-methylol alkyl ether, and when the crosslinkable functional group is a hydroxyl group or an amino group, polyisocyanate. Examples thereof include a crosslinking agent such as a compound or a modified product thereof, an epoxy resin, and an aminoplast resin. Among these, in combination with a group having active hydrogen, a polyisocyanate compound and / or an epoxy resin is preferable.
In the acrylic copolymer, a combination in which the crosslinkable functional group is a hydroxyl group and the crosslinker is an isocyanate compound is desirable in terms of component reactivity, weather resistance derived therefrom, hardness and flexibility of the coating film. .

In the acrylic UV-absorbing coating film in the laminated film of the present invention, as described above, it is preferable to use an isocyanate compound as a crosslinking agent, and polyisocyanate is preferably used as the isocyanate compound. The polyisocyanate may be a diisocyanate, a dimer thereof (uretdione), a trimer thereof (isocyanurate, a triol adduct, a burette), or a mixture of two or more thereof. For example, as the diisocyanate component, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3′-dimethoxy -4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 4,4'-diisocyanate diphenyl ether, 1,5-xylylene diisocyanate, 1,3-diisocyanate methylcyclohexane, 1,4 -Diisocyanate methylcyclohexane, 4,4'-diisocyanate cyclohexane, 4,4'-diisocyanate cyclohexyl methane, isophor Down diisocyanate, dimer acid diisocyanate, norbornene diisocyanate. Also, xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and the like are preferred from the viewpoint of non-yellowing. Moreover, the isocyanurate body and burette body of hexamethylene diisocyanate are good in terms of fastness, gas barrier properties, and weather resistance.

The amount of the crosslinking agent used is not particularly limited and can be appropriately determined depending on the type of the crosslinking agent, etc., but the crosslinkable group (for example, hydroxyl group) of the acrylic copolymer and the crosslinking group of the crosslinkable compound. The reactive group ratio is preferably hydroxyl group: crosslinking group = 1: 1 to 1:20 in terms of cohesive strength in the layer and interlayer adhesion, and more preferably 1: 1 to 1:10. A crosslinking group ratio in the above range is advantageous in terms of adhesion, high temperature and high humidity resistance, gas barrier properties, blocking resistance, and the like.

(Formation method of UV-absorbing coating film)
In the laminated film of the present invention, an ultraviolet absorbing coating film is laminated on at least one side of the base film. As a preferred method for forming the coating film, in the present invention, a method of applying a solvent-based paint and drying it is adopted. In this case, since the coating and drying are performed while partially dissolving the surface layer, an ultraviolet-absorbing coating film having excellent adhesion is laminated on the base film.
Specifically, a solvent-based paint containing an ultraviolet-absorbing group or an acrylic copolymer having a UV-absorbing group and a light-stable group and having a crosslinking point such as a hydroxyl group and a crosslinking agent such as an isocyanate compound. For example, reverse roll coater, gravure coater, rod coater, air doctor coater, coating using spray or brush coating method, hot air drying at a temperature of about 80 to 200 ° C., hot roll drying, etc. Acrylic UV absorption as a UV-absorbing coating film that has excellent weather resistance over a long period of time by evaporating and drying the solvent using a known drying method such as heat drying or infrared drying. A characteristic coating film is formed. Examples of the solvent include methyl ethyl ketone, methyl isobutyl ketone, xylene, toluene, ethyl acetate, methanol, isopropyl alcohol, and water. These solvents may be used alone or in a combination of two or more. The solid content concentration of the solvent-based paint is not particularly limited as long as it can be applied.
The thickness of the ultraviolet absorbing coating film is preferably about 0.005 to 10 μm, more preferably 0.01 to 8 μm. If the thickness is 10 μm or less, the slipperiness is good, there is almost no peeling from the base film due to the internal stress of the coating film itself, and if the thickness is 0.005 μm or more, a uniform thickness is obtained. This is preferable because it can be maintained.

[Substrate film of two types and three layers laminated structure]
In the polyphenylene ether-based laminated film of the present invention, the base film is a laminated film having at least an intermediate layer and surface layers on both sides thereof, and the intermediate layer is composed of a resin composition A containing polyphenylene ether and a pigment. In addition, the surface layer provided on both sides of the resin composition B may include a resin composition B that includes polyphenylene ether and a styrene-based resin and substantially does not include any pigment.
In this case, the base film is a laminated film of two types and three layers.

[Middle layer]
The intermediate | middle layer of a base film is comprised from the resin composition A containing polyphenylene ether and a pigment. The resin composition A is preferably blended with a styrene resin for the purpose of improving physical properties such as extrusion moldability, impact resistance, flame retardancy, and adhesiveness.
The types, blending ratios, and pigments of polyphenylene ether and styrene resin in the resin composition A constituting the intermediate layer are as described in the description of the resin composition constituting the base film described above.
In addition, the above-mentioned polyphenylene ether in the intermediate layer and the surface layer described later is a range that does not impair the effects of the present invention for the purpose of improving physical properties such as extrusion moldability, impact resistance, heat resistance, flame retardancy, and adhesiveness. Thus, if necessary, other resin components can be appropriately blended. About this other resin component, it is as having shown by description of the resin composition which comprises the base film mentioned above.

[Surface]
The surface layer in the base film of the two-type / three-layer configuration is provided on both sides of the intermediate layer described above.
This surface layer is composed of a resin composition B that contains polyphenylene ether and contains substantially no pigment. The resin composition B is preferably blended with a styrene resin for the purpose of improving physical properties such as extrusion moldability, impact resistance, flame retardancy, and adhesiveness.
The types of polyphenylene ether and styrene resin and the blending ratio thereof are as described in the description of the intermediate layer.
In addition, as in the case of the intermediate layer described above, polyphenylene ether has a range that does not impair the effects of the present invention for the purpose of improving physical properties such as extrusion moldability, impact resistance, heat resistance, flame retardancy, and adhesiveness. Thus, if necessary, other resin components can be appropriately blended. Other resin components are as described in the description of the intermediate layer.
In the present invention, the fact that the resin composition B constituting the surface layer contains substantially no pigment means that the content of the pigment in the resin composition B is 0.1% by mass or less. Point to.

In such a two-layer / three-layer base film, since the surface layer is substantially free of pigment, the surface state of the surface layer is extremely good and the secondary processability is excellent, and therefore at least one side of the surface layer. In addition, the UV-absorbing coating film can be efficiently laminated with a uniform thickness.

In the polyphenylene ether-based laminated film of the present invention, the base film having a two-kind / three-layer structure preferably has a thickness of 10 to 500 μm, more preferably 20 to 200 μm, from the viewpoint of flame retardancy and economy. .
Further, the thickness ratio of the surface layer / intermediate layer / surface layer described above is 0.01 to from the viewpoint of the balance of improving the formability without impairing the essence of the film performance while bearing the essence of the film performance in the intermediate layer. It is preferably 2 / 9.98 to 6 / 0.01 to 2, more preferably 0.1 to 2 / 9.9 to 6 / 0.1 to 2, and 0.15 to 2/9. 7 to 6 / 0.15 to 2 is more preferable, and 0.5 to 1/9 to 8 / 0.5 to 1 is particularly preferable.

The base film of the two-kind three-layer structure is formed by, for example, extrusion using an extruder equipped with a two-kind three-layer multilayer T die and setting the barrel temperature to 220 to 300 ° C. and the die temperature to 290 ° C. Can be manufactured.
Specifically, while carrying out nitrogen purge, raw materials (resin composition A, resin composition B) are charged, the molten raw material is extruded from a T-die die, cooled and solidified with a cast roll, and the speed of the cast roll By adjusting the above, a base film having a two-layer / three-layer structure having a predetermined thickness is manufactured.

[2] Solar Cell Sheet Next, the solar cell sheet of the present invention will be described. Examples of the solar cell sheet of the present invention include first to third solar cell sheets.
[First solar cell sheet]
The 1st sheet | seat for solar cells is a sheet | seat for solar cells which uses the polyphenylene ether-type laminated | multilayer film of this invention mentioned above.
The first solar cell sheet is a sheet used for constituting a solar cell module, and particularly includes a front or back surface sealing sheet (front sheet or back sheet), a substrate sheet, and the like, and particularly as a back sheet. It is a solar cell sheet that can be suitably used.
In addition to the first solar cell sheet, an easy adhesion layer, a light reflective colored layer, a hard coat layer, or the like may be provided on the surface.

Next, the second solar cell sheet will be described.
[Second solar cell sheet]
The second solar cell sheet is a solar cell sheet obtained by further laminating a gas barrier layer on the first solar cell sheet described above.

(Gas barrier layer)
As a gas barrier layer in the 2nd sheet | seat for solar cells, the thing of the layer structure containing an inorganic thin film layer can be used conveniently. In addition, a metal thin film such as an aluminum foil or a thermoplastic polymer can be used as the gas barrier layer, and any material that can be used for ordinary packaging materials can be used without any particular limitation.
Specifically, polyolefins such as homopolymers or copolymers such as ethylene, propylene and butene, amorphous polyolefins such as cyclic polyolefin, polyesters such as polyethylene terephthalate and polyethylene-2,6-naphthalate, nylon 6, nylon 66, polyamide such as nylon 12, copolymer nylon, ethylene-vinyl acetate copolymer partial hydrolyzate (partially saponified product, EVOH), polyimide, polyetherimide, polysulfone, polyethersulfone, polyetheretherketone, polycarbonate , Polyvinyl butyral, polyarylate, acrylate resin and the like. Among these, polyester, polyamide, and polyolefin are preferable from the viewpoint of film properties. Of these, polyethylene terephthalate and polyethylene naphthalate are more preferable from the viewpoint of film strength. Furthermore, polyethylene naphthalate is preferable in terms of weather resistance and hydrolysis resistance.

Examples of the inorganic substance constituting the inorganic thin film layer include silicon, aluminum, magnesium, zinc, tin, nickel, titanium, hydrogenated carbon, etc., or oxides, carbides, nitrides, or mixtures thereof. Diamond-like carbon mainly composed of silicon oxide, aluminum oxide, and hydrogenated carbon is preferable. In particular, silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxide are preferable in that high gas barrier properties can be stably maintained.

As a method for forming an inorganic thin film layer of a laminated film having a gas barrier layer, any of a vapor deposition method and a coating method can be used, but a vapor deposition method is preferable in that a uniform thin film having a high gas barrier property can be obtained. This vapor deposition method includes methods such as physical vapor deposition (PVD) or chemical vapor deposition (CVD). Examples of physical vapor deposition include vacuum deposition, ion plating, and sputtering, and chemical vapor deposition includes plasma CVD using plasma and a catalyst that thermally decomposes a material gas using a heated catalyst body. Examples include chemical vapor deposition (Cat-CVD).

The thickness of the gas barrier layer is usually about 5 to 500 μm, preferably 10 to 400 μm, more preferably 25 to 300 μm, from the viewpoint of performance as a gas barrier layer and economy.
The second solar cell sheet is a sheet used for constituting a solar cell module, and particularly includes a front or back surface sealing sheet (front sheet or back sheet), a substrate sheet, and the like, and particularly as a back sheet. It is a solar cell sheet that can be suitably used.
In addition to the second solar cell sheet, an easy adhesion layer, a light reflective colored layer, a hard coat layer, or the like may be provided on the gas barrier layer.

Next, the third solar cell sheet will be described.
[Third solar cell sheet]
The third solar cell sheet is a solar cell sheet formed by laminating and integrating the first or second solar cell sheet and the sealing resin layer.

<Sealing resin layer>
The sealing resin layer of the layers constituting the third solar cell sheet is not particularly limited, but is preferably made of a resin composition containing a polyolefin resin or a modified polyolefin resin as a main component. Specific polyolefin resins and modified polyolefin resins are exemplified below, but these resins may be used alone or in combination of two or more. The sealing resin layer may be a single layer or a laminate of two or more layers as long as each is a layer composed of a resin composition mainly composed of a polyolefin resin or a modified polyolefin resin. .

[Polyolefin resin]
The kind of the polyolefin resin is not particularly limited, but is preferably at least one resin selected from the group consisting of a polyethylene polymer, a polypropylene polymer, and a cyclic olefin polymer.

[Polyethylene polymer]
The type of the polyethylene polymer is not particularly limited, and specifically, ultra-low density polyethylene, low density polyethylene, linear low density polyethylene (ethylene-α-olefin copolymer), medium density polyethylene. , High density polyethylene, or ultra high density polyethylene. Among these, linear low density polyethylene (ethylene-α-olefin copolymer) has low crystallinity and excellent transparency and flexibility, which impedes the power generation characteristics of the solar cell element and causes excessive stress to the solar cell element. In addition, it is preferable because it is difficult to cause defects such as damage.

The ethylene-α-olefin copolymer may be a random copolymer or a block copolymer. The type of α-olefin copolymerized with ethylene is not particularly limited, but usually an α-olefin having 3 to 20 carbon atoms is preferably used. Examples of the α-olefin copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 3-methyl-butene. -1,4-methyl-pentene-1 and the like. In the present invention, propylene, 1-butene, 1-hexene, and 1-octene are preferably used as the α-olefin copolymerized with ethylene from the viewpoints of industrial availability, various characteristics, and economical efficiency. It is done. The α-olefin copolymerized with ethylene may be used alone or in combination of two or more.

Further, the content of α-olefin copolymerized with ethylene is not particularly limited, but is usually 2 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and usually It is 40 mol% or less, preferably 30 mol% or less, more preferably 25 mol% or less. Within this range, the crystallinity is reduced by the copolymerization component, so that the transparency is improved and problems such as blocking of the raw material pellets are less likely to occur.

Specific examples of the polyethylene-based polymer used for the sealing resin layer include trade names “Hizex”, “Neozex”, “Ultzex” manufactured by Prime Polymer Co., Ltd., Japan. Trade names “Novatec HD”, “Novatech LD”, “Novatech LL”, trade names “Engage”, “Affinity”, “Infinity” manufactured by Dow Chemical Co., Ltd. "Fuse", Mitsui Chemicals' brand names "TAFMER A", "TAFMER P", Nippon Polyethylene's brand name "Kernel", etc. It can be illustrated.

[Polypropylene polymer]
The type of the polypropylene polymer is not particularly limited, and specific examples include a propylene homopolymer, a propylene copolymer, a reactor type polypropylene thermoplastic elastomer, and a mixture thereof. It is done.
As a copolymer of propylene, a random copolymer (random polypropylene) of propylene and ethylene or other α-olefin, or a block copolymer (block polypropylene), a block copolymer or a graft copolymer containing a rubber component Etc. The other α-olefin copolymerizable with propylene is preferably one having 4 to 12 carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4 -Methyl-1-pentene, 1-decene and the like, and one or a mixture of two or more thereof are used.

Further, the content of α-olefin copolymerized with propylene is not particularly limited, but is usually 2 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and usually It is 40 mol% or less, preferably 30 mol% or less, more preferably 25 mol% or less. Within this range, the crystallinity is reduced by the copolymerization component, so that the transparency is improved and problems such as blocking of the raw material pellets are less likely to occur.

Specific examples of polypropylene used in the sealing resin layer include trade names “Novatech PP” and “Wintech” manufactured by Nippon Polypro Co., Ltd., and “Prime Polypro” and “Prime” manufactured by Prime Polymer Co., Ltd. Examples include TPO "and trade name" Nobren "manufactured by Sumitomo Chemical Co., Ltd.

[Cyclic olefin polymer]
The type of the cyclic olefin polymer is not particularly limited, and specifically, a cyclic olefin polymer obtained by ring-opening polymerization of one or more cyclic olefins, a hydride thereof, and a linear chain. And a block copolymer of a linear α-olefin and a cyclic olefin, and a random copolymer of a linear α-olefin and a cyclic olefin.

The type of the cyclic olefin constituting the cyclic olefin polymer is not particularly limited, but bicyclohept-2-ene (2-norbornene) and its derivatives such as norbornene, 6-methylnorbornene, 6-ethyl Norbornene, 6-n-butylnorbornene, 5-propylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,6-dimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclo-3-dodecene and its derivatives For example, 8-methyltetracyclo-3-dodecene, 8-ethyltetracyclo-3-dodecene, 8-hexyltetracyclo-3-dodecene, 10-dimethyltetracyclo-3-dodecene, 5,10-dimethyl Tetracyclo-3-dodece And the like. In the present invention, norbornene, tetracyclododecene, and the like are preferably used from the viewpoints of industrial availability, various characteristics, economy, and the like.

The type of linear α-olefin copolymerized with the cyclic olefin is not particularly limited, but usually a linear α-olefin having 2 to 20 carbon atoms is preferably used. Examples of the linear α-olefin copolymerized with the cyclic olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. Etc. In the present invention, ethylene is preferably used as the linear α-olefin copolymerized with the cyclic olefin from the viewpoints of industrial availability, various characteristics, economy, and the like. The linear α-olefin copolymerized with the cyclic olefin may be used alone or in combination of two or more.

The content of the cyclic olefin copolymerized with the linear α-olefin is not particularly limited, but is usually 5 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more. And, it is usually 70 mol% or less, preferably 60 mol% or less, more preferably 50 mol% or less. When the content of the cyclic olefin is increased, the heat resistance, the barrier property and the transparency can be improved, and when the content is decreased, the flexibility is improved, which is preferable. If the content of the cyclic olefin is within this range, it is preferable because the crystallinity is reduced by the copolymerization component, transparency is exhibited, and problems such as blocking of raw material pellets hardly occur.

Specific examples of the cyclic olefin-based polymer used in the sealing resin layer include a product name “APEL” manufactured by Mitsui Chemicals, Inc., and a product name “TOPAS (TOPAS) manufactured by Topas Advanced Polymers Co., Ltd. ) ”, Trade names“ ZEONOR ”and“ ZEONEX ”manufactured by Nippon Zeon Co., Ltd. can be exemplified.

[Modified polyolefin resin]
The type of the modified polyolefin resin constituting the sealing resin layer in the present invention is not particularly limited, but EVA (ethylene-vinyl acetate copolymer), EVOH (ethylene-vinyl alcohol copolymer), E- MMA (ethylene-methyl methacrylate copolymer), E-EAA (ethylene-ethyl acrylate copolymer), E-GMA (ethylene-glycidyl methacrylate copolymer), ionomer resin (ionic crosslinkable ethylene-methacrylic acid copolymer) It is preferably at least one resin selected from the group consisting of a polymer, an ion crosslinkable ethylene-acrylic acid copolymer), a silane crosslinkable polyolefin, and a maleic anhydride graft copolymer.

The content of various monomers that modify the modified polyolefin resin is not particularly limited, but is usually 0.5 mol% or more, preferably 1 mol% or more, more preferably 2 mol% or more. And, it is usually 40 mol% or less, preferably 30 mol% or less, more preferably 25 mol% or less. Within this range, the crystallinity is reduced by the copolymerization component, so that the transparency is improved and problems such as blocking of the raw material pellets are less likely to occur.

Specific examples of the modified polyolefin resin used in the sealing resin layer include EVA (ethylene-vinyl acetate copolymer), trade name “Novatech EVA” manufactured by Nippon Polyethylene Co., Ltd., Mitsui DuPont Polychemical The product name “EVAFLEX” manufactured by Nihon Kayaku Co., Ltd., the “NUC” series manufactured by Nihon Unicar Co., Ltd., and the EVOH (ethylene-vinyl alcohol copolymer) product name manufactured by Nippon Synthetic Chemical Co., Ltd. “Soarnol”, trade name “Eval” manufactured by Kuraray Co., Ltd., and E-MMA (ethylene-methyl methacrylate copolymer) are trade names “ACRIFT” manufactured by Sumitomo Chemical Co., Ltd. As an acrylate copolymer), trade name “REXPEARL EEA” manufactured by Nippon Polyethylene Co., Ltd. E-GMA (ethylene-glycidyl methacrylate copolymer) is a trade name “BONDAST” manufactured by Sumitomo Chemical Co., Ltd., and an ionomer resin is a product name “HIMILAN” manufactured by Mitsui DuPont Polychemical Co., Ltd. As a silane crosslinkable polyolefin, trade name “Rychlon” manufactured by Mitsubishi Chemical Corporation can be exemplified, and as a maleic anhydride graft copolymer, “Admer” manufactured by Mitsui Chemicals, Inc. can be exemplified.

The resin composition constituting the encapsulating resin layer is described above for the purpose of further improving various physical properties (flexibility, heat resistance, transparency, adhesiveness, etc.), molding processability, and economical efficiency as necessary. Resins other than polyolefin resins and modified polyolefin resins can be mixed.
Examples of the resin include other polyolefin resins and various elastomers (olefin-based, styrene-based, etc.), modified with polar groups such as carboxyl group, amino group, imide group, hydroxyl group, epoxy group, oxazoline group, and thiol group. Resin and tackifying resin.

Moreover, various additives can be added to the resin composition constituting the sealing resin layer as necessary. Examples of the additive include radical generators (crosslinking agents / crosslinking aids), silane coupling agents, antioxidants, ultraviolet absorbers, weathering stabilizers, light diffusing agents, nucleating agents, pigments (for example, white pigments) ), Flame retardants, discoloration inhibitors and the like. In the present invention, it is preferable that at least one additive selected from a radical generator, a silane coupling agent, an antioxidant, an ultraviolet absorber, and a weathering stabilizer is added.

The thickness of the sealing resin layer is not particularly limited, but is usually 30 μm or more, preferably 50 μm or more, more preferably 100 μm or more, and about 1000 μm (1.0 mm) or less, preferably 700 μm or less. Preferably, it may be 500 μm or less.
Since the third solar cell sheet has a laminated structure of a flexible sealing resin layer and a rigid first or second solar cell sheet, the handling property is reduced even if the thickness is thin. The sealing resin layer may be thinned according to the type and configuration of the solar cell to be applied and in view of economy.

As a method for forming the sealing resin layer, there are known methods such as a single-screw extruder, a multi-screw extruder, a Banbury mixer, a kneader and other melt mixing equipment, and an extrusion casting method and a calendar method using a T die. In the present invention, an extrusion casting method using a T die is preferably used from the viewpoints of handling properties and productivity. The molding temperature in the extrusion casting method using a T die is appropriately adjusted depending on the flow characteristics and film forming properties of the resin composition to be used, but is generally 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, More preferably, the temperature is 140 ° C. or higher, and is generally 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 180 ° C. or lower. A radical generator or a silane coupling agent is added. In such a case, it is preferable to lower the molding temperature in order to suppress an increase in resin pressure and a fish eye accompanying the crosslinking reaction.

The solar cell sheet of the present invention has a surface such as scratch resistance and antifouling on the surface that is the outermost surface when formed as a solar cell module, that is, on the surface opposite to the surface in contact with the sealing resin layer. In order to develop the characteristics, a known hard coat treatment or antifouling treatment may be performed.

[Solar cell module]
The solar cell module of the present invention is provided with the aforementioned solar cell sheet of the present invention. Specifically, as shown in FIG. 1, the transparent substrate 10, the sealing resin layer 12A, the solar cell elements 14A and 14B, the sealing resin layer 12B, and the solar cell sheet of the present invention (in order from the sunlight receiving side) In this case, a back sheet 16 is laminated, and a junction box 18 (a terminal box for connecting wiring for taking out electricity generated from the solar cell element) is bonded to the lower surface of the solar cell sheet 16. Being done. The solar cell elements 14A and 14B are connected by a wiring 20 in order to conduct the generated current to the outside. The wiring 20 is taken out through a through hole (not shown) provided in the solar cell sheet 16 and connected to the junction box 18.
Since the solar cell module deteriorates when moisture enters the inside, when attaching accessories such as a junction box, ensure sufficient sealing so that outside air does not enter the inside of the solar cell module. Although it is necessary, according to the solar cell sheet of the present invention, since it can be bonded only by heat treatment, it is possible to easily and reliably prevent the intrusion of outside air.

As the transparent substrate, glass or a single-layer or multilayer plastic sheet such as acrylic resin, polycarbonate, polyester, fluorine-containing resin is used. In the case of plastic, for the purpose of providing gas barrier properties, an inorganic thin film is formed in the same manner as the gas barrier film constituting the solar cell sheet, or heat resistance, weather resistance, mechanical strength, chargeability, dimensions For the purpose of improving stability and the like, a crosslinking agent, an antioxidant, a light stabilizer, an ultraviolet absorber, an antistatic agent, a reinforcing fiber, a flame retardant, a preservative, and the like are added. Or a film can be laminated | stacked. The thickness of the transparent substrate can be appropriately set in view of strength, gas barrier properties, durability, and the like.
Moreover, about the sealing resin layer, it is as having demonstrated with the sheet | seat for 3rd solar cells.

The solar cell element is arranged and wired between the sealing resin layers. Examples thereof include a single crystal silicon type, a polycrystalline silicon type, an amorphous silicon type, various compound semiconductor types, a dye sensitized type, and an organic thin film type.

A method for producing a solar cell module when any one of the first to third solar cell sheets is used as a back sheet is not particularly limited. Generally, a transparent substrate, a sealing resin layer, a solar cell element, It has the process of laminating | stacking the sealing resin layer and the sheet | seat for solar cells in order, and the process of vacuum-sucking them and carrying out thermocompression bonding.
The solar cell module can be suitably used for various applications regardless of small size, large size, indoors, and outdoors due to the excellent durability, flame retardancy, dimensional stability and high mechanical strength of the solar cell sheet.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these examples.
In addition, the weather resistance was evaluated about the film obtained in each case.
<Weather resistance of the film obtained in each example>
Sunshine carbon-arc weathering tester (SWOM: Sunshine Weather-O-Meter) [made by Suga Test Instruments Co., Ltd., model name “Sunshine Weather Meter S80”] The subsequent breaking strength was measured with a tensile tester [manufactured by Shimadzu Corp., model name “Autograph AGS-500B”, speed: 100 mm / min, between chucks: 40 mm], and the residual ratio against the breaking strength before exposure (% ) And weather resistance was evaluated.

Production Example 1 Production of Resin Composition 1 Polystyrene ether (PPE) resin [trade name “PPO646” manufactured by SABIC Innovation Plastics Co., Ltd.] 90 parts by mass and styrene resin [trade name “Tuftec H1051” 10 A resin composition obtained by adding 7.5 parts by mass of a phosphorus flame retardant [made by Daihachi Chemical Co., Ltd., trade name “PX200”] and 3 parts by mass of carbon black as a pigment, and melt-kneading at 300 ° C. Product 1 was produced.

Production Example 2 Production of Resin Composition 2 A resin composition 2 was produced by adding 10 parts by mass of a styrene resin (above) to 90 parts by mass of a PPE resin (above), and melt-kneading at 300 ° C.

Production Example 3 Production of Coating Solution A (1) Production of Acrylic Resin Solution (a) In a polymerization can, 300 parts by mass of deionized water, 0.8 part by mass of potassium persulfate, disodium phosphate 12 hydrate. After 5 parts by mass and 0.3 parts by mass of sodium hydrogenphosphate dihydrate were charged and sufficiently substituted with nitrogen, the internal temperature was raised to 70 ° C. While maintaining the internal temperature at this temperature and stirring, 19.6 parts by mass of styrene, 69.9 parts by mass of butyl acrylate, 0.9 parts by mass of allyl methacrylate, 2.5 parts by mass of sodium dioctyl sulfosuccinate (emulsifier) The mixture consisting of was added continuously over 2 hours.
Immediately after the addition, a mixture comprising 1.0 part by mass of t-butylperoxy-2-ethylhexanoate, 2.2 parts by mass of styrene, 7.7 parts by mass of butyl acrylate, and 0.1 parts by mass of allyl acrylate Was added. After 30 minutes had elapsed after the addition, the internal temperature was raised to 90 ° C., and the reaction was continued at this temperature for 3 hours to obtain a crosslinked elastic body emulsion.
This crosslinked elastic body had an average particle size of 0.20 μm, a gel content of 97.1% by mass, and a degree of swelling of 7.2.
(B) Production of Graft Copolymer The polymerization can was charged with 400 parts by mass of the cross-linked elastic emulsion obtained in (i) above, purged with nitrogen while stirring, and then the internal temperature was raised to 80 ° C. While maintaining the internal temperature at this temperature and stirring, after adding a solution obtained by dissolving 0.15 parts by mass of sodium formaldehyde sulfoxylate in 3.0 parts by mass of deionized water, 30.0 parts by mass of methyl methacrylate, A mixture of 0.03 parts by mass of n-octyl mercaptan and 0.15 parts by mass of paramentane hydroperoxide (50% by mass solution) was continuously added over 30 minutes. After completion of the addition, the polymerization reaction was continued for another 30 minutes to obtain a graft copolymer emulsion.
The obtained graft copolymer emulsion was salted out according to a conventional method, and the polymer was collected by filtration, washed with water and dried to obtain a graft copolymer powder.
(2) Preparation of acrylic resin solution Beads 13 of methacrylic resin (methyl methacrylate / copolymer having an ethyl methacrylate mass ratio of 96/4) were added to 6.5 parts by mass of the graft copolymer obtained in (b) above. .5 parts by mass are mixed, this mixture is put into a mixed solvent consisting of 64 parts by mass of methyl ethyl ketone and 16 parts by mass of toluene, dissolved with stirring, and an acrylic resin solution having a solid content concentration of 20% by mass is prepared. did.
(3) Preparation of coating solution A containing an ultraviolet absorber 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole as a UV absorber is added to the acrylic resin solution prepared by the method (2) above. It added in the ratio of 14 mass% with respect to solid content, and prepared the coating liquid A containing a ultraviolet absorber.

Production Example 4 Production of Coating Solution B As a benzotriazole-based monomer, 5.0 parts by mass of 2- [2-hydroxy-5- (methacryloyloxyethyl) phenyl] -2H-benzotriazole, 40.0 parts by mass of cyclohexyl methacrylate Piperidine 2.5 parts by mass, acrylic acid 10 parts by mass, methyl methacrylate 14.0 parts by mass, butyl methacrylate 22.5 parts by mass, 2-ethylhexyl acrylate 10.0 parts by mass and glycidyl methacrylate 5.0 parts by mass Polymerization was carried out according to the method, and the resulting acrylic copolymer was dissolved in ethyl acetate to produce a coating solution B having a solid content concentration of 20% by mass.

Example 1
(1) Manufacture of a base film having a two-layer / three-layer structure Using the resin composition 1 obtained in Production Example 1 as an intermediate layer, the surface layer using the resin composition 2 obtained in Production Example 2 on both sides thereof A base film having a two-layer / three-layer structure having the following structure was produced as follows.
As a test lab machine, a 50 mmφ, 35 mmφ extruder equipped with two kinds of three-layer multi-layer T-die was used. The barrel temperature was set to 220 to 300 ° C., the die temperature was set to 290 ° C., and the thickness was 50 μm by extrusion (5 μm / each layer). 40 μm / 5 μm) of a base film having a two-layer / three-layer structure was formed.
Specifically, the resin composition 1 and the resin composition 2 are put into the extruder while performing a nitrogen purge, the molten raw material is extruded from a T die die, and cooled and solidified with a cast roll. Was adjusted to form a base film having a predetermined thickness (50 μm) and a two-layer / three-layer structure.
(2) Formation of weather-resistant coating film The coating liquid A obtained in Production Example 3 was continuously applied by the roll coating method on the base film having the two-layered three-layer structure manufactured in (1) above. The film was held in a drying oven at 100 ° C. for 1 minute to volatilize the solvent and heat-treated, and the film on which the weather-resistant coating film had been formed was wound up. The amount of the coated film on the obtained film was about 5 g / m ² (about 5 μm).
The weather resistance of the base film having a two-layer / three-layer structure in which the weather-resistant coating film was formed was evaluated. The results are shown in Table 1.

Example 2
In Example 1 (2), except that the coating liquid B obtained in Production Example 4 was used in place of the coating liquid A, the same operation as in Example 1 was performed, and a weather-resistant coating film was formed to a thickness of 50 μm. A base film having a two-layer three-layer structure was obtained. The amount of the coated film on the film was about 5 g / m ² (about 5 μm).
The weather resistance of the base film having a two-layer / three-layer structure in which the weather-resistant coating film was formed was evaluated. The results are shown in Table 1.

Comparative Example 1
About the base material film of 2 types and 3 layer lamination structure obtained in Example 1, the weather resistance was evaluated without forming a weather resistant coating film. The results are shown in Table 1.

Comparative Example 2
Using the resin composition 2 obtained in Production Example 2, a transparent PPE monolayer film having a thickness of 50 μm was obtained in the same manner as in Example 1 (1), and then the same as in Example 1 (2). A weather-resistant coating film consisting of A was formed to obtain a transparent PPE film on which the weather-resistant coating film was formed. The amount of the coated film on the film was about 5 g / m ² (about 5 μm).
The weather resistance of the transparent PPE film on which this weather resistant coating film was formed was evaluated. The results are shown in Table 1.

Comparative Example 3
Using the resin composition 2 obtained in Production Example 2, a transparent PPE single layer film having a thickness of 50 μm was obtained in the same manner as in Example 1 (1). A weather-resistant coating film was formed to obtain a transparent PPE film on which the weather-resistant coating film was formed. The amount of the coated film on the film was about 5 g / m ² (about 5 μm).
The weather resistance of the transparent PPE film on which this weather resistant coating film was formed was evaluated. The results are shown in Table 1.

Comparative Example 4
Using the resin composition 2 obtained in Production Example 2, a transparent PPE single layer film having a thickness of 50 μm was obtained in the same manner as in Example 1 (1).
About this transparent PPE single layer film, the weather resistance was evaluated without forming a weather resistant coating film. The results are shown in Table 1.

In addition, in the accelerated weather resistance test of each film obtained in Examples 1 and 2 and Comparative Examples 1 to 4, the relationship between the exposure time and the residual ratio (%) to obtain the breaking strength before exposure is shown in FIG. It shows with.

As can be seen from FIG. 2, the films of Examples 1 and 2 in which a weather-resistant coating film is provided on a base film having a two-layer / three-layer structure comprising a pigment (carbon black) in the intermediate layer Compared to the film of Comparative Example 1 in which no film was provided, the residual ratio of breaking strength was high and the weather resistance was excellent. Moreover, the film of the comparative examples 2 and 3 which provided the weather resistant coating film in the transparent PPE single layer film which does not use the pigment (carbon black) is the comparative example which does not provide the weather resistant coating film in the same transparent PPE single layer film. Although a significant difference was observed in the residual ratio of the breaking strength with respect to the exposure up to 310 hours as compared with the film of No. 4, the deterioration was advanced so that the film could not be used as a film in the exposure at 522 hours.
That is, it can be seen that the blending of the pigment (carbon black) and the formation of the weather-resistant coating film exhibit excellent weather resistance due to a synergistic effect.
Although no significant difference was found between Example 1 and Example 2 regarding the weather resistance in the above test, the embodiment of Example 2 using the coating liquid B having an ultraviolet absorbing group in the copolymer was long. It is presumed that this is a preferred embodiment from the viewpoint of preventing bleeding out of the weatherable active ingredient due to the use of a period.

Example 3
(1) Production of Black PPE Film Using the resin composition 1 obtained in Production Example 1 and using an extruder equipped with a T die, extrusion molding was performed under the following conditions, and a black PPE single having a thickness of 50 μm. A layer film was produced.
<Extrusion molding conditions>
A 50 mmφ extruder equipped with a T die was used as a test laboratory machine, a barrel temperature was set to 220 to 300 ° C., a die temperature was set to 290 ° C., and a 50 μm-thick single layer sheet was formed by extrusion molding.
Specifically, while performing a nitrogen purge to the extruder, the raw material is charged, the melted raw material is extruded from a T-die die, cooled and solidified with a cast roll, and the speed of the cast roll is adjusted to obtain a predetermined value. A single-layer sheet having a thickness (50 μm) was formed.

(2) Formation of weather-resistant coating film The same operation as in Example 1 (2) was performed on one surface of the black PPE monolayer film obtained in (1) to form a weather-resistant coating film. The amount of the coated film on the film was about 5 g / m ² (about 5 μm).

Example 4
In Example 3 (2), except that the coating liquid B obtained in Production Example 4 was used in place of the coating liquid A, the same operation as in Example 3 was performed, and the thickness of the weather-resistant coating film formed was 50 μm. A base film having a two-layer three-layer structure was obtained. The amount of the coated film on the film was about 5 g / m ² (about 5 μm).

For the case of the base film of the two-layered three-layer structure of Examples 1 and 2 and the case of the black PPE single-layer film of Examples 3 and 4, the weather-resistant coating film by application of coating solutions A and B Compared with the case of the single-layer film of Examples 3 and 4, the surface condition of the film before coating is better in the base film of the two-layer / three-layer structure of Examples 1 and 2 than in the case of the single-layer films of Examples 3 and 4. In addition, from the viewpoint of secondary workability, it was confirmed that the base film having a two-layer / three-layer structure of Examples 1 and 2 was a more preferable embodiment. In addition, even if it is a single layer film, it is estimated that there exists an effect similarly about a weather resistance.

The polyphenylene ether-based laminated film of the present invention is suitably used as a solar cell sheet used for protecting a solar cell module.

DESCRIPTION OF SYMBOLS 10 ... Transparent substrate 12A, 12B ... Sealing resin layer 14A, 14B ... Solar cell element 16 ... Sheet | seat 18 for solar cells ... Junction box 20 ... Wiring

Claims (14)

A polyphenylene ether-based laminated film obtained by laminating an ultraviolet-absorbing coating film on at least one side of a base film composed of a resin composition containing polyphenylene ether and a pigment. The polyphenylene ether-based laminated film according to claim 1, further comprising a styrene-based resin in the resin composition. The polyphenylene ether-based laminated film according to claim 1 or 2, wherein the ultraviolet absorbing coating film is an acrylic ultraviolet absorbing coating film. 4. The polyphenylene ether-based laminated film according to claim 2 or 3, wherein the content ratio of the polyphenylene ether and the styrene resin in the resin composition is 99: 1 to 60:40 by mass ratio. The said acrylic ultraviolet-absorbing coating film is formed using the copolymer of the acrylic monomer which has an ultraviolet-absorbing group, and an acrylic monomer other than that. Polyphenylene ether laminated film. The polyphenylene ether-based laminated film according to any one of claims 3 to 5, wherein the acrylic ultraviolet-absorbing coating film is formed by applying a solvent-based paint and drying. The polyphenylene ether-based laminated film according to any one of claims 1 to 6, wherein the pigment in the resin composition is a black pigment. The base film is a laminated film having at least an intermediate layer and surface layers on both sides thereof, and the intermediate layer is composed of a resin composition A containing polyphenylene ether and a pigment, and is provided on both sides thereof. The polyphenylene ether-based laminated film according to any one of claims 1 to 7, which comprises a resin composition B that contains polyphenylene ether and substantially does not contain any pigment. The polyphenylene ether-based laminated film according to claim 8, further comprising a styrene-based resin in the resin composition A and / or the resin composition B. A solar cell sheet using the polyphenylene ether-based laminated film according to any one of claims 1 to 9. A solar cell sheet obtained by further laminating a gas barrier layer on the solar cell sheet according to claim 10. A solar cell sheet obtained by laminating and integrating the solar cell sheet according to claim 10 or 11 and a sealing resin layer. A solar cell module comprising the solar cell sheet according to any one of claims 10 to 12. The solar cell module according to claim 13, wherein the solar cell sheet is used as a back sheet.

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