JP2010177384A - Backsheet for solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a backsheet for a solar cell which has dark-colored appearance and is superior in heat resistance, flexibility, weatherability and resistance to scratches, and to provide a solar cell module with the backsheet. <P>SOLUTION: The backsheet (1) for the solar cell sequentially includes a first resin layer (11), a second resin layer (12), a third resin layer (13) and a fourth resin layer (14). At least one of the first resin layer, the second resin layer and the third resin layer is an infrared-transparent colored resin layer. The fourth resin layer is a rear protective layer. A thickness H<SB>A</SB>of the first resin layer, a thickness H<SB>B</SB>of the second resin layer and a thickness H<SB>C</SB>of the third resin layer satisfy formulas of 0.4≤(H<SB>A</SB>+H<SB>C</SB>)/H<SB>B</SB>≤2.4 and 0.7≤H<SB>A</SB>/H<SB>C</SB>≤1.3. In addition, when light with a wavelength of 800-1,400 nm is radiated to the surface of the first resin layer of the backsheet for the solar cell, reflectivity against the light is less than 50%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention has a dark appearance and absorbs visible light when irradiated with light but transmits infrared light to prevent heat storage, and has heat resistance, flexibility, weather resistance and scratch resistance. The present invention relates to a solar cell backsheet that is superior to the above and a solar cell module including the same.

In recent years, solar cells have received more attention as energy supply means in place of petroleum, which is an energy source that forms carbon dioxide, which causes global warming. The demand for solar cells is also increasing, and stable supply and cost reduction of various members constituting solar cell modules included in solar cells have been required. In addition, the demand for improving the power generation efficiency of solar cells has increased.
In the solar cell module, a large number of plate-like solar cell elements are arranged, and these are wired in series and in parallel, and packaged to protect the elements and unitized. And this solar cell module usually uses a composition containing an ethylene / vinyl acetate copolymer having a high transparency and excellent moisture resistance by covering the surface of the solar cell element that is exposed to sunlight with a glass plate. Thus, the gap between the solar cell elements is filled to form a filler portion, and the back surface (the lower surface of the filler portion) is sealed with a member called a solar cell backsheet.

As a back sheet for a solar cell, a sheet in which a white thermoplastic resin sheet is laminated on both sides of a polyester sheet is known in order to increase the reflectance of sunlight and increase the power generation efficiency of the solar cell (Patent Document 1). 2).
When arranging solar cells on the roof of a house, etc., it is preferred to be colored in a dark color such as black from the viewpoint of appearance, and for that reason, it is colored in a dark color There is a need for solar cell backsheets.

As a back sheet for a solar cell colored in a dark color, a sheet using carbon black is generally used. In this embodiment, the carbon black absorbs sunlight and the temperature rises, so that not only the power generation efficiency of the solar cell is lowered but also the durability may be lowered.
Moreover, as another solar cell backsheet, a sheet made of a low heat storage thermoplastic resin composition containing a thermoplastic resin and an inorganic pigment having infrared reflection characteristics is known (see Patent Document 3).
Furthermore, a solar cell backsheet that is provided with a black resin layer containing a perylene pigment on the surface thereof and prevents heat storage by reflecting near infrared rays with a reflectance of light having a wavelength of 800 to 1,100 nm of 30% or more. It is known (see Patent Document 4).

  Moreover, in a solar cell module including a solar cell backsheet, when water, water vapor, or the like enters from the solar cell backsheet side, the solar cell element may be deteriorated, and the power generation efficiency may be lowered.

JP 2006-270025 A JP 2007-177136 A JP 2007-103813 A JP 2007-128943 A

  An object of this invention is to provide the solar cell backsheet which has a dark-colored external appearance, and is excellent in heat resistance, flexibility, a weather resistance, and a flaw resistance, and a solar cell module provided with the same.

The present invention is shown below.
1. In the solar cell backsheet comprising a first resin layer, a second resin layer, a third resin layer, and a fourth resin layer in order, of the first resin layer, the second resin layer, and the third resin layer. At least one layer is an infrared transparent colored resin layer, the fourth resin layer is a back surface protective layer, the thickness of the first resin layer (H _A ), the thickness of the second resin layer (H _B ) and thickness of the third resin layer _{(H C)} satisfies the following formula (1) and 2, and the light of wavelength 800～1,400Nm, above the backsheet for the solar cell the The solar cell backsheet, wherein when reflected on the surface of one resin layer, the reflectance with respect to the light is less than 50%.
_{0.4 ≦ (H A + H C} ) / H B ≦ 2.4 (1)
_{0.7 ≦ H A / H C ≦} 1.3 (2)
2. 2. The solar cell backsheet as described in 1 above, wherein when light having a wavelength of 400 to 700 nm is radiated to the surface of the first resin layer in the solar cell backsheet, the light absorption rate is 60% or more.
3. The solar cell backsheet according to 1 or 2 above, wherein the dimensional change rate when left at 150 ° C. for 30 minutes is ± 1% or less.
4). The thermoplastic resin that constitutes the first resin layer, the thermoplastic resin that constitutes the second resin layer, and the thermoplastic resin that constitutes the third resin layer are all thermoplastic resins containing an aromatic vinyl resin. The solar cell backsheet according to any one of 1 to 3 above.
5). The glass transition temperature of the thermoplastic resin constituting the first resin layer and the glass transition temperature of the thermoplastic resin constituting the third resin layer are both glass of the thermoplastic resin constituting the second resin layer. The solar cell backsheet according to any one of 1 to 4 above, which is lower than a transition temperature.
6). The solar cell backsheet according to any one of 1 to 5, wherein the fourth resin layer is a resin layer having flame retardancy.
7). The solar cell backsheet according to any one of 1 to 6, further comprising a water vapor barrier layer between the third resin layer and the fourth resin layer.
8). The back sheet for a solar cell according to any one of 1 to 7 above, wherein the water vapor barrier layer is formed of a vapor deposition film in which a film containing a metal and / or a metal oxide is formed on a surface thereof.
9. 9. The solar cell backsheet according to 8 above, wherein the solar cell backsheet has a thickness of 50 to 1,000 μm.
10. A solar cell module comprising the solar cell backsheet according to any one of 1 to 9 above.

According to the solar cell backsheet of the present invention, it has a dark appearance and is excellent in heat resistance (dimensional stability), flexibility, weather resistance and scratch resistance. When light with a wavelength of 800 to 1,400 nm is radiated to the surface of the first resin layer in the solar cell backsheet, the reflectance with respect to the light is less than 50%. It can suppress that the solar cell backsheet and a solar cell module provided with this store heat, and the durability of the solar cell backsheet, the solar cell module, and the solar cell is reduced by light. For example, when the first resin layer, the second resin layer, and the third resin layer are infrared transmissive colored resin layers, the wavelengths 800 to 1, which are incident from the first resin layer side in the solar cell backsheet. Since the light of 400 nm tends to be transmitted to the fourth resin layer side in the solar cell backsheet, the above-described suppression effect is particularly excellent.
When light having a wavelength of 400 to 700 nm is radiated to the surface of the first resin layer in the solar cell backsheet, if the light absorption rate is 60% or more, the infrared transparent colored resin layer According to the color, it is possible to provide a solar cell module excellent in dark appearance, and when the solar cell module provided with this sheet is arranged on the roof of a house, it is possible to obtain excellent appearance, design, etc. it can.
When the dimensional change rate when the solar cell backsheet of the present invention is allowed to stand at 150 ° C. for 30 minutes is ± 1% or less, the heat resistance is excellent.
The thermoplastic resin that constitutes the first resin layer, the thermoplastic resin that constitutes the second resin layer, and the thermoplastic resin that constitutes the third resin layer are all thermoplastic resins containing an aromatic vinyl resin. In some cases, it is excellent in hydrolysis resistance, dimensional stability, impact resistance and the like.
The glass transition temperature of the thermoplastic resin constituting the first resin layer and the glass transition temperature of the thermoplastic resin constituting the third resin layer are both glass of the thermoplastic resin constituting the second resin layer. When the temperature is lower than the transition temperature, it is possible to suppress the occurrence of cracks and the like when bent and to balance heat resistance and flexibility.
In the case where the fourth resin layer is a resin layer having flame retardancy, a solar cell backsheet that is more excellent in fire resistance from the back surface can be obtained.
When a water vapor barrier layer is provided between the third resin layer and the fourth resin layer, a solar cell back sheet having excellent water vapor barrier properties can be obtained.
When the water vapor barrier layer is formed of a vapor deposition film having a film containing a metal and / or metal oxide formed on the surface thereof, the balance between heat resistance (dimensional stability) and flexibility is lowered. No water vapor barrier property. Moreover, deterioration of the solar cell element can be suppressed.
When the thickness of the solar cell backsheet is 50 to 1,000 μm, the flexibility is excellent.

  Since the solar cell module of the present invention includes the solar cell backsheet of the present invention, a solar cell excellent in heat resistance, weather resistance, design properties, water vapor barrier properties and scratch resistance can be formed. This solar cell is suitable for outdoor use exposed to sunlight or wind and rain for a long time.

It is a schematic sectional drawing which shows an example of the solar cell backsheet. It is a schematic sectional drawing which shows the other example of the solar cell backsheet. It is a schematic sectional drawing which shows an example of the solar cell module of this invention.

  The present invention will be described in detail below. In this specification, “(co) polymerization” means homopolymerization and copolymerization. Further, “(meth) acryl” means acryl and methacryl, and “(meth) acrylate” means acrylate and methacrylate.

The solar cell backsheet of the present invention is a sheet comprising a first resin layer, a second resin layer, a third resin layer, and a fourth resin layer in sequence, and its schematic cross section is exemplified in FIG. That is, the solar cell backsheet 1 of FIG. 1 is a laminated sheet that includes the first resin layer 11, the second resin layer 12, the third resin layer 13, and the fourth resin layer 15 in order. Moreover, in the solar cell backsheet of this invention, the schematic cross section in the case of providing a water vapor | steam barrier layer between the said 3rd resin layer and the said 4th resin layer is illustrated by FIG. That is, the solar cell backsheet 1 ′ in FIG. 2 includes a first resin layer 11, a second resin layer 12, a third resin layer 13, a water vapor barrier layer 14, and a fourth resin layer 15 in order. It is.
In the solar cell backsheet of the present invention, the surface (upper surface side) of the first resin layer 11 is adhered to a filler part including an ethylene / vinyl acetate copolymer composition and the like embedding the solar cell element. Used for.

The first resin layer is preferably a thermoplastic resin composition (hereinafter referred to as “first thermoplastic resin composition”) containing a thermoplastic resin (hereinafter referred to as “thermoplastic resin (I)”). In the solar cell backsheet of the present invention, it is a layer having an effect of imparting flexibility. The second resin layer is preferably a thermoplastic resin composition (hereinafter referred to as “second thermoplastic resin composition”) containing a thermoplastic resin (hereinafter referred to as “thermoplastic resin (II)”). It is a layer obtained by using, and is a base layer in the solar cell backsheet of the present invention and is a layer having heat resistance. The third resin layer is preferably a thermoplastic resin composition (hereinafter referred to as “third thermoplastic resin composition”) containing a thermoplastic resin (hereinafter referred to as “thermoplastic resin (III)”). .), And is a layer having an effect of imparting flexibility in the solar cell backsheet of the present invention.
The fourth resin layer is a back surface protective layer, and is preferably a thermoplastic resin composition (hereinafter referred to as “fourth heat”) containing a thermoplastic resin (hereinafter referred to as “thermoplastic resin (IV)”). It is a layer obtained using a “plastic resin composition”. The fourth resin layer mainly protects the solar cell backsheet of the present invention, thereby suppressing the impact, heat, damage, deterioration, etc. caused by the force from the back surface, and the solar cell backsheet. It is a layer which has an effect | action which provides durability etc. to a solar cell module provided with.
The first thermoplastic resin composition, the second thermoplastic resin composition, the third thermoplastic resin composition, and the fourth thermoplastic resin composition are preferably compositions having film-forming properties. is there.

The glass transition temperature (hereinafter referred to as “Tg”) of the thermoplastic resin (I) contained in the first thermoplastic resin composition is from the viewpoint of imparting flexibility to the solar cell backsheet of the present invention. The temperature is preferably 90 ° C to 200 ° C, more preferably 95 ° C to 180 ° C, still more preferably 100 ° C to 170 ° C, and particularly preferably 110 ° C to 160 ° C.
The glass transition temperature (Tg) of the thermoplastic resin (II) contained in the second thermoplastic resin composition is preferably 120 ° C. to from the viewpoint of imparting heat resistance to the solar cell backsheet of the present invention. It is 220 degreeC, More preferably, it is 130 degreeC-200 degreeC, More preferably, it is 140 degreeC-190 degreeC.
The glass transition temperature (Tg) of the thermoplastic resin (III) contained in the third thermoplastic resin composition is preferably 90 from the viewpoint of imparting flexibility to the solar cell backsheet of the present invention. C. to 200.degree. C., more preferably 95.degree. C. to 180.degree. C., still more preferably 100.degree. C. to 170.degree. C., and particularly preferably 110.degree.
The Tg can be measured by a differential scanning calorimeter (DSC).

In the solar cell backsheet of the present invention, preferred embodiments for obtaining excellent heat resistance and flexibility are as follows. That is, the Tg of the thermoplastic resin (I) and the Tg of the thermoplastic resin (III) are the same as or lower than the Tg of the thermoplastic resin (II). In order to impart sufficient flexibility, the Tg of the thermoplastic resin (I) and the Tg of the thermoplastic resin (III) are preferably lower than the Tg of the thermoplastic resin (II). The difference between the Tg of the thermoplastic resin (I) and the Tg of the thermoplastic resin (II) is preferably 10 ° C. or higher, more preferably 15 ° C. or higher, and the Tg of the thermoplastic resin (II) and the thermoplastic resin (III ) Is preferably 10 ° C. or higher, more preferably 15 ° C. or higher.
When two or more types of thermoplastic resins are included in each resin layer and a plurality of Tg values are obtained by the DSC curve, the higher Tg value is adopted.

In the present invention, at least one of the first resin layer, the second resin layer, and the third resin layer is an infrared transparent colored resin layer. That is, all of the first resin layer, the second resin layer, and the third resin layer may be an infrared transparent colored resin layer, two layers may be an infrared transparent colored resin layer, One layer may be an infrared transparent colored resin layer. In order to form the infrared transparent colored resin layer, a thermoplastic resin and a colorant having a property of absorbing visible light and transmitting infrared light (hereinafter also referred to as “infrared transparent colorant”) are contained. A thermoplastic resin composition is used.
A preferable aspect as a solar cell backsheet of this invention is mentioned later.

Hereinafter, each layer will be described in order.
The thermoplastic resin (I) contained in the first thermoplastic resin composition forming the first resin layer is not particularly limited as long as it is a resin having thermoplasticity. Examples of the thermoplastic resin (I) constituting the first resin layer include aromatic vinyl resins, polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl acetate resins, saturated polyester resins, polycarbonate resins, and acrylic resins. (For example, (co) polymers of (meth) acrylic acid ester compounds), fluororesins, ethylene / vinyl acetate resins and the like. These can be used alone or in combination of two or more. Of these, aromatic vinyl resins are preferred from the viewpoints of hydrolysis resistance and dimensional stability.

  The aromatic vinyl resin is a rubber-reinforced aromatic vinyl resin obtained by polymerizing an aromatic vinyl compound or the like in the presence of a rubbery polymer; an aromatic vinyl compound such as an acrylonitrile / styrene copolymer. (Co) polymers and the like using a vinyl monomer containing In the present invention, the aromatic vinyl resin is preferably a rubber-reinforced aromatic vinyl resin. When the thermoplastic resin (I) contains a rubber-reinforced aromatic vinyl resin, a first resin layer excellent in hydrolysis resistance, dimensional stability, and impact resistance can be formed.

Examples of the aromatic vinyl resin include a rubber-reinforced aromatic vinyl resin (I-) obtained by polymerizing a vinyl monomer (b11) containing an aromatic vinyl compound in the presence of the rubber polymer (a11). 1), (co) polymer (I-2) of vinyl monomer (b12) containing an aromatic vinyl compound, and rubber-reinforced aromatic vinyl resin (I-1) and (co) polymer ( The mixture of I-2) is mentioned.
The rubber-reinforced aromatic vinyl resin (I-1) usually includes a copolymer resin obtained by graft copolymerization of a vinyl monomer (b11) containing an aromatic vinyl compound with a rubber polymer (a11); The ungrafted component which is not grafted on the rubber polymer (a11), that is, the (co) polymer by the remaining vinyl monomer (b11) is included.

  As described above, the aromatic vinyl resin preferably contains at least one rubber-reinforced aromatic vinyl resin (I-1), and one or more kinds of rubber-reinforced aromatic vinyl resin (I-1). Or, a combination of one or more of rubber-reinforced aromatic vinyl resins (I-1) and one or more of (co) polymer (I-2) is particularly preferred. In these cases, the content of the rubbery polymer (a11) in the aromatic vinyl resin is preferably 5 to 40% by mass, more preferably 8 to 30% by mass with respect to 100% by mass of the aromatic vinyl resin. %, More preferably 10 to 20% by mass, particularly preferably 12 to 18% by mass. When the content exceeds 40% by mass, the heat resistance is not sufficient, and it may be difficult to form the first resin layer using the first thermoplastic resin composition. On the other hand, if the content is less than 5% by mass, flexibility may not be sufficient.

  The rubbery polymer (a11) used for forming the rubber-reinforced aromatic vinyl resin (I-1) is not particularly limited as long as it is rubbery at room temperature, and any of a homopolymer and a copolymer may be used. Good. Further, the rubbery polymer (a11) may be either a crosslinked polymer or a non-crosslinked polymer.

The rubbery polymer (a11) is not particularly limited, but is conjugated diene rubber, hydrogenated conjugated diene rubber, ethylene / α-olefin copolymer rubber, acrylic rubber, silicone rubber, silicone / acrylic composite. Rubber etc. are mentioned. These can be used alone or in combination of two or more.
Of the above, conjugated diene rubbers are preferable from the viewpoint of impact resistance, and acrylic rubbers, silicone rubbers, silicone / acrylic composite rubbers, ethylene / α-olefin copolymer rubbers and hydrogenated resins from the viewpoint of weather resistance. Conjugated diene rubber is preferred.

  The shape of the rubbery polymer (a11) is not particularly limited, and may be particulate (spherical or substantially spherical), linear, curved, or the like. When it is particulate, the volume average particle diameter is preferably 5 to 2,000 nm, more preferably 10 to 1,800 nm, and still more preferably 50 to 1,500 nm. If the volume average particle diameter is in the above range, the processability of the first thermoplastic resin composition and the impact resistance of the obtained first resin layer are excellent. The volume average particle diameter can be measured by image analysis using an electron micrograph, a laser diffraction method, a light scattering method, or the like.

Examples of the conjugated diene rubber include polybutadiene, butadiene / styrene random copolymer, butadiene / styrene block copolymer, butadiene / acrylonitrile copolymer, and the like. These can be used alone or in combination of two or more.
In the present invention, the conjugated diene rubber preferably has a glass transition temperature of −20 ° C. or lower from the viewpoints of flexibility, low temperature impact property and the like.

  As said acrylic rubber, 80 mass% or more is included with respect to the whole quantity of the structural unit which comprises the said acrylic rubber for the structural unit derived from the alkyl group C2-C8 acrylic acid alkyl ester (co). Polymers are preferred.

  Examples of the alkyl acrylate having 2 to 8 carbon atoms in the alkyl group include ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate. Etc. These may be used alone or in combination of two or more. Preferred alkyl acrylates are n-butyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate.

  When the acrylic rubber contains a structural unit derived from another monomer, other monomers include vinyl chloride, vinylidene chloride, acrylonitrile, vinyl ester, methacrylic acid alkyl ester, (meth) acrylic acid, Monofunctional monomers such as styrene; mono- or polyethylene glycol di (such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate ( Di- or triallyl compounds such as (meth) acrylate, divinylbenzene, diallyl phthalate, diallyl maleate, diallyl succinate, triallyl triazine, allyl compounds such as allyl (meth) acrylate, conjugated diene-based compounds such as 1,3-butadiene Crosslinkable monomer such as things like.

In the present invention, the acrylic rubber preferably has a glass transition temperature of −10 ° C. or lower from the viewpoints of flexibility, low temperature impact property and the like. The acrylic rubber having the glass transition temperature is usually a copolymer containing a structural unit derived from the crosslinkable monomer.
The content of the structural unit derived from the crosslinkable monomer constituting the preferred acrylic rubber is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass with respect to the total amount of the structural unit. %, More preferably 0.1 to 5% by mass.

  The volume average particle diameter of the acrylic rubber is preferably 5 to 500 nm, more preferably 10 to 450 nm, and still more preferably 20 to 400 nm from the viewpoints of flexibility, low temperature impact property and the like.

  The acrylic rubber is produced by a known method, but a preferred production method is an emulsion polymerization method.

  The silicone rubber is preferably a rubber contained in latex in order to facilitate emulsion polymerization, which is a suitable method for producing the rubber-reinforced aromatic vinyl resin (I-1). Therefore, the silicone rubber is, for example, a polyorganosiloxane rubber produced by the method described in US Pat. Nos. 2,891,920, 3,294,725, etc. Can do.

  The polyorganosiloxane rubber is obtained by, for example, shear-mixing organosiloxane and water in the presence of a sulfonic acid-based emulsifier such as alkylbenzene sulfonic acid or alkyl sulfonic acid using a homomixer or an ultrasonic mixer. The silicone rubber contained in the latex obtained by the condensation method is preferable. Alkylbenzenesulfonic acid is suitable because it acts as an emulsifier for organosiloxane and also as a polymerization initiator. In this case, it is preferable to use an alkylbenzene sulfonic acid metal salt, an alkyl sulfonic acid metal salt, or the like in combination because the silicone rubber is stably maintained when the rubber-reinforced aromatic vinyl resin (I-1) is produced. The polymer end of the polyorganosiloxane rubber may be sealed with, for example, a hydroxyl group, an alkoxy group, a trimethylsilyl group, a methyldiphenylsilyl group, or the like. Further, if necessary, a graft crossing agent and / or a crosslinking agent may be co-condensed within a range not impairing the target performance of the present invention. By using these, impact resistance can be improved.

The organosiloxane used in the above reaction is, for example, the general formula [R ¹ _m SiO _{(4-m) / 2} ] (wherein R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, and m is 0 to 0. 3 represents an integer of 3.). The structure of this compound is linear, branched or cyclic, but is preferably an organosiloxane having a cyclic structure. R ¹ possessed by the organosiloxane, that is, monovalent hydrocarbon groups include alkyl groups such as methyl group, ethyl group, propyl group and butyl group; aryl groups such as phenyl group and tolyl group; vinyl groups and allyl groups An alkenyl group such as: a group in which a part of hydrogen atoms bonded to carbon atoms in these hydrocarbon groups is substituted with a halogen atom, a cyano group, or the like; and at least one hydrogen atom in an alkyl group is substituted with a mercapto group Group and the like.

Examples of the organosiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. In addition to a cyclic compound such as a linear or branched organosiloxane. These can be used alone or in combination of two or more.
The organosiloxane may be a polyorganosiloxane condensed in advance, for example, having an Mw of about 500 to 10,000. When the organosiloxane is a polyorganosiloxane, the molecular chain terminal may be sealed with a hydroxyl group, an alkoxy group, a trimethylsilyl group, a methyldiphenylsilyl group, or the like.

  The graft crossing agent is usually a compound having a carbon-carbon unsaturated bond and an alkoxysilyl group. For example, p-vinylphenylmethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, 3- (P-Vinylbenzoyloxy) propylmethyldimethoxysilane and the like.

  The amount of the grafting agent used is usually 10 parts by mass or less, preferably 0.2 to 10 parts by mass, and more preferably 0.000 parts by mass when the total of the organosiloxane, the grafting agent and the crosslinking agent is 100% by mass. 5 to 5 parts by mass. If the amount of the graft crossing agent used is too large, the molecular weight of the graft copolymer is lowered, and as a result, sufficient impact resistance may not be obtained. In addition, there is a case where a rubber-reinforced aromatic vinyl resin having a good weather resistance cannot be obtained because oxidation degradation is more likely to proceed than the double bond of the polyorganosiloxane rubber after grafting.

  Examples of the crosslinking agent include trifunctional crosslinking agents such as methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane, and tetrafunctional crosslinking agents such as tetraethoxysilane. A crosslinkable prepolymer obtained by condensation polymerization of these compounds in advance may be used. These may be used alone or in combination of two or more.

  The amount of the crosslinking agent used is usually 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 0.01 to 5 parts by mass, when the total of the organosiloxane, the grafting agent and the crosslinking agent is 100% by mass. Part. When there is too much usage-amount of the said crosslinking agent, the softness | flexibility of the polyorganosiloxane type rubber | gum obtained will be impaired and the flexibility of a film may fall.

  The volume average particle diameter of the silicone rubber is usually 5 to 500 nm, preferably 10 to 400 nm, and more preferably 50 to 400 nm. This volume average particle diameter can be easily controlled by the amount of emulsifier and water used during production, the degree of dispersion when mixed using a homomixer or an ultrasonic mixer, or the method of charging the organosiloxane. If the volume average particle diameter exceeds 500 nm, the appearance may be inferior, such as a decrease in gloss.

  The silicone / acrylic composite rubber is a rubbery polymer containing a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber. A preferable silicone-acrylic composite rubber is a composite rubber having a structure in which polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber are intertwined with each other so that they cannot be separated.

As the polyorganosiloxane rubber, a copolymer obtained by copolymerizing an organosiloxane can be preferably used. Examples of the organosiloxane include various reduced products having three or more members, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, Tetramethyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane are preferred. These organosiloxanes can be used alone or in combination of two or more.
The content of the structural unit derived from the organosiloxane constituting the polyorganosiloxane rubber is preferably 50% by mass or more, more preferably 70% by mass or more based on the total amount of the structural unit.

The acrylic rubber is preferably methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, lauryl methacrylate. A rubber obtained by (co) polymerizing a monomer containing a (meth) acrylic acid alkyl ester compound such as stearyl methacrylate. These (meth) acrylic acid alkyl ester compounds can be used alone or in combination of two or more.
In addition to (meth) acrylic acid alkyl ester compounds, the above monomers include aromatic vinyl compounds such as styrene, α-methylstyrene and vinyl toluene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methacrylic acid modified Various vinyl monomers such as silicone and fluorine-containing vinyl compound may be contained as a copolymerization component in a range of 30% by mass or less.

  The acrylic rubber is preferably a copolymer having two or more glass transition temperatures since it can impart sufficient flexibility to the film.

  As the silicone-acrylic composite rubber, for example, those manufactured by the methods described in JP-A-4-239010, JP-A-4-100812, and the like can be used.

  The volume average particle diameter of the silicone / acrylic composite rubber is preferably 5 to 500 nm, more preferably 10 to 450 nm, and still more preferably 20 to 400 nm from the viewpoints of flexibility, low temperature impact property and the like.

The ethylene / α-olefin copolymer rubber is a copolymer including an ethylene unit and a unit composed of an α-olefin having 3 or more carbon atoms, and includes an ethylene / α-olefin copolymer and an ethylene / α-olefin. -Nonconjugated diene copolymers and the like can be mentioned.
Examples of the ethylene / α-olefin copolymer include an ethylene / propylene copolymer and an ethylene / butene-1 copolymer. Examples of the ethylene / α-olefin / non-conjugated diene copolymer include an ethylene / propylene / non-conjugated diene copolymer and an ethylene / butene-1 / non-conjugated diene copolymer.

  The α-olefin is preferably an α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1 -Heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-eicocene and the like. In the α-olefin, a more preferable carbon number is 3 to 12, and further preferably 3 to 8.

  The proportion of ethylene units and α-olefin units constituting the ethylene / α-olefin copolymer rubber is preferably 5 to 95% by mass and 5 to 95%, respectively, when the total of these is 100% by mass. More preferably, they are 50-90 mass% and 10-50 mass%, More preferably, they are 60-88 mass% and 12-40 mass%, Most preferably, they are 70-85 mass% and 15-30 mass%. When there is too much content rate of the said alpha olefin unit, flexibility may fall.

When the ethylene / α-olefin copolymer rubber is an ethylene / α-olefin / non-conjugated diene copolymer, examples of the non-conjugated diene include alkenyl norbornene such as 5-ethylidene-2-norbornene; dicyclopentadiene Cyclic dienes such as aliphatic diene and the like. These compounds can be used alone or in combination of two or more.
The content of the structural unit derived from the non-conjugated diene is preferably 1 to 30% by mass, more preferably 2 with respect to the total amount of the structural unit constituting the ethylene / α-olefin / non-conjugated diene copolymer. ˜20 mass%. When there is too much content rate of a nonconjugated diene unit, a shaping | molding external appearance property and weather resistance may fall.

The amount of unsaturated groups in the ethylene / α-olefin copolymer rubber is preferably 4 to 40 in terms of iodine value.
The Mooney viscosity (ML _{1 + 4} , 100 ° C .; conforming to JIS K6300) of the ethylene / α-olefin copolymer rubber is preferably 5 to 80, more preferably 10 to 65, and still more preferably 15 to 45. is there. When the Mooney viscosity is in the above range, the impact resistance and flexibility are excellent.

The hydrogenated conjugated diene rubber is not particularly limited as long as it is a (co) polymer obtained by hydrogenating a (co) polymer containing a structural unit derived from a conjugated diene compound.
Examples of the hydrogenated conjugated diene rubber include hydrogenated conjugated diene block copolymers having the following structure. That is, a polymer block A composed of a structural unit derived from an aromatic vinyl compound; a double bond portion of a polymer composed of a structural unit derived from a conjugated diene compound having a 1,2-vinyl bond content exceeding 25 mol%. Polymer block B formed by hydrogenation of 95 mol% or more; 95 mol% or more of a double bond portion of a polymer composed of a structural unit derived from a conjugated diene compound having a 1,2-vinyl bond content of 25 mol% or less Hydrogenated polymer block C formed by hydrogenation; and 95 mol% or more of a double bond portion of a copolymer composed of a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound. It is a block copolymer which consists of what combined 2 or more types among the polymer blocks D formed.

The molecular structure of the block copolymer may be branched, radial, or a combination thereof. The block structure may be a diblock, triblock, multiblock, or a combination thereof.
As the structure of the block copolymer, A- (BA) n, (AB) n, A- (BC) n, C- (BC) n, (BC) n , A- (DA) n, (AD) n, A- (DC) n, C- (DC) n, (DC) n, A- (BCD) ) N, (A-B-C-D) n [n is an integer of 1 or more. Etc., preferably AB-A, A-B-A-B, A-B-C, A-D-C and C-B-C.

The aromatic vinyl compound used for forming the polymer blocks A and D constituting the block copolymer is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. . Examples thereof include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, and the like. . These compounds can be used alone or in combination of two or more. Of these, styrene is preferred.
The content ratio of the polymer block A constituting the block copolymer is preferably 0 to 65% by mass, more preferably 10 to 40% by mass with respect to the whole polymer. When there is too much content of the polymer block A, impact resistance may not be enough.

  The polymer blocks B, C and D are formed by hydrogenating a pre-hydrogenation block copolymer obtained using a conjugated diene compound and an aromatic vinyl compound. Examples of the conjugated diene compound used for forming the polymer blocks B, C, and D include 1,3-butadiene, isoprene, 1,3-pentadiene, chloroprene, and the like. These compounds can be used alone or in combination of two or more. Of these, 1,3-butadiene and isoprene are preferred because they can be utilized industrially and have excellent physical properties.

The hydrogenation rates of the polymer blocks B, C and D are all 95 mol% or more, preferably 96 mol% or more.
The 1,2-vinyl bond content in the polymer block B is preferably more than 25 mol% and 90 mol% or less, more preferably 30 to 80 mol%. If the 1,2-vinyl bond content is 25 mol% or less, the rubbery properties are lost and the impact resistance may not be sufficient. On the other hand, when it exceeds 90 mol%, chemical resistance may not be sufficient.
The 1,2-vinyl bond content in the polymer block C is preferably 25% mol or less, more preferably 20 mol% or less.

The 1,2-vinyl bond content in the polymer block D is preferably 25 to 90 mol%, more preferably 30 to 80 mol%. If the 1,2-vinyl bond content is less than 25 mol%, the rubbery properties are lost and the impact resistance may not be sufficient. On the other hand, when it exceeds 90 mol%, chemical resistance may not be sufficient.
The amount of the aromatic vinyl compound unit in the polymer block D is preferably 25% by mass or less, more preferably 20% by mass or less. If the amount of the aromatic vinyl compound unit exceeds 25% by mass, rubber properties may be lost and impact resistance may not be sufficient.

  Examples of the hydrogenated conjugated diene rubber include hydrogenated polybutadiene, hydrogenated styrene / butadiene rubber, styrene / ethylene butylene / olefin crystal block polymer, olefin crystal / ethylene butylene / olefin crystal block polymer, styrene / ethylene butylene / styrene block polymer. And a hydrogenated product of a butadiene / acrylonitrile copolymer.

  The weight average molecular weight (Mw) of the hydrogenated conjugated diene rubber is preferably 10,000 to 1,000,000, more preferably 30,000 to 800,000, and still more preferably 50,000 to 500,000. When Mw is in the above range, the flexibility is excellent.

  Next, the vinyl monomer (b11) used for forming the rubber-reinforced aromatic vinyl resin (I-1) contains an aromatic vinyl compound. That is, this vinyl monomer (b11) may be composed only of an aromatic vinyl compound, or composed of an aromatic vinyl compound and another monomer copolymerizable with this compound. Also good. Other monomers include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, and epoxy group-containing unsaturated compounds. Compounds, oxazoline group-containing unsaturated compounds, and the like. These can be used alone or in combination of two or more.

  The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. Examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene, monochlorostyrene, dichloromethane. Examples thereof include styrene, monobromostyrene, dibromostyrene, tribromostyrene, and fluorostyrene. These compounds can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.

  Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile and the like. These compounds can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.

  Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Examples include cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. These compounds can be used alone or in combination of two or more.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methyl). Phenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) ) Maleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. Of these, N-phenylmaleimide is preferred. Moreover, these compounds can be used individually or in combination of 2 or more. As another method for introducing a structural unit derived from a maleimide compound into the rubber-reinforced aromatic vinyl resin (I-1), for example, an unsaturated dicarboxylic anhydride of maleic anhydride is copolymerized. Then, a method of imidization may be used.

Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These compounds can be used alone or in combination of two or more.
Examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and the like. These compounds can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing unsaturated compound include 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (Meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylic (Meth) acrylic acid ester having a hydroxyl group such as a compound obtained by adding ε-caprolactone to 2-hydroxyethyl acid; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α -Methylstyrene M-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, 2-hydroxymethyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylstyrene, 4 -Hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinylnaphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenylnaphthalene 8-hydroxymethyl-1-isopropenylnaphthalene, p-vinylbenzyl alcohol, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy- 2-butene, 3-hydroxy-2-me Examples include til-1-propene. These compounds can be used alone or in combination of two or more.

Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, and methallyl glycidyl ether. These compounds can be used alone or in combination of two or more.
Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline.

  In the present invention, the vinyl monomer (b11) preferably contains an aromatic vinyl compound and a vinyl cyanide compound, and the total amount used thereof is molding processability, chemical resistance, hydrolysis resistance, dimensions. From the viewpoints of stability, molded appearance, etc., the content is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total amount of the vinyl monomer (b11). The use ratio of the aromatic vinyl compound and the vinyl cyanide compound was 100% by mass in total from the viewpoint of molding processability, chemical resistance, hydrolysis resistance, dimensional stability, molding appearance, and the like. In such a case, it is preferably 5 to 95% by mass and 5 to 95% by mass, more preferably 50 to 95% by mass and 5 to 50% by mass, still more preferably 60 to 95% by mass and 5 to 40% by mass, respectively.

  Moreover, heat resistance can be provided to the 1st resin layer because the said vinyl-type monomer (b11) contains a maleimide-type compound. The preferable content of the structural unit derived from the maleimide compound contained in the aromatic vinyl resin will be described later.

As the rubber-reinforced aromatic vinyl resin (I-1), preferred resins are as follows.
[1-1] A rubber-reinforced aromatic vinyl resin obtained by polymerizing a vinyl monomer (b11) comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer (a11). [1-2] Rubber-reinforced aroma obtained by polymerizing vinyl monomer (b11) composed of an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound in the presence of rubber polymer (a11). Group vinyl resin [1-3] obtained by polymerizing a vinyl monomer (b11) comprising an aromatic vinyl compound, a vinyl cyanide compound and a methacrylic ester compound in the presence of a rubbery polymer (a11). Rubber Reinforced Aromatic Vinyl Resin

  The rubber-reinforced aromatic vinyl resin (I-1) can be produced by polymerizing the vinyl monomer (b11) in the presence of the rubber polymer (a11). As a polymerization method, emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these can be used.

  In the production of the rubber-reinforced aromatic vinyl resin (I-1), the rubber polymer (a11) and the vinyl monomer (b11) are reacted with each other in the reaction system. (A11) In the presence of the total amount, the above-mentioned vinyl monomer (b11) may be added all at once to initiate the polymerization, or the polymerization may be carried out while being divided or continuously added. Further, in the presence or absence of a part of the rubber polymer (a11), the vinyl monomer (b11) may be added all at once to initiate polymerization, or divided or continuously. May be added. At this time, the remainder of the rubbery polymer (a11) may be added in a batch, divided or continuously during the reaction.

  When the rubber-reinforced aromatic vinyl resin (I-1) is produced by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used.

As the polymerization initiator, a redox in which an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, or the like and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation are combined. System initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate. These can be used alone or in combination of two or more. Moreover, the usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (b11) whole quantity.
The polymerization initiator can be added to the reaction system all at once or continuously.

Examples of the chain transfer agent include octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan, and other mercaptans; Examples include α-methylstyrene dimers. These can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2.0% by mass with respect to the total amount of the vinyl monomer (b11).
The chain transfer agent can be added to the reaction system all at once or continuously.

  Examples of the emulsifier include anionic surfactants and nonionic surfactants. Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates, aliphatic phosphates, etc. Is mentioned. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used alone or in combination of two or more. The usage-amount of the said emulsifier is 0.3-5.0 mass% normally with respect to the said vinylic monomer (b11) whole quantity.

Emulsion polymerization can be carried out under known conditions depending on the type of vinyl monomer (b11), polymerization initiator, and the like. The latex obtained by this emulsion polymerization is usually purified by coagulation with a coagulant to form a polymer component in powder form, and then washing and drying the polymer component. Examples of the coagulant include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid.
When two or more rubber-reinforced aromatic vinyl resins (I-1) are contained in the aromatic vinyl resin, the resin may be isolated from each latex and then mixed. As the method, there is a method of coagulating a latex mixture containing each resin.

  A known method can be applied to the method for producing the rubber-reinforced aromatic vinyl resin (I-1) by solution polymerization, bulk polymerization and bulk-suspension polymerization.

  The graft ratio of the rubber-reinforced aromatic vinyl resin (I-1) is preferably 20 to 170%, more preferably 30 to 170%, and still more preferably 40 to 150%. If this graft ratio is too low, the flexibility of the first resin layer may not be sufficient. On the other hand, when the graft ratio is too high, the viscosity of the first thermoplastic resin composition becomes high, and it may be difficult to reduce the thickness.

The graft ratio can be determined by the following formula.
Graft rate (%) = {(S−T) / T} × 100
In the above formula, S represents 1 gram of rubber-reinforced aromatic vinyl resin (I-1) in 20 ml of acetone (acetonitrile when the rubbery polymer (a11) is an acrylic rubber). Then, after shaking with a shaker for 2 hours, the mixture is centrifuged for 60 minutes in a centrifuge (rotation speed: 23,000 rpm) under a temperature condition of 5 ° C. to separate insoluble and soluble components. The mass (g) of the insoluble matter obtained, and T is the mass (g) of the rubber polymer (a11) contained in 1 gram of the rubber-reinforced aromatic vinyl resin (I-1). The mass of the rubbery polymer (a11) can be obtained by a method of calculating from the polymerization prescription and the polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.

  The rubber-reinforced aromatic vinyl resin (I-1) can be used alone or in combination of two or more.

  As described above, the aromatic vinyl resin was obtained by polymerizing a rubber-reinforced aromatic vinyl resin (I-1) and a vinyl monomer (b12) containing an aromatic vinyl compound ( It may be a mixture of (co) polymer (I-2). In this case, the (co) polymer (I-2) may be either a homopolymer or a copolymer, or a combination thereof.

  The vinyl monomer (b12) may be an aromatic vinyl compound alone or a combination of this aromatic vinyl compound and another monomer. Other monomers include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, and epoxy group-containing unsaturated compounds. Compounds, oxazoline group-containing unsaturated compounds, and the like. These can be used alone or in combination of two or more. The compound illustrated in the said vinyl monomer (b11) is applied to each said compound.

The (co) polymer (I-2) is preferably a copolymer. In the present invention, the vinyl monomer (b12) is preferably composed of an aromatic vinyl compound and another monomer. Other monomers are preferably vinyl cyanide compounds and maleimide compounds.
When the vinyl monomer (b12) contains an aromatic vinyl compound and a vinyl cyanide compound, the total amount thereof is preferably 40 to 100 mass with respect to the entire vinyl monomer (b12). %, More preferably 50 to 100% by mass. The use ratio of the aromatic vinyl compound and the vinyl cyanide compound was 100% by mass in total from the viewpoint of molding processability, chemical resistance, hydrolysis resistance, dimensional stability, molding appearance, and the like. In such a case, it is preferably 5 to 95% by mass and 5 to 95% by mass, more preferably 40 to 95% by mass and 5 to 60% by mass, still more preferably 50 to 90% by mass and 10 to 50% by mass, respectively.

When the (co) polymer (I-2) is a copolymer, preferred polymers are as follows.
[1-4] A structural unit derived from an aromatic vinyl compound (hereinafter referred to as “structural unit (s)”) and a structural unit derived from a vinyl cyanide compound (hereinafter referred to as “structural unit (t)”). [1-5] a structural unit derived from an aromatic vinyl compound (s), a structural unit derived from a vinyl cyanide compound (t), and a structural unit derived from a maleimide compound (hereinafter referred to as a structural unit). , “Structural unit (u)”))

When the (co) polymer (I-2) is the above embodiment [1-4], the content ratio of the structural unit (s) and the structural unit (t) is determined by molding processability, chemical resistance, and hydrolysis resistance. From the viewpoints of properties, dimensional stability, molding appearance, etc., when these totals are 100% by mass, preferably 5 to 95% by mass and 5 to 95% by mass, more preferably 40 to 95% by mass and It is 5-60 mass%, More preferably, it is 50-90 mass% and 10-50 mass%.
Examples of the copolymer of the above embodiment [1-4] include acrylonitrile / styrene copolymer, acrylonitrile / α-methylstyrene copolymer, and the like.

When the (co) polymer (I-2) is the above embodiment [1-5], the content ratio of the structural unit (s), the structural unit (t), and the structural unit (u) is determined by molding processability and heat resistance. From the viewpoints of properties, chemical resistance, hydrolysis resistance, dimensional stability, flexibility, etc., when these totals are 100% by mass, preferably 20 to 90% by mass, 5 to 50% by mass and 1-40 mass%, More preferably, it is 25-85 mass%, 10-45 mass%, and 5-35 mass%, More preferably, they are 30-80 mass%, 10-40 mass%, and 10-30 mass%.
As said aspect [1-5], an acrylonitrile * styrene * N-phenylmaleimide copolymer etc. are mentioned.
In addition, an acrylonitrile / styrene / methyl methacrylate copolymer can be used as the (co) polymer (I-2).

  The (co) polymer (I-2) can be produced by polymerizing a vinyl monomer (b12) containing an aromatic vinyl compound in the presence or absence of a polymerization initiator. When a polymerization initiator is used as the polymerization method, solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like are suitable, and these polymerization methods may be used in combination. Moreover, when not using a polymerization initiator, it can be set as thermal polymerization.

As said polymerization initiator, the compound illustrated by description of the manufacturing method of the said rubber reinforced aromatic vinyl-type resin (I-1) can be used individually by 1 type or in combination of 2 or more types. The usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (b12) whole quantity.
In addition, the chain transfer agent, emulsifier, etc. which can be used at the time of manufacture of the said rubber reinforced aromatic vinyl-type resin (I-1) can be used as needed.

  In the production of the (co) polymer (I-2), the polymerization may be started in a state in which the entire amount of the vinyl monomer (b12) is accommodated in the reaction system, or an arbitrarily selected single amount You may superpose | polymerize by adding a body component separately or continuously. Furthermore, when using the said polymerization initiator, it can add to a reaction system collectively or continuously.

The said (co) polymer (I-2) can be used individually by 1 type or in combination of 2 or more types.
In addition, when the said aromatic vinyl-type resin is a (co) polymer (I-2), the said (co) polymer (I-2) of the said description can be used as it is.

  When the aromatic vinyl resin is made of rubber-reinforced aromatic vinyl resin (I-1), and rubber-reinforced aromatic vinyl resin (I-1) and (co) polymer (I-2) In any case of the mixture, the intrinsic viscosity [η] (methyl ethyl ketone) of the component soluble in acetone of the aromatic vinyl resin (but acetonitrile if the rubbery polymer is an acrylic rubber) (Measured at 30 ° C.) is preferably 0.1 to 2.5 dl / g, more preferably 0.2 to 1.5 dl / g, and still more preferably 0.25 to 1.2 dl / g. When the intrinsic viscosity [η] is within the above range, the moldability of the first thermoplastic resin composition is excellent, and the thickness accuracy of the first resin layer is also excellent.

Here, the intrinsic viscosity [η] can be obtained in the following manner.
When the graft ratio in the above aromatic vinyl resin (including rubber-reinforced aromatic vinyl resin (I-1)) is determined, acetone-soluble matter recovered after centrifugation (the rubbery polymer is an acrylic rubber). In this case, acetonitrile soluble component) is dissolved in methyl ethyl ketone, 5 different concentrations are prepared, and the reduced viscosity of each concentration is measured at 30 ° C. using an Ubbelohde viscosity tube, and the intrinsic viscosity [η] is obtained. .

The graft ratio and intrinsic viscosity [η] are the polymerization initiator and chain transfer used when the rubber-reinforced aromatic vinyl resin (I-1) and the (co) polymer (I-2) are produced. It can be easily controlled by adjusting the type and amount of the agent, the emulsifier, the solvent, etc., the polymerization time, the polymerization temperature and the like.
In addition, the intrinsic viscosity [η] of the aromatic vinyl resin is appropriately selected from rubber-reinforced aromatic vinyl resins (I-1) and (co) polymers (I-2) having different intrinsic viscosities [η]. It can also be adjusted by selecting.

In the case where sufficient heat resistance is imparted to the first resin layer, the aromatic vinyl resin preferably includes a structural unit (u) derived from a maleimide compound. The structural unit (u) may be derived from the rubber-reinforced aromatic vinyl resin (I-1) or may be derived from the (co) polymer (I-2). Moreover, you may originate in both.
The content of the structural unit (u) for making the first resin layer excellent in heat resistance is preferably 1 to 40% by mass, more preferably 3 when the thermoplastic resin (I) is 100% by mass. It is -35 mass%, More preferably, it is 5-30 mass%. When there is too much content of the said structural unit (u), the flexibility of a 1st resin layer may fall.

  The said 1st thermoplastic resin composition shall contain an additive according to the objective, a use, etc. This additive includes antioxidants, ultraviolet absorbers, anti-aging agents, plasticizers, fluorescent brighteners, weathering agents, fillers, antistatic agents, flame retardants, antifogging agents, antibacterial agents, antifungal agents, Antifouling agents, tackifiers, silane coupling agents and the like can be mentioned. Specific compounds in these additives and their blending amounts will be described later.

  In order to contain the additive, a melt-kneading method is usually used. Examples of the apparatus used for melt kneading include a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, and a continuous kneader.

  The thickness of the first resin layer is usually 5 to 500 μm, preferably 8 to 400 μm.

The thermoplastic resin (II) contained in the second thermoplastic resin composition forming the second resin layer is not particularly limited as long as it is a resin having thermoplasticity. Examples of the thermoplastic resin (II) constituting the second resin layer include aromatic vinyl resins, polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl acetate resins, saturated polyester resins, polycarbonate resins, and acrylic resins. , Fluororesin, ethylene / vinyl acetate resin and the like. These can be used alone or in combination of two or more. Of these, aromatic vinyl resins are preferred from the viewpoints of hydrolysis resistance and dimensional stability.
The thermoplastic resin (II) may be the same as or different from the thermoplastic resin (I).

  The aromatic vinyl resin is a rubber-reinforced aromatic vinyl resin obtained by polymerizing an aromatic vinyl compound in the presence of a rubbery polymer as described above; a vinyl resin containing an aromatic vinyl compound. (Co) polymers and the like using monomers. In the present invention, the aromatic vinyl resin is preferably a rubber-reinforced aromatic vinyl resin. When the thermoplastic resin (II) contains a rubber-reinforced aromatic vinyl resin, a second resin layer excellent in hydrolysis resistance, dimensional stability, and impact resistance can be formed.

  As the aromatic vinyl resin, a rubber-reinforced aromatic vinyl resin (II-) obtained by polymerizing a vinyl monomer (b21) containing an aromatic vinyl compound in the presence of the rubbery polymer (a21). 1), (co) polymer (II-2) of vinyl monomer (b22) containing an aromatic vinyl compound, and rubber-reinforced aromatic vinyl resin (II-1) and (co) polymer ( The mixture of II-2) is mentioned.

  As described above, the aromatic vinyl resin preferably contains at least one rubber-reinforced aromatic vinyl resin (II-1). From the viewpoint of impact resistance and flexibility, the rubber-reinforced aromatic vinyl is preferable. A combination of one or more of the resin series (II-1) and one or more of the (co) polymer (II-2) is particularly preferred. In this case, the content of the rubber-like polymer (a21) in the aromatic vinyl resin is preferably 5 to 40% by mass, more preferably 8 to 30% by mass with respect to 100% by mass of the aromatic vinyl resin. More preferably, it is 10 to 20% by mass, particularly preferably 12 to 18% by mass. When the content exceeds 40% by mass, the heat resistance is not sufficient, and it may be difficult to form the second resin layer using the second thermoplastic resin composition. On the other hand, if the content is less than 5% by mass, flexibility may not be sufficient.

As the rubbery polymer (a21) used for forming the rubber-reinforced aromatic vinyl resin (II-1), the rubber-reinforced aromatic vinyl resin (I-) contained in the first thermoplastic resin composition is used. The polymer illustrated as a rubbery polymer (a11) used for formation of 1) can be used. The rubbery polymer (a21) is preferably an acrylic rubber, an ethylene / α-olefin rubber, a hydrogenated conjugated diene rubber, a silicone rubber and a silicone / acrylic composite rubber from the viewpoint of weather resistance. From the viewpoint, a conjugated diene rubber is preferable.
The shape and volume average particle diameter of the rubber polymer (a21) can be the same as those described in the rubber polymer (a11).
The type, shape and volume average particle diameter of the rubber polymer (a21) may be the same as or different from the shape and volume average particle diameter of the rubber polymer (a11), respectively.

As the vinyl monomer (b21) used for forming the rubber-reinforced aromatic vinyl resin (II-1), the rubber-reinforced aromatic vinyl resin (I) contained in the first thermoplastic resin composition is used. The compound illustrated as a vinyl-type monomer (b11) used for formation of -1) can be used. Preferred vinyl monomers (b21) are an aromatic vinyl compound and a vinyl cyanide compound. As the aromatic vinyl compound, styrene and α-methylstyrene are preferable, and as the vinyl cyanide compound, acrylonitrile is preferable.
The vinyl monomer (b21) may be the same as or different from the vinyl monomer (b11).

  In the vinyl monomer (b21), the total amount of the aromatic vinyl compound and the vinyl cyanide compound used is from the viewpoint of molding processability, chemical resistance, hydrolysis resistance, dimensional stability, molding appearance, and the like. The amount is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total amount of the vinyl monomer (b21). The use ratio of the aromatic vinyl compound and the vinyl cyanide compound was 100% by mass in total from the viewpoint of molding processability, chemical resistance, hydrolysis resistance, dimensional stability, molding appearance, and the like. In such a case, it is preferably 5 to 95% by mass and 5 to 95% by mass, more preferably 50 to 95% by mass and 5 to 50% by mass, still more preferably 60 to 90% by mass and 10 to 40% by mass, respectively.

  Moreover, heat resistance can be provided to the 2nd resin layer because the said vinyl-type monomer (b21) contains a maleimide-type compound. The preferable content of the structural unit derived from the maleimide compound contained in the aromatic vinyl resin will be described later.

As the rubber-reinforced aromatic vinyl resin (II-1), preferred resins are as follows.
[2-1] A rubber-reinforced aromatic vinyl resin obtained by polymerizing a vinyl monomer (b21) comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of the rubbery polymer (a21). [2-2] Rubber-reinforced aroma obtained by polymerizing vinyl monomer (b21) composed of an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound in the presence of rubbery polymer (a21) Group vinyl resin [2-3] obtained by polymerizing a vinyl monomer (b21) comprising an aromatic vinyl compound, a vinyl cyanide compound and a methacrylic ester compound in the presence of the rubbery polymer (a21). Rubber Reinforced Aromatic Vinyl Resin

  The method for producing the rubber-reinforced aromatic vinyl resin (II-1) is the same as the method for producing the rubber-reinforced aromatic vinyl resin (I-1).

  The graft ratio of the rubber-reinforced aromatic vinyl resin (II-1) is preferably 20 to 170%, more preferably 30 to 170%, still more preferably 40 to 150%. If this graft ratio is too low, the flexibility of the second resin layer may not be sufficient. On the other hand, if the graft ratio is too high, the viscosity of the second thermoplastic resin composition becomes high, and it may be difficult to reduce the thickness.

  The rubber-reinforced aromatic vinyl resin (II-1) can be used alone or in combination of two or more.

  As described above, a preferred aromatic vinyl resin was obtained by polymerizing a rubber-reinforced aromatic vinyl resin (II-1) and a vinyl monomer (b22) containing an aromatic vinyl compound ( It is a mixture of (co) polymer (II-2). In this case, the (co) polymer (II-2) may be either a homopolymer or a copolymer, or a combination thereof.

The vinyl monomer (b22) may be an aromatic vinyl compound alone or a combination of this aromatic vinyl compound and another monomer. Other monomers include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, and epoxy group-containing unsaturated compounds. Compounds, oxazoline group-containing unsaturated compounds, and the like. These can be used alone or in combination of two or more. The compounds exemplified in the vinyl monomer (b11) are applied to the above compounds.
The vinyl monomer (b22) was the same as the vinyl monomer (b12) used for forming the (co) polymer (I-2) contained in the first thermoplastic resin composition. May be different or different.

The (co) polymer (II-2) is preferably a copolymer. In the present invention, the vinyl monomer (b22) is preferably composed of an aromatic vinyl compound and another monomer. Other monomers are preferably vinyl cyanide compounds and maleimide compounds.
When the vinyl monomer (b22) contains an aromatic vinyl compound and a vinyl cyanide compound, the total amount thereof is preferably 40 to 100 mass with respect to the entire vinyl monomer (b22). %, More preferably 50 to 100% by mass. The use ratio of the aromatic vinyl compound and the vinyl cyanide compound was 100% by mass in total from the viewpoint of molding processability, chemical resistance, hydrolysis resistance, dimensional stability, molding appearance, and the like. In such a case, it is preferably 5 to 95% by mass and 5 to 95% by mass, more preferably 40 to 95% by mass and 5 to 60% by mass, still more preferably 50 to 90% by mass and 10 to 50% by mass, respectively.

When the (co) polymer (II-2) is a copolymer, preferred polymers are as follows.
[2-4] Copolymer composed of structural unit (s) derived from aromatic vinyl compound and structural unit (t) derived from vinyl cyanide compound [2-5] Structure derived from aromatic vinyl compound Copolymer comprising unit (s), structural unit (t) derived from vinyl cyanide compound, and structural unit (u) derived from maleimide compound

  The method for producing the (co) polymer (II-2) is the same as the method for producing the (co) polymer (I-2).

Said (co) polymer (II-2) can be used individually by 1 type or in combination of 2 or more types.
In addition, when the said aromatic vinyl-type resin is (co) polymer (II-2), the said (co) polymer (II-2) can be used as it is.

  When the aromatic vinyl resin is made of rubber-reinforced aromatic vinyl resin (II-1), and rubber-reinforced aromatic vinyl resin (II-1) and (co) polymer (II-2) In any case of the mixture, the intrinsic viscosity [η] (methyl ethyl ketone) of the component soluble in acetone of the aromatic vinyl resin (but acetonitrile if the rubbery polymer is an acrylic rubber) (Measured at 30 ° C.) is preferably 0.1 to 2.5 dl / g, more preferably 0.2 to 1.5 dl / g, and still more preferably 0.25 to 1.2 dl / g. When the intrinsic viscosity [η] is within the above range, the second thermoplastic resin composition is excellent in molding processability and the thickness accuracy of the second resin layer.

In the case where sufficient heat resistance is imparted to the second resin layer, the aromatic vinyl resin preferably includes a structural unit (u) derived from a maleimide compound. This structural unit (u) may be derived from the rubber-reinforced aromatic vinyl resin (II-1) or may be derived from the (co) polymer (II-2). Moreover, you may originate in both.
The content of the structural unit (u) for making the second resin layer excellent in heat resistance is preferably 1 to 50% by mass, more preferably 5 when the thermoplastic resin (II) is 100% by mass. It is -45 mass%, More preferably, it is 10-40 mass%. When there is too much content of the said structural unit (u), the flexibility of a 2nd resin layer may fall.

  The said 2nd thermoplastic resin composition shall contain an additive according to the objective, a use, etc. This additive includes antioxidants, ultraviolet absorbers, anti-aging agents, plasticizers, fluorescent brighteners, weathering agents, fillers, antistatic agents, flame retardants, antifogging agents, antibacterial agents, antifungal agents, Antifouling agents, tackifiers, silane coupling agents and the like can be mentioned. Specific compounds in these additives and their blending amounts will be described later.

  The thickness of the second resin layer is usually 10 to 990 μm, preferably 20 to 500 μm.

The thermoplastic resin (III) contained in the third thermoplastic resin composition forming the third resin layer is not particularly limited as long as it is a resin having thermoplasticity. Examples of the thermoplastic resin (III) constituting the third resin layer include aromatic vinyl resins, polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl acetate resins, saturated polyester resins, polycarbonate resins, and acrylic resins. , Fluororesin, ethylene / vinyl acetate resin and the like. These can be used alone or in combination of two or more. Of these, aromatic vinyl resins are preferred from the viewpoints of hydrolysis resistance and dimensional stability.
The thermoplastic resin (III) may be the same as or different from the thermoplastic resin (I). The thermoplastic resin (III) may be the same as or different from the thermoplastic resin (II).

  The aromatic vinyl resin is a rubber-reinforced aromatic vinyl resin obtained by polymerizing an aromatic vinyl compound in the presence of a rubbery polymer as described above; a vinyl resin containing an aromatic vinyl compound. (Co) polymers and the like using monomers. In the present invention, the aromatic vinyl resin is preferably a rubber-reinforced aromatic vinyl resin. When the thermoplastic resin (III) contains a rubber-reinforced aromatic vinyl resin, a third resin layer excellent in hydrolysis resistance, dimensional stability, and impact resistance can be formed.

  Examples of the aromatic vinyl resin include a rubber-reinforced aromatic vinyl resin (III-) obtained by polymerizing a vinyl monomer (b31) containing an aromatic vinyl compound in the presence of the rubber polymer (a31). 1), (co) polymer (III-2) of vinyl monomer (b32) containing an aromatic vinyl compound, and rubber-reinforced aromatic vinyl resin (III-1) and (co) polymer ( The mixture of III-2) is mentioned.

  As described above, the aromatic vinyl resin preferably contains at least one rubber-reinforced aromatic vinyl resin (III-1), and one or more rubber-reinforced aromatic vinyl resins (III-1) are used. Or a combination of one or more of rubber-reinforced aromatic vinyl resins (III-1) and one or more of (co) polymer (III-2). In these cases, the content of the rubber-like polymer (a31) in the aromatic vinyl resin is preferably 5 to 40% by mass, more preferably 8 to 30% by mass with respect to 100% by mass of the aromatic vinyl resin. %, More preferably 10 to 20% by mass, particularly preferably 12 to 18% by mass. When the content exceeds 40% by mass, the heat resistance is not sufficient, and it may be difficult to form the third resin layer using the third thermoplastic resin composition. On the other hand, if the content is less than 5% by mass, flexibility may not be sufficient.

As the rubbery polymer (a31) used for forming the rubber-reinforced aromatic vinyl resin (III-1), the rubber-reinforced aromatic vinyl resin (I-) contained in the first thermoplastic resin composition is used. The polymer illustrated as a rubbery polymer (a11) used for formation of 1) can be used. The rubbery polymer (a31) is preferably an acrylic rubber, an ethylene / α-olefin rubber, a hydrogenated conjugated diene rubber, a silicone rubber, or a silicone / acrylic composite rubber from the viewpoint of weather resistance. From the viewpoint, conjugated diene rubber is preferable.
The shape and volume average particle diameter of the rubber polymer (a31) can be the same as those described in the rubber polymer (a11).
The type, shape and volume average particle diameter of the rubber polymer (a31) may be the same as or different from the shape and volume average particle diameter of the rubber polymer (a11), respectively. Further, the type, shape and volume average particle diameter of the rubber polymer (a31) may be the same as or different from the shape and volume average particle diameter of the rubber polymer (a21), respectively. Good.

As the vinyl monomer (b31) used for forming the rubber-reinforced aromatic vinyl resin (III-1), the rubber-reinforced aromatic vinyl resin (I) contained in the first thermoplastic resin composition is used. The compound illustrated as a vinyl-type monomer (b11) used for formation of -1) can be used. Preferred vinyl monomers (b31) are an aromatic vinyl compound and a vinyl cyanide compound. As the aromatic vinyl compound, styrene and α-methylstyrene are preferable, and as the vinyl cyanide compound, acrylonitrile is preferable.
The vinyl monomer (b31) may be the same as or different from the vinyl monomer (b11). The vinyl monomer (b31) may be the same as or different from the vinyl monomer (b21).

  In the vinyl monomer (b31), the total use amount of the aromatic vinyl compound and the vinyl cyanide compound is from the viewpoint of molding processability, chemical resistance, hydrolysis resistance, dimensional stability, molding appearance, and the like. The amount is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total amount of the vinyl monomer (b31). The use ratio of the aromatic vinyl compound and the vinyl cyanide compound was 100% by mass in total from the viewpoint of molding processability, chemical resistance, hydrolysis resistance, dimensional stability, molding appearance, and the like. In such a case, it is preferably 5 to 95% by mass and 5 to 95% by mass, more preferably 50 to 95% by mass and 5 to 50% by mass, still more preferably 60 to 90% by mass and 10 to 40% by mass, respectively.

  Moreover, heat resistance can be provided to the 3rd resin layer because the said vinyl-type monomer (b31) contains a maleimide-type compound. The preferable content of the structural unit derived from the maleimide compound contained in the aromatic vinyl resin will be described later.

As the rubber-reinforced aromatic vinyl resin (III-1), preferred resins are as follows.
[3-1] A rubber-reinforced aromatic vinyl resin obtained by polymerizing a vinyl monomer (b31) composed of an aromatic vinyl compound and a vinyl cyanide compound in the presence of the rubbery polymer (a31). [3-2] A rubber-reinforced aroma obtained by polymerizing a vinyl monomer (b31) composed of an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound in the presence of the rubbery polymer (a31). Obtained by polymerizing a vinyl monomer (b31) comprising an aromatic vinyl compound, a vinyl cyanide compound and a methacrylic acid ester compound in the presence of an aromatic vinyl resin [3-3] rubbery polymer (a31). Rubber Reinforced Aromatic Vinyl Resin

  The method for producing the rubber-reinforced aromatic vinyl resin (III-1) is the same as the method for producing the rubber-reinforced aromatic vinyl resin (I-1).

  The graft ratio of the rubber-reinforced aromatic vinyl resin (III-1) is preferably 20 to 170%, more preferably 30 to 170%, and still more preferably 40 to 150%. If this graft ratio is too low, the flexibility of the third resin layer may not be sufficient. On the other hand, if the graft ratio is too high, the viscosity of the third thermoplastic resin composition increases, and it may be difficult to reduce the thickness.

  The rubber-reinforced aromatic vinyl resin (III-1) can be used alone or in combination of two or more.

  As described above, a preferred aromatic vinyl resin was obtained by polymerizing a rubber-reinforced aromatic vinyl resin (III-1) and a vinyl monomer (b32) containing an aromatic vinyl compound ( It is a mixture of (co) polymer (III-2). In this case, the (co) polymer (III-2) may be either a homopolymer or a copolymer, or a combination thereof.

The vinyl monomer (b32) may be only an aromatic vinyl compound or a combination of this aromatic vinyl compound and another monomer. Other monomers include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, and epoxy group-containing unsaturated compounds. Compounds, oxazoline group-containing unsaturated compounds, and the like. These can be used alone or in combination of two or more. The compounds exemplified in the vinyl monomer (b11) are applied to the above compounds.
The vinyl monomer (b32) was the same as the vinyl monomer (b12) used for forming the (co) polymer (I-2) contained in the first thermoplastic resin composition. May be different or different. The vinyl monomer (b32) is the same as the vinyl monomer (b22) used for forming the (co) polymer (II-2) contained in the second thermoplastic resin composition. It may be different or different.

The (co) polymer (III-2) is preferably a copolymer. In the present invention, the vinyl monomer (b32) is preferably composed of an aromatic vinyl compound and another monomer. Other monomers are preferably vinyl cyanide compounds and maleimide compounds.
When the vinyl monomer (b32) contains an aromatic vinyl compound and a vinyl cyanide compound, the total amount thereof is preferably 40 to 100 mass with respect to the entire vinyl monomer (b32). %, More preferably 50 to 100% by mass. The use ratio of the aromatic vinyl compound and the vinyl cyanide compound was 100% by mass in total from the viewpoint of molding processability, chemical resistance, hydrolysis resistance, dimensional stability, molding appearance, and the like. In such a case, it is preferably 5 to 95% by mass and 5 to 95% by mass, more preferably 40 to 95% by mass and 5 to 60% by mass, still more preferably 50 to 90% by mass and 10 to 50% by mass, respectively.

When the (co) polymer (III-2) is a copolymer, preferred polymers are as follows.
[3-4] Copolymer composed of structural unit (s) derived from aromatic vinyl compound and structural unit (t) derived from vinyl cyanide compound [3-5] Structure derived from aromatic vinyl compound Copolymer comprising unit (s), structural unit (t) derived from vinyl cyanide compound, and structural unit (u) derived from maleimide compound

  The method for producing the (co) polymer (III-2) is the same as the method for producing the (co) polymer (I-2).

The said (co) polymer (III-2) can be used individually by 1 type or in combination of 2 or more types.
In addition, when the said aromatic vinyl-type resin is (co) polymer (III-2), the said (co) polymer (III-2) can be used as it is.

  When the aromatic vinyl resin (III) is composed of a rubber-reinforced aromatic vinyl resin (III-1), and the rubber-reinforced aromatic vinyl resin (III-1) and (co) polymer (III- 2) In any case of the mixture of 2), the limit of components soluble in acetone of this aromatic vinyl resin (III) (but acetonitrile in the case where the rubber polymer is an acrylic rubber) Viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) is preferably 0.1 to 2.5 dl / g, more preferably 0.2 to 1.5 dl / g, still more preferably 0.25 to 1.2 dl. / G. When the intrinsic viscosity [η] is within the above range, the third thermoplastic resin composition is excellent in molding processability and the thickness accuracy of the third resin layer is also excellent.

In the case where sufficient heat resistance is imparted to the third resin layer, the aromatic vinyl resin preferably includes a structural unit (u) derived from a maleimide compound. This structural unit (u) may be derived from the rubber-reinforced aromatic vinyl resin (III-1) or may be derived from the (co) polymer (III-2). Moreover, you may originate in both.
The content of the structural unit (u) for making the third resin layer excellent in heat resistance is preferably 1 to 40% by mass, more preferably 3 when the thermoplastic resin (III) is 100% by mass. It is -35 mass%, More preferably, it is 5-30 mass%. When there is too much content of the said structural unit (u), the flexibility of the 3rd resin layer may fall.

  The third thermoplastic resin composition may contain an additive depending on the purpose and application. This additive includes antioxidants, ultraviolet absorbers, anti-aging agents, plasticizers, fluorescent brighteners, weathering agents, fillers, antistatic agents, flame retardants, antifogging agents, antibacterial agents, antifungal agents, Antifouling agents, tackifiers, silane coupling agents and the like can be mentioned. Specific compounds in these additives and their blending amounts will be described later.

  The thickness of the third resin layer is usually 5 to 500 μm, preferably 8 to 400 μm.

  As described above, in the solar cell backsheet of the present invention, at least one of the first resin layer, the second resin layer, and the third resin layer is an infrared transparent colored resin layer. Therefore, when at least one of the first resin layer, the second resin layer, and the third resin layer is an infrared transparent colored resin layer, the thermoplastic resin composition that forms the infrared transparent colored resin layer The product is a composition containing a thermoplastic resin and an infrared transmitting colorant (hereinafter referred to as “infrared transmitting colorant-containing composition”).

  The infrared transmissive colorant usually has a color other than white, and is preferably a dark color such as black, brown, dark blue, or dark green.

〔式中、Ｒ^２及びＲ^３は、互いに同一又は異なって、ブチル基、フェニルエチル基、メトキシエチル基又は４−メトキシフェニルメチル基である。〕

〔式中、Ｒ^４及びＲ^５は、互いに同一又は異なって、フェニレン基、３−メトキシフェニレン基、４−メトキシフェニレン基、４−エトキシフェニレン基、炭素数１〜３のアルキルフェニレン基、ヒドロキシフェニレン基、４，６−ジメチルフェニレン基、３，５−ジメチルフェニレン基、３−クロロフェニレン基、４−クロロフェニレン基、５−クロロフェニレン基、３−ブロモフェニレン基、４−ブロモフェニレン基、５−ブロモフェニレン基、３−フルオロフェニレン基、４−フルオロフェニレン基、５−フルオロフェニレン基、ナフチレン基、ナフタレンジイル基、ピリジレン基、２，３−ピリジンジイル基、３，４−ピリジンジイル基、４−メチル−２，３−ピリジンジイル基、５−メチル−２，３−ピリジンジイル基、６−メチル−２，３−ピリジンジイル基、５−メチル−３，４−ピリジンジイル基、４−メトキシ−２，３−ピリジンジイル基又は４−クロロ−２，３−ピリジンジイル基である。〕

〔式中、Ｒ^６及びＲ^７は、互いに同一又は異なって、フェニレン基、３−メトキシフェニレン基、４−メトキシフェニレン基、４−エトキシフェニレン基、炭素数１〜３のアルキルフェニレン基、ヒドロキシフェニレン基、４，６−ジメチルフェニレン基、３，５−ジメチルフェニレン基、３−クロロフェニレン基、４−クロロフェニレン基、５−クロロフェニレン基、３−ブロモフェニレン基、４−ブロモフェニレン基、５−ブロモフェニレン基、３−フルオロフェニレン基、４−フルオロフェニレン基、５−フルオロフェニレン基、ナフチレン基、ナフタレンジイル基、ピリジレン基、２，３−ピリジンジイル基、３，４−ピリジンジイル基、４−メチル−２，３−ピリジンジイル基、５−メチル−２，３−ピリジンジイル基、６−メチル−２，３−ピリジンジイル基、５−メチル−３，４−ピリジンジイル基、４−メトキシ−２，３−ピリジンジイル基又は４−クロロ−２，３−ピリジンジイル基である。〕 Examples of the infrared transmissive colorant include perylene pigments. As the perylene pigment, compounds represented by the following general formulas (I) to (III) can be used.

[Wherein, R ² and R ³ are the same or different from each other, and are a butyl group, a phenylethyl group, a methoxyethyl group, or a 4-methoxyphenylmethyl group. ]

[Wherein, R ⁴ and R ⁵ are the same as or different from each other, and include a phenylene group, a 3-methoxyphenylene group, a 4-methoxyphenylene group, a 4-ethoxyphenylene group, an alkylphenylene group having 1 to 3 carbon atoms, and a hydroxyphenylene. Group, 4,6-dimethylphenylene group, 3,5-dimethylphenylene group, 3-chlorophenylene group, 4-chlorophenylene group, 5-chlorophenylene group, 3-bromophenylene group, 4-bromophenylene group, 5- Bromophenylene group, 3-fluorophenylene group, 4-fluorophenylene group, 5-fluorophenylene group, naphthylene group, naphthalenediyl group, pyridylene group, 2,3-pyridinediyl group, 3,4-pyridinediyl group, 4- Methyl-2,3-pyridinediyl group, 5-methyl-2,3-pyridinediyl group, 6- Le-2,3-pyridinediyl group, 5-methyl-3,4-pyridinediyl group, 4-methoxy-2,3-pyridinediyl group, or a 4-chloro-2,3-pyridinediyl group. ]

[Wherein, R ⁶ and R ⁷ are the same or different from each other, and include a phenylene group, a 3-methoxyphenylene group, a 4-methoxyphenylene group, a 4-ethoxyphenylene group, an alkylphenylene group having 1 to 3 carbon atoms, and a hydroxyphenylene. Group, 4,6-dimethylphenylene group, 3,5-dimethylphenylene group, 3-chlorophenylene group, 4-chlorophenylene group, 5-chlorophenylene group, 3-bromophenylene group, 4-bromophenylene group, 5- Bromophenylene group, 3-fluorophenylene group, 4-fluorophenylene group, 5-fluorophenylene group, naphthylene group, naphthalenediyl group, pyridylene group, 2,3-pyridinediyl group, 3,4-pyridinediyl group, 4- Methyl-2,3-pyridinediyl group, 5-methyl-2,3-pyridinediyl group, 6- Le-2,3-pyridinediyl group, 5-methyl-3,4-pyridinediyl group, 4-methoxy-2,3-pyridinediyl group, or a 4-chloro-2,3-pyridinediyl group. ]

In addition, as the perylene-based pigment, commercially available products such as “Paligen Black S 0084”, “Palogen Black L 0086”, “Lumogen Black FK4280”, “Lumogen Black FK4281” (all of which are trade names manufactured by BASF) are used. Can be used.
The infrared transmissive colorant can be used alone or in combination of two or more.

  The content ratio of the infrared transmitting colorant in the infrared transmitting colorant-containing composition is preferably 10 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin from the viewpoints of infrared transparency and visible light absorption. More preferably, it is 0.01-6 mass parts, More preferably, it is 0.05-5 mass parts. The content ratio of the infrared transmitting colorant may be the same or different in the first thermoplastic resin composition, the second thermoplastic resin composition, and the third thermoplastic resin composition.

In the present invention, the infrared-transmitting colorant-containing composition may contain other colorants depending on the purpose, application, and the like, unless the infrared-transmitting color resin layer is reduced in infrared transmittance. it can.
Examples of other colorants include a cyan colorant (blue color material), a magenta colorant (red color material), and a yellow colorant (yellow color material).

For example, as other colorants, yellow pigments, blue pigments, and the like are used, and solar cell modules having various appearances can be obtained by the following combinations.
[1] Brown coloration by combination of black-based infrared transmissive colorant and yellow pigment [2] Dark blue coloration by combination of black-based infrared transmissive colorant and blue pigment When using other colorants, the above infrared transmission The content of the colorant-containing composition is usually 60 parts by mass or less, preferably 0.01 to 55 parts by mass with respect to 100 parts by mass of the infrared transmitting colorant. In addition, the content rate of another coloring agent may be the same in a 1st thermoplastic resin composition, a 2nd thermoplastic resin composition, and a 3rd thermoplastic resin composition, and may differ.

  Carbon black is known as a dark colorant. Since this carbon black absorbs light having a wavelength in the infrared region, when sunlight leaks into the layer containing carbon black, the temperature of the filler material portion including the solar cell element is stored from the stored solar cell backsheet. There is a problem that the power generation efficiency is lowered. In the present invention, when the first resin layer includes an infrared transmitting colorant, a decrease in power generation efficiency can be suppressed.

  Next, if the thermoplastic resin (IV) contained in the 4th thermoplastic resin composition which forms the said 4th resin layer (back surface protective layer) is a resin which has thermoplasticity, it will not specifically limit. Examples of the thermoplastic resin (IV) include saturated polyester resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polyolefin resins such as polyethylene and polypropylene; polyvinyl fluoride, ethylene / tetrafluoroethylene copolymer, and the like. Fluorine resin; Polycarbonate resin; Polyamide resin; Polyarylate resin; Polyethersulfone resin; Polysulfone resin; Polyacrylonitrile; Cellulose resin such as cellulose acetate; Acrylic resin; Aromatic vinyl resin such as polystyrene and ABS resin. These can be used alone or in combination of two or more. Of these, saturated polyester resins such as polyethylene terephthalate and fluororesins are preferred.

The fourth thermoplastic resin composition may contain an additive depending on the purpose and application. These additives include colorants, antioxidants, UV absorbers, anti-aging agents, plasticizers, optical brighteners, weathering agents, fillers, antistatic agents, flame retardants, antifogging agents, antibacterial agents, Examples include fungicides, antifouling agents, tackifiers, and silane coupling agents. Specific compounds in these additives and their blending amounts will be described later.
The fourth resin layer may have a single layer structure or a multilayer structure. In the case of the latter, the film etc. which consist of the mutually same composition may be laminated | stacked, and the film etc. which consist of a mutually different composition may be laminated | stacked. Furthermore, the layer which consists of another substance or another composition may be formed in one side or both surfaces, such as a film which consists of said 4th thermoplastic resin composition.

The fourth resin layer is preferably a flame retardant resin layer, may be a layer derived from a fourth thermoplastic resin composition containing a flame retardant, an aromatic ring in the molecular skeleton, It may be a layer derived from a composition containing a hetero atom, and an organic / inorganic hybrid material is provided on one side or both sides of a film made of the fourth thermoplastic resin composition (regardless of flame retardant). A stacked layer may be used.
As for the flame retardancy of the fourth resin layer, it is preferable that the flammability conforming to the UL94 standard is a class of VTM-2 or higher.
As said 4th resin layer, the commercial item which is a resin film which has a flame retardance can also be used. For example, “Melinex 238” (trade name) manufactured by Teijin DuPont, “SR55” (trade name) manufactured by SKC, “Lumirror X10P”, “Lumirror ZV10” (trade name) manufactured by Toray Industries, Inc., and the like can be used.

  The thickness of the fourth resin layer is usually 10 to 500 μm, preferably 15 to 400 μm, and more preferably 20 to 300 μm. If the fourth resin layer is too thin, the effect of protecting the solar cell backsheet is not sufficient. On the other hand, if it is too thick, the flexibility as a sheet tends to be insufficient.

  Next, the additive contained in said 1st thermoplastic resin composition, 2nd thermoplastic resin composition, 3rd thermoplastic resin composition, and 4th thermoplastic resin composition is demonstrated.

Examples of the antioxidant include hindered amine compounds, hydroquinone compounds, hindered phenol compounds, sulfur-containing compounds, and phosphorus-containing compounds. These can be used alone or in combination of two or more.
Content of the said antioxidant is 100 mass of each thermoplastic resin contained in the said 1st thermoplastic resin composition, a 2nd thermoplastic resin composition, a 3rd thermoplastic resin composition, and a 4th thermoplastic resin composition. Preferably it is 0.05-10 mass parts with respect to a part.

Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, and triazine compounds. These can be used alone or in combination of two or more.
Content of the said ultraviolet absorber is 100 mass parts of each thermoplastic resin contained in the 1st thermoplastic resin composition, the 2nd thermoplastic resin composition, the 3rd thermoplastic resin composition, and the 4th thermoplastic resin composition. The amount is preferably 0.05 to 10 parts by mass.

Examples of the anti-aging agent include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds, thiols. Examples thereof include bisphenol compounds, hindered phenol compounds, phosphite compounds, imidazole compounds, nickel dithiocarbamate salts, phosphoric compounds, and the like. These can be used alone or in combination of two or more.
The content of the antioxidant is 100 parts by mass of each thermoplastic resin contained in the first thermoplastic resin composition, the second thermoplastic resin composition, the third thermoplastic resin composition, and the fourth thermoplastic resin composition. The amount is preferably 0.05 to 10 parts by mass.

Examples of the plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di- (2-ethylhexyl) phthalate, diisooctyl phthalate, and diisodecyl phthalate; dimethyl adipate , Diisobutyl adipate, di- (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyl decyl adipate, di- (2-ethylhexyl) azelate, diisooctyl azelate, diisobutyl azelate, dibutyl sebacate, di- Fatty acid esters such as (2-ethylhexyl) sebacate, diisooctyl sebacate; trimellitic acid isodecyl ester, trimellitic acid octy Esters, trimellitic acid esters such as trimellitic acid n-octyl ester, trimellitic acid isononyl ester; di- (2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinolate, trilauryl phosphate, tristearyl phosphate, Examples include tri- (2-ethylhexyl) phosphate and epoxidized soybean oil. These can be used alone or in combination of two or more.
Content of the said plasticizer is 100 mass parts of each thermoplastic resin contained in the 1st thermoplastic resin composition, the 2nd thermoplastic resin composition, the 3rd thermoplastic resin composition, and the 4th thermoplastic resin composition. On the other hand, it is preferably 0.05 to 10 parts by mass.

The preferable structure of the 1st resin layer in the solar cell backsheet of this invention, the 2nd resin layer, and the 3rd resin layer is shown below.
(A) The first resin layer is an infrared transparent colored resin layer obtained by using a first thermoplastic resin composition containing an infrared transparent colorant, and the second resin layer contains an infrared transparent colorant. Infrared ray obtained by using the third thermoplastic resin composition obtained using the second thermoplastic resin composition containing the infrared ray transparent colored resin layer, wherein the third resin layer contains the infrared ray transparent colorant. Sheet (a), which is a transmissive colored resin layer, is a first resin layer, which is an infrared transmissive colored resin layer obtained using a first thermoplastic resin composition containing an infrared transmissive colorant, and a second resin layer Is an infrared transmissive colored resin layer obtained by using a second thermoplastic resin composition containing an infrared transmissive colorant, and the third resin layer does not contain an infrared transmissive colorant. The sheet (c) first resin layer, which is a layer obtained using the composition, is infrared An infrared transmissive colored resin layer obtained by using a first thermoplastic resin composition containing a transient colorant, wherein the second resin layer contains a second thermoplastic resin composition that does not contain an infrared transmissive colorant. A sheet (D) first resin which is a layer obtained by using the infrared ray transmitting colored resin layer obtained by using the third thermoplastic resin composition containing the infrared ray transmitting colorant. The layer is an infrared transmissive colored resin layer obtained using the first thermoplastic resin composition containing an infrared transmissive colorant, and the second resin layer does not contain an infrared transmissive colorant. Sheet (e) First resin which is a layer obtained by using a resin composition and the third resin layer is a layer obtained by using a third thermoplastic resin composition not containing an infrared transmitting colorant The layer is obtained using a first thermoplastic resin composition that does not contain an infrared transmitting colorant. The second resin layer is an infrared transmissive colored resin layer obtained by using a second thermoplastic resin composition containing an infrared transmissive colorant, and the third resin layer is an infrared transmissive colorant. A sheet (f) first resin layer, which is an infrared transmissive colored resin layer obtained using a third thermoplastic resin composition containing the first thermoplastic resin composition containing no infrared transmissive colorant, is used. The second resin layer is a layer obtained by using the second thermoplastic resin composition containing an infrared transmitting colorant, and the third resin layer is an infrared transmitting colorant. A layer obtained by using the first thermoplastic resin composition in which the sheet (g) first resin layer, which is a layer obtained by using the third thermoplastic resin composition not containing, does not contain the infrared transmitting colorant. The second resin layer uses a second thermoplastic resin composition that does not contain an infrared transmitting colorant. And the third resin layer is a layer obtained by using a third thermoplastic resin composition containing an infrared transmitting colorant.

In the above aspects (a), (b), (c), and (d), the degree of coloring of the first resin layer that is the infrared transparent colored resin layer is as long as the infrared transparency in the first resin layer is satisfied. There is no particular limitation. The L value of the surface on the first resin layer side in the solar cell backsheet (hereinafter referred to as “L value as a solar cell backsheet”) is preferably 40 or less, more preferably 35 or less, and even more preferably 30. It only needs to be colored to the following extent.
Further, in an embodiment in which the first resin layer is not an infrared transparent colored resin layer, that is, in the above embodiments (e), (f), (ki) and (ku), the L value as a back sheet for a solar battery back sheet. (L value of the surface on the first resin layer side) is preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less.

In the said aspect (I), it is preferable that a 3rd resin layer is a layer obtained using the 3rd thermoplastic resin composition which does not contain an infrared rays transparent colorant and a white-type colorant.
In the said aspect (c), it is preferable that a 2nd resin layer is a layer obtained using the 2nd thermoplastic resin composition which does not contain an infrared rays transparent colorant and a white-type colorant.
In the above aspect (d), the second resin layer is a layer obtained using a second thermoplastic resin composition that does not contain an infrared transmitting colorant and a white colorant, and the third resin layer is an infrared ray. It is preferable that it is a layer obtained using the 3rd thermoplastic resin composition which does not contain a transparent colorant and a white colorant.
Examples of the white colorant include titanium oxide, zinc oxide, calcium carbonate, barium sulfate, calcium sulfate, alumina, silica, 2PbCO ₃ .Pb (OH) ₂ , [ZnS + BaSO ₄ ], talc, and gypsum. .
In the above aspects (a), (c) and (d), if the L value of the surface on the first resin layer side in the solar cell backsheet is preferably 40 or less, each layer is white. A system colorant may be included. When the white colorant is contained in each of the above layers, the upper limit of the content is usually 3 parts by mass, preferably 1 part by mass, more preferably 0.5 parts by mass with respect to 100 parts by mass of the thermoplastic resin. is there.

In the said aspect (e), it is preferable that a 1st resin layer is a layer obtained using the 1st thermoplastic resin composition which does not contain an infrared rays transparent colorant and a white-type colorant.
In the said aspect (f), it is preferable that a 1st resin layer is a layer obtained using the 1st thermoplastic resin composition which does not contain an infrared rays transparent colorant and a white-type colorant.
In the above aspect (G), the first resin layer is a layer obtained using the first thermoplastic resin composition that does not contain an infrared transmitting colorant and a white colorant, and the second resin layer is an infrared ray. It is preferable that it is a layer obtained using the 2nd thermoplastic resin composition which does not contain a transparent colorant and a white colorant.

  Of the above, the embodiments (a) and (c) are preferred, and the embodiment (a) is particularly preferred. By setting it as the said aspect (a), the effect of this invention is fully exhibited.

The first resin layer, the second resin layer, the third resin layer, and the fourth resin layer may be continuously laminated (see FIG. 1), the first resin layer, the second resin layer, or the second resin layer. The resin layer and the third resin layer may be in a continuously laminated state, and the third resin layer and the fourth resin layer may have a structure joined via an adhesive layer (not shown). . In the latter case, the configuration of the adhesive layer can be a polyurethane resin composition or the like.
Furthermore, you may have the contact bonding layer which joins each resin layer between the said 2nd resin layer and the said 3rd resin layer between the said 1st resin layer and the said 2nd resin layer (not shown). ). In this case, the configuration of the adhesive layer can be a polyurethane resin composition or the like.

  As described above, the solar cell backsheet of the present invention may be provided with a water vapor barrier layer between the third resin layer and the fourth resin layer (see FIG. 2).

The water vapor barrier layer has a moisture permeability (also referred to as “water vapor permeability”) measured under conditions of a temperature of 40 ° C. and a humidity of 90% RH in accordance with JIS K7129, preferably 3 g / (m ² · day) or less. More preferably, the layer has a performance of 1 g / (m ² · day) or less, and further preferably 0.7 g / (m ² · day) or less.
The water vapor barrier layer is preferably a layer made of an electrically insulating material.

  The water vapor barrier layer may have a single layer structure or a multilayer structure made of one kind of material, or may have a multilayer structure made of two or more kinds of materials. In this invention, it is preferable that it is a vapor deposition film by which the film | membrane which consists of a metal and / or a metal oxide is formed in the surface. Both the metal and the metal oxide may be a single substance or two or more kinds.

Examples of the metal include aluminum.
Examples of the metal compound include oxides of elements such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, and yttrium. Of these, silicon oxide, aluminum oxide, and the like are particularly preferable from the viewpoint of water vapor barrier properties.
The film made of the metal and / or metal oxide may be formed by a method such as plating, vacuum deposition, ion plating, sputtering, plasma CVD, or microwave CVD. Two or more of these methods may be combined.

  Examples of the resin layer in the vapor deposition film include polyester films such as polyethylene terephthalate film and polyethylene naphthalate; polyolefin films such as polyethylene and polypropylene; polyvinylidene chloride film, polyvinyl chloride film, fluororesin film, polysulfone film, polystyrene film, polyamide Examples thereof include a film, a polycarbonate film, a polyacryl nitrilo film, and a polyimide film. The thickness of this resin film is preferably 5 to 50 μm, more preferably 8 to 20 μm.

  The said water vapor | steam barrier layer shall be formed using the commercial item. For example, “Tech Barrier AX” manufactured by Mitsubishi Plastics, “GX Film” manufactured by Toppan Printing Co., Ltd., “Ecosia VE500” manufactured by Toyobo Co., Ltd. Can do.

  The arrangement of the water vapor barrier layer between the third resin layer and the fourth resin layer is not particularly limited, and a film made of a metal and / or a metal oxide is placed on either the third resin layer or the fourth resin layer. You may face.

  The water vapor barrier layer may be formed of a three-layer film in which a film made of a metal and / or a metal oxide is disposed between an upper layer side resin part and a lower layer side resin part.

  The thickness of the water vapor barrier layer is preferably 5 to 300 μm, more preferably 8 to 250 μm, and still more preferably 10 to 200 μm. If the water vapor barrier layer is too thin, the water vapor barrier property may be insufficient. If it is too thick, the flexibility as a sheet may not be sufficient.

  When the solar cell backsheet of the present invention includes a water vapor barrier layer, an adhesive layer can be provided between the third resin layer and / or the fourth resin layer and the water vapor barrier layer. The configuration of the adhesive layer can be a polyurethane resin composition, an epoxy resin composition, an acrylic resin composition, or the like.

The solar cell backsheet of the present invention is of the following two types.
[P] Sheet comprising first resin layer, second resin layer, third resin layer, and fourth resin layer (back surface protective layer) in sequence [Q] first resin layer, and second resin layer And a third resin layer, a water vapor barrier layer, and a fourth resin layer (back surface protective layer) in sequence.

The manufacturing method of the solar cell backsheet of the present invention is not particularly limited, and is selected according to the constituent material of each layer, that is, each thermoplastic resin.
As the method for producing the sheet of the above embodiment [P], (1) a method for producing a laminated sheet by a co-extrusion method using each thermoplastic resin composition or the like, and (2) using each thermoplastic resin composition. A method of thermally fusing or dry laminating the four types of resin sheets produced, (3) After producing a laminate composed of the first resin layer, the second resin layer and the third resin layer by a coextrusion method or the like, separately And a method of bonding a film constituting the prepared fourth resin layer to the surface of the third resin layer by heat fusion, dry lamination, or adhesive.
Moreover, as a manufacturing method of the sheet of the above embodiment [Q], (1) a co-extrusion method using the first thermoplastic resin composition, the second thermoplastic resin composition, and the third thermoplastic resin composition, etc. A laminated sheet is produced, and then the surface of the third resin layer in the laminated sheet and the water vapor barrier layer forming sheet (or film) are joined by heat fusion, dry lamination or an adhesive to form a water vapor barrier layer. Then, using the fourth thermoplastic resin composition, a method of forming the fourth resin layer on the surface of the water vapor barrier layer, (2) the first thermoplastic resin composition, the second thermoplastic resin composition, and Using the third thermoplastic resin composition, a laminated sheet is produced as described above, and then the surface of the third resin layer in the laminated sheet and the water vapor barrier layer forming sheet (or film) are heated. Fusion or A water vapor barrier layer is formed by bonding with a dry laminate or an adhesive, and then a separately prepared film using the fourth thermoplastic resin composition is thermally fused or dry laminated on the surface of the water vapor barrier layer. Or the method of joining by an adhesive agent, (3) The film which comprises a 4th resin layer, and the sheet | seat (or film) for water vapor | steam barrier layer formation are joined by heat sealing | fusion or dry lamination, or an adhesive agent. A laminated sheet formed using a first thermoplastic resin composition, a second thermoplastic resin composition, and a third thermoplastic resin composition, which is formed by forming a water vapor barrier layer and then separately preparing the surface of the water vapor barrier layer And a method of joining the third resin layer by thermal fusion, dry lamination, or an adhesive.

The thickness of the solar cell backsheet of the present invention is preferably 50 to 1,000 μm, more preferably 60 to 800 μm, and still more preferably 80 to 600 μm, regardless of the structure of each layer. When it is the said thickness, it is excellent in flexibility, and is excellent in the shape followability and workability | operativity at the time of manufacturing a solar cell module.
In addition, between each layer in the solar cell backsheet of this invention, in the range which does not impair the effect of this invention, other layers, such as a layer which consists of a decorative layer, a coating layer, and the recycled resin produced at the time of manufacture, as desired Can also be laminated.

In the present invention, from the viewpoint of the balance between heat resistance and flexibility of the solar cell backsheet of the present invention and shape stability, the thickness ( _HA ) of the first resin layer, the second resin layer, and the like. There is a specific relationship between the thickness (H _B ) and the thickness (H _C ) of the third resin layer, which is shown below.
_{0.4 ≦ (H A + H C} ) / H B ≦ 2.4 (1)
_{0.7 ≦ H A / H C ≦} 1.3 (2)

By satisfy | filling said Formula (1), it is excellent in the balance of the heat resistance in the solar cell backsheet of this invention, and flexibility. In the present _invention, if it is _{(H A + H C) /} H B <0.4, flexibility is inferior. On the other _hand, if, poor heat resistance _{(H A + H C) /} H B> 2.4. In the present invention, the above formula (1) is
_{0.5 ≦ (H A + H C} ) / H B ≦ 2.2
It is preferable that

Moreover, it is excellent in the shape stability in the solar cell backsheet of this invention by satisfy | filling said Formula (2). In the present invention, if it is _H A _/ H C _<0.7, the heat is applied, curling (first resin layer side is warped) the fourth resin layer side tends. On the other _hand, if it is H _A / H C> 1.3, when heat is applied, (warps fourth resin layer side) to curl the first resin layer side tends. In the present invention, the above formula (2) is
_{0.75 ≦ H A / H C ≦} 1.25
It is preferable that

  In this invention, when the thickness of the said 1st resin layer, the said 2nd resin layer, and the said 3rd resin layer exists in the said preferable range, and the relationship of each thickness satisfy | fills said Formula (1) and (2). The solar cell backsheet of the present invention is excellent in shape stability, that is, it is easy to bend and warp on the side of the first resin layer bonded to the filler part, so that the solar cell element is embedded. The sheet can be efficiently arranged according to the surface shape of the material part. If the third resin layer is omitted and the second resin layer is thickened, the balance of the layer structure is not sufficient, and the excellent effect of the present invention is hardly obtained.

Moreover, in this invention, when the light of wavelength 800-1400nm is radiated | emitted on the surface of the said 1st resin layer in the said solar cell backsheet, the reflectance with respect to the said light is less than 50%, Preferably 1- 40%, and when receiving sunlight, the solar cell backsheet and the solar cell module including the same are stored by the light, and the durability of the solar cell backsheet, the solar cell module, and the solar cell is reduced. Can be suppressed.
“The reflectance for light with a wavelength of 800 to 1,400 nm is less than 50%” means that the reflectance of light in the wavelength range from 800 nm to 1,400 nm is measured every 800 nm or every 1,400 nm to 20 nm. In addition, it means that the average value calculated using each reflectance is less than 50%, and it does not require that all the reflectances of light in the wavelength range are less than 50%.

  In the present invention, when light having a wavelength of 400 to 700 nm is radiated to the surface of the first resin layer in the solar cell backsheet, the light absorption rate is preferably 60% or more, more preferably 70% or more, and further Preferably it is 80% or more. The higher the absorptance, the lower the brightness of the solar cell backsheet, and the darker solar cell backsheet is formed. Thereby, when a solar cell module is arrange | positioned on the roof etc. of a house, it is excellent in an external appearance property and designability. “Absorptivity with respect to light having a wavelength of 400 to 700 nm is 60% or more” means that the absorptance of light in the wavelength region from 400 nm to 700 nm is measured every 400 nm or from 700 nm to 20 nm, and each absorptivity is used. It means that the calculated average value is 60% or more, and it does not require that the light absorption rate in the wavelength range is 60% or more.

  By providing these preferable performances, in the solar cell backsheet of the present invention, preferably, 60% or more of light having a wavelength of 400 to 700 nm emitted to the surface of the first resin layer is absorbed, and a wavelength of 800 Excellent transmittance of light of ˜1,400 nm.

  The solar cell backsheet of the present invention is excellent in heat resistance, and the dimensional change rate when the solar cell backsheet is allowed to stand at 150 ° C. for 30 minutes is preferably ± 1% or less.

When the solar cell backsheet of the present invention includes a water vapor barrier layer, the water vapor barrier property from the fourth resin layer side (water vapor barrier layer side) is excellent, and the water vapor permeability of the solar cell backsheet is in accordance with JIS K7129. When measured under conditions of a temperature of 40 ° C. and a humidity of 90% RH, it is preferably 3 g / (m ² · day) or less, more preferably 1 g / (m ² · day) or less. Since it has the above performance, deterioration of the solar cell element due to intrusion of water, water vapor, and the like, and further reduction in power generation efficiency can be suppressed, and a solar cell module excellent in durability can be provided.

  Moreover, the solar cell backsheet of this invention is excellent in the scratch resistance in the back surface, ie, the surface of a 4th resin layer.

The solar cell module of the present invention includes the above-described solar cell backsheet of the present invention. A schematic diagram of the solar cell module of the present invention is shown in FIG.
The solar cell module 2 in FIG. 3 includes a surface-side transparent protective member 21, a surface-side sealing film (surface-side filler portion) 23, a solar cell element 25, and a back surface side from the sunlight receiving surface side (upper side in the drawing). The sealing film (back surface side filler part) 27 and the solar cell backsheet 1 of the present invention may be arranged in this order. In addition, the solar cell module of this invention can also be equipped with various members as needed other than the said component as needed as needed (not shown).

As the said surface side transparent protection member 21, what consists of a material excellent in water vapor | steam barrier property is preferable, and the transparent substrate which consists of glass, resin, etc. is used normally. In addition, although glass is excellent in transparency and weather resistance, since impact resistance is not enough and it is heavy, when it is set as the solar cell mounted on the roof of a house, it is preferable to use a weather resistant transparent resin. Examples of the transparent resin include a fluorine-based resin.
The thickness of the surface side transparent protective member 21 is usually about 1 to 5 mm when glass is used, and is usually about 0.1 to 5 mm when transparent resin is used.

  The solar cell element 25 has a power generation function by receiving sunlight. As such a solar cell element, if it has a function as a photovoltaic power, it will not be specifically limited, A well-known thing can be used. For example, a crystalline silicon solar cell element such as a single crystal silicon type solar cell element or a polycrystalline silicon type solar cell element; an amorphous silicon solar cell element having a single bond type or a tandem structure type; gallium arsenide (GaAs) III-V compound semiconductor solar cell elements such as InP); II-VI compound semiconductor solar cell elements such as cadmium tellurium (CdTe) and copper indium selenide (CuInSe2). Of these, a crystalline silicon solar cell element is preferable, and a polycrystalline silicon solar cell element is particularly preferable. A thin film polycrystalline silicon solar cell element, a thin film microcrystalline silicon solar cell element, a hybrid element of a thin film crystalline silicon solar cell element and an amorphous silicon solar cell element, or the like can be used.

  Although not shown in FIG. 3, the solar cell element 25 usually includes a wiring electrode and a take-out electrode. The wiring electrode has an action of collecting electrons generated in the plurality of solar cell elements by receiving sunlight, for example, a solar cell element on the surface side sealing film (surface side filler part) 21 side, It connects so that the solar cell element by the side of the back surface side sealing film (back surface side filler material part) 27 side may be connected. The take-out electrode has an action of taking out electrons collected by the wiring electrode or the like as a current.

The front-side sealing film (front-side filler part) 21 and the back-side sealing film (back-side filler part) 27 (hereinafter collectively referred to as “sealing film”) are usually identical to each other. Alternatively, after using a different sealing film forming material to form a sheet-shaped or film-shaped sealing film in advance, between the surface-side transparent protective member 21 and the solar cell backsheet 1, the solar cell element 25, etc. It is formed by thermocompression bonding.
The thickness of each sealing film (filler part) is usually about 100 μm to 4 mm, preferably about 200 μm to 3 mm, more preferably about 300 μm to 2 mm. If the thickness is too thin, the solar cell element 25 may be damaged. On the other hand, if the thickness is too thick, the manufacturing cost increases, which is not preferable.

  The sealing film forming material is usually a resin composition or a rubber composition. Examples of the resin include an olefin resin, an epoxy resin, a polyvinyl butyral resin, and the like. Examples of the rubber include silicone rubber and hydrogenated conjugated diene rubber. Of these, olefin resins and hydrogenated conjugated diene rubbers are preferred.

  Examples of olefin resins include olefins such as ethylene, propylene, butadiene, and isoprene, or polymers obtained by polymerizing diolefins, and ethylene and other monomers such as vinyl acetate and acrylate esters. Copolymers, ionomers and the like can be used. Specific examples include polyethylene, polypropylene, polymethylpentene, ethylene / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid ester copolymer, ethylene / vinyl alcohol copolymer, chlorine. Examples thereof include chlorinated polyethylene and chlorinated polypropylene. Among these, an ethylene / vinyl acetate copolymer and an ethylene / (meth) acrylic acid ester copolymer are preferable, and an ethylene / vinyl acetate copolymer is particularly preferable.

  Examples of hydrogenated conjugated diene rubber include hydrogenated styrene / butadiene rubber, styrene / ethylene butylene / olefin crystal block polymer, olefin crystal / ethylene butylene / olefin crystal block polymer, styrene / ethylene butylene / styrene block polymer, and the like. It is done. Preferably, a hydrogenated conjugated diene block copolymer having the following structure, that is, a polymer block A containing an aromatic vinyl compound unit; a conjugated diene compound having a 1,2-vinyl bond content exceeding 25 mol% Polymer block B formed by hydrogenating 80 mol% or more of a double bond portion of a polymer containing a unit; Double of a polymer containing a conjugated diene compound unit having a 1,2-vinyl bond content of 25 mol% or less Polymer block C obtained by hydrogenating 80 mol% or more of the bonded portion; and a polymer block C obtained by hydrogenating 80 mol% or more of the double bond portion of the copolymer containing the aromatic vinyl compound unit and the conjugated diene compound unit. It is a block copolymer having at least two selected from the combined block D.

The sealing film-forming material may contain a crosslinking agent, a crosslinking aid, a silane coupling agent, an ultraviolet absorber, a hindered phenol-based or phosphite-based antioxidant, a hindered amine-based light stabilizer, a light as necessary. Additives such as diffusing agents, flame retardants, and anti-discoloring agents can be contained.
As described above, the material forming the front surface side sealing film (front surface side filler part) 23 and the material forming the back surface side sealing film (back surface side filler part) 27 are the same or different. However, the same is preferable from the viewpoint of adhesiveness.

The solar cell module of the present invention includes, for example, the surface-side transparent protective member, the surface-side sealing film, the solar cell element, the back-side sealing film, and the solar cell backsheet of the present invention, which are arranged in this order. Can be manufactured by a lamination method or the like, in which heat bonding is performed while vacuum suction is performed.
The lamination temperature in this lamination method is usually about 100 ° C. to 250 ° C. from the viewpoint of adhesiveness of the solar cell backsheet of the present invention. The laminating time is usually about 3 to 30 minutes.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. In the following, “part” and “%” are based on mass unless otherwise specified.

1. Evaluation method Measurement methods for various evaluation items are shown below.
1-1. Rubber content in thermoplastic resin composition Calculated from the composition at the time of raw material charging.
1-2. N-phenylmaleimide unit content Calculated from the composition at the time of raw material charging.
1-3. Glass transition temperature (Tg)
Based on JIS K 7121, it was measured with a differential scanning calorimeter “DSC2910” (model name) manufactured by TA Instruments. In addition, when two or more types of thermoplastic resins were contained in the thermoplastic resin composition and a plurality of Tg were obtained by the DSC curve, the higher Tg was adopted.

1-4. Absorptivity (%) for light having a wavelength of 400 to 700 nm
A solar cell back sheet (50 mm × 50 mm, thickness is listed in the table) is used as a measurement sample, and transmittance and reflectance are measured with an ultraviolet-visible near-infrared spectrophotometer “V-670” (model name) manufactured by JASCO Corporation. Was measured. That is, light was emitted to the surface of the first resin layer of the measurement sample, and the transmittance and reflectance in the wavelength region from 400 nm to 700 nm were measured every 20 nm, and the average value thereof was calculated. The absorptance was calculated by the following formula using the average value of transmittance and the average value of reflectance.
Absorptivity (%) = 100− {transmittance (%) + reflectance (%)}

1-5. Reflectance (%) for light with a wavelength of 800 to 1,400 nm
A solar cell backsheet (50 mm × 50 mm, thickness is listed in the table) was used as a measurement sample, and the reflectance was measured with an ultraviolet-visible near-infrared spectrophotometer “V-670” (model name) manufactured by JASCO Corporation. . That is, light was emitted to the surface of the first resin layer of the measurement sample, the reflectance in the wavelength range from 800 nm to 1,400 nm was measured every 20 nm, and the average value of these was calculated.

1-6. L value Using a spectrophotometer “TCS-II” (model name) manufactured by Toyo Seiki Seisakusho Co., Ltd., the first resin layer side surface and the fourth surface in the solar cell backsheet (50 mm × 50 mm, thickness is shown in the table) The L value of the resin layer side surface was measured.

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×：変形があった 1-7. Heat resistance A solar cell backsheet (thickness is described in the table) was cut to prepare a test piece having a size of 120 mm (MD; resin extrusion direction) × 120 mm (TD; direction orthogonal to MD). Next, a square mark of 100 mm (MD) × 100 mm (TD) was drawn at the center of the test piece, and left at 150 ° C. for 30 minutes in a thermostatic bath. Then, it cooled, the length in the said marked line was measured, and the dimensional change rate was computed from the following formula.

Moreover, the shape of the test piece after a process was observed visually, and the following reference | standard determined.
○: No deformation △: Very slightly deformed ×: Deformed

1-8. The solar cell backsheet (thickness is listed in the table) was cut to prepare a test piece having a size of 100 mm (MD) × 100 mm (TD). Next, after bending along the symmetry axis in the MD direction, bending was performed along the symmetry axis in the TD direction. The folded test piece was reciprocated twice on each crease at a speed of 5 mm / sec using a manual crimping roll (2,000 g) according to JIS Z0237. Thereafter, the folds were widened to return to the original state, the test piece was visually observed, and judged according to the following criteria. Those in which the folds are not broken are excellent in flexibility.
◯: The crease is not cracked, and the crease is not cracked even if it is folded or expanded again.
(Triangle | delta): Although a crease | fold is not cracked, if it folds again and spreads, a crease | fold will be cracked.
X: The crease is broken.

1-9. Hydrolysis resistance (holding breaking stress)
A back sheet for solar cell (thickness is described in the table) was cut to prepare a test piece having a size of 200 mm (MD) × 200 mm (TD). Next, this test piece was left for 300 hours under conditions of a temperature of 105 ° C. and a humidity of 100% RH, then cut into a strip shape having a length of 200 mm × width of 15 mm, and manufactured by Shimadzu Corporation according to JIS K7127. Using a precision universal material testing machine “Autograph AG2000” (model name), the breaking stress was measured. The distance between chucks when the measurement sample was set was 100 mm, and the tensile speed was 300 mm / min. From the measured value of the breaking stress obtained, the retention rate of the breaking stress was determined by the following formula.
Breaking stress retention rate (%) = (breaking stress after treatment for 300 hours at a temperature of 105 ° C. and humidity of 100% RH (N / 15 mm)) ÷ (breaking stress in the initial stage (before treatment (N / 15 mm))) × 100
○: Retention rate exceeded 80% Δ: Retention rate was 50% to 80% ×: Retention rate was less than 50%

1-10. Hydrolysis resistance (measurement of deformation state)
The test piece after the high-temperature and high-humidity treatment in 1-9 above was visually observed and judged according to the following criteria.
○: No deformation △: Very slightly deformed ×: Deformed

1-11. Thermal storage Back sheet for solar cell (80 mm x 80 mm, thickness is listed in the table) is used as a measurement sample. The surface of one resin layer was irradiated with an infrared lamp (output: 100 W) from a height of 200 mm. The surface temperature after 60 minutes of irradiation was measured using a surface thermometer. The unit is ° C.

1-12. Weather resistance A solar cell backsheet (thickness is listed in the table) was cut to prepare a test piece having a size of 500 mm (MD) × 30 mm (TD). Next, the conditions of Steps 1 to 4 shown below were repeated on the surface of the test piece on the first resin layer side to be subjected to an exposure test, and a color tone change value ΔE before exposure and after 100 hours of exposure was calculated. The processing apparatus is a metering weather meter “MV3000” (model name) manufactured by Suga Test Instruments Co., Ltd.
Step 1: Irradiation 0.53 kW / m ² , 63 ° C., 50% RH, 4 hours Step 2: Irradiation + rainfall 0.53 kW / m ² , 63 ° C., 95% RH, 1 minute Step 3: Dark 0 kW / m ² , 30 ° C., 98% RH, 4 hours Step 4: Irradiation + rainfall 0.53 kW / m ² , 63 ° C., 95% RH, 1 minute

ΔE was calculated from Lab (L: brightness, a: redness, b: yellowness) data using a spectrophotometer “V670” (model name) manufactured by JASCO Corporation according to the following equation.
ΔE = √ {(L ₁ −L ₀ ) ² + (a ₁ −a ₀ ) ² + (b ₁ −b ₀ ) ² }
(In the formula, L ₁ , a ₁ and b ₁ are values after exposure, and L ₀ , a ₀ and b ₀ are values before exposure.)
The smaller the value of ΔE, the smaller the change in color and the better the weather resistance. The weather resistance was determined according to the following criteria.
○: ΔE was 10 or less ×: ΔE exceeded 10

1-13. Flame retardance Solar cell backsheet (20mm x 100mm, thickness is listed in the table) is used as a test piece, this test piece is suspended vertically and a burner for UL94 V test is used from the burner tip to the lower end of the test piece. With the distance of 10 mm until, the lower end of the test piece was indirectly flamed for 5 seconds. After the completion of flame contact, the combustion state of the flame contact portion of the test piece was visually observed and judged according to the following criteria.
○: not ignited ×: ignited

1-14. Scratch resistance The surface on the fourth resin layer side of the back sheet for solar cells was subjected to 500 reciprocating frictions using a reciprocating friction tester manufactured by Tohken Seimitsu Kogyo Co., Ltd. with cotton canvas No. 3 and a vertical load of 500 g. The subsequent surface was visually observed and judged according to the following criteria.
○: No scratch was observed Δ: Scratch was slightly observed ×: Scratch was clearly observed

1-15. Water vapor barrier property Water vapor permeability is measured according to JIS K7129B using MOPER's water vapor permeability measuring device “PERMATRAN W3 / 31” (model name) under conditions of a temperature of 40 ° C. and a humidity of 90% RH. did. As the transmission surface, the surface on the fourth resin layer side was disposed on the water vapor side.

2. 2. Raw materials for producing solar cell backsheet 2-1. Silicone / acrylic composite rubber reinforced styrene resin (rubber reinforced resin A1)
“Metablene SX-006” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. was used. This is a resin obtained by grafting an acrylonitrile / styrene copolymer onto a silicone / acrylic composite rubber. The content of the silicone / acrylic composite rubber is 50%, the grafting rate is 80%, the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C) 0.38 dl / g, glass transition temperature (Tg) 135 ° C).

2-2. Silicone rubber reinforced styrene resin (rubber reinforced resin A2)
1.3 parts of p-vinylphenylmethyldimethoxysilane and 98.7 parts of octamethylcyclotetrasiloxane are mixed, and this is put into 300 parts of distilled water in which 2.0 parts of dodecylbenzenesulfonic acid is dissolved, and 3 parts by a homogenizer. The mixture was stirred and dispersed for emulsification. This emulsified dispersion was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, and heated at 90 ° C. for 6 hours while stirring. Subsequently, it was kept at 5 ° C. for 24 hours to complete the condensation, and a latex containing a polyorganosiloxane rubber was obtained. The condensation rate was 93%. Thereafter, the latex was neutralized to pH 7 using an aqueous sodium carbonate solution. The obtained polyorganosiloxane rubber had a volume average particle size of 300 nm.
Next, in a 7-liter glass flask equipped with a stirrer, 100 parts of ion exchange water, 1.5 parts of potassium oleate, 0.01 parts of potassium hydroxide, 0.1 part of tert-dodecyl mercaptan, A batch polymerization component consisting of a latex adjusted to pH 7 containing 40 parts of an organosiloxane rubber, 15 parts of styrene and 5 parts of acrylonitrile was added, and the temperature was raised while stirring. When the temperature reaches 45 ° C., the activity comprises 0.1 part of sodium ethylenediaminetetraacetate, 0.003 part of ferrous sulfate, 0.2 part of sodium formaldehyde sulfoxylate dihydrate and 15 parts of ion-exchanged water. Aqueous agent aqueous solution and 0.1 part of diisopropylbenzene hydroperoxide were added and polymerization was carried out for 1 hour.
Thereafter, 50 parts of ion exchange water, 1 part of potassium oleate, 0.02 part of potassium hydroxide, 0.1 part of tert-dodecyl mercaptan, 0.2 part of diisopropylbenzene hydroperoxide, 30 parts of styrene and An incremental polymerization component consisting of 10 parts of acrylonitrile was added continuously over 3 hours to continue the polymerization. After completion of the addition, stirring was further continued. One hour later, 0.2 part of 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) was added to terminate the polymerization, and a latex containing a silicone rubber reinforced styrene resin (rubber reinforced resin A2) was added. Obtained. Next, 1.5 parts of sulfuric acid is added to the latex to coagulate the resin component at 90 ° C., and then the resin component is washed with water, dehydrated and dried to obtain a silicone rubber reinforced styrene resin (rubber reinforced resin A2). Got. The glass transition temperature (Tg) was 108 ° C., the polyorganosiloxane rubber content was 40%, the graft ratio was 84%, and the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) was 0.60 dl / g.

2-3. Acrylic rubber reinforced aromatic vinyl resin (rubber reinforced resin A3)
The reactor contains an acrylic rubbery polymer (volume average particle size: 100 nm, gel content: 90%) obtained by emulsion polymerization of 99 parts of n-butyl acrylate and 1 part of allyl methacrylate. 50 parts of latex having a solid content concentration of 40% (in terms of solid content) was added, and further diluted with 1 part of sodium dodecylbenzenesulfonate and 150 parts of ion-exchanged water. Thereafter, the inside of the reactor was replaced with nitrogen gas, and 0.02 part of disodium ethylenediaminetetraacetate, 0.005 part of ferrous sulfate and 0.3 part of sodium formaldehydesulfoxylate were added, and the mixture was stirred up to 60 ° C. The temperature rose.
On the other hand, 50 parts of a mixture of 37.5 parts of styrene and 12.5 parts of acrylonitrile, 1.0 part of terpinolene and 0.2 part of cumene hydroperoxide are placed in a container, and the inside of the container is replaced with nitrogen gas. A mass composition was obtained.
Next, the monomer composition was added to the reactor at a constant flow rate over 5 hours, and polymerization was performed at 70 ° C. to obtain a latex. Magnesium sulfate was added to this latex to coagulate the resin component. Then, acrylic rubber reinforced aromatic vinyl resin (rubber reinforced resin A3) was obtained by washing with water and drying. The acrylic rubbery polymer content was 50%, the graft ratio was 93%, the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) was 0.30 dl / g, and the glass transition temperature (Tg) was 108 ° C.

2-4. Butadiene rubber reinforced aromatic vinyl resin (rubber reinforced resin A4)
In a glass reaction vessel equipped with a stirrer, 75 parts of ion exchange water, 0.5 part of potassium rosinate, 0.1 part of tert-dodecyl mercaptan, polybutadiene latex (volume average particle size: 270 nm, gel content: 90% ) 32 parts (in terms of solid content), styrene / butadiene copolymer latex (styrene unit content: 25%, volume average particle size: 550 nm, gel content: 50%), 8 parts (in terms of solid content), 15 parts of styrene and acrylonitrile 5 parts was added, and the temperature was raised with stirring in a nitrogen stream. When the internal temperature reached 45 ° C., an aqueous solution in which 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose were dissolved in 20 parts of ion-exchanged water was added. . Thereafter, 0.07 part of cumene hydroperoxide was added, polymerization was started at 70 ° C., and polymerization was performed for 1 hour.
Thereafter, 50 parts of ion exchange water, 0.7 part of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.05 part of tert-dodecyl mercaptan and 0.01 part of cumene hydroperoxide are continuously added over 3 hours. The polymerization was continued. After the polymerization for 1 hour, 0.2 part of 2,2′-methylenebis (4-ethylene-6-tert-butylphenol) was added to complete the polymerization to obtain a latex.
Next, magnesium sulfate was added to the latex to coagulate the resin component. Then, butadiene rubber reinforced aromatic vinyl resin (rubber reinforced resin A4) was obtained by washing with water and drying. The content of butadiene rubber was 40%, the graft ratio was 72%, the intrinsic viscosity [η] of the acetone-soluble component was 0.47 dl / g, and the glass transition temperature (Tg) was 108 ° C.

2-5. Acrylonitrile / styrene copolymer AS resin “SAN-H” (trade name) manufactured by Technopolymer Co., Ltd. was used. The glass transition temperature (Tg) is 108 ° C.

2-6. Acrylonitrile / styrene / N-phenylmaleimide copolymer Acrylonitrile / styrene / N-phenylmaleimide copolymer “Polyimilex PAS1460” (trade name) manufactured by Nippon Shokubai Co., Ltd. was used. The amount of N-phenylmaleimide units is 40%, the amount of styrene units is 51%, and the Mw in terms of polystyrene by GPC is 120,000. The glass transition temperature (Tg) is 173 ° C.

2-7. Infrared transmitting colorant A perylene-based black pigment “Lumogen BLACK FK4280” (trade name) manufactured by BASF was used.

2-8. Yellow colorant A quinophthalone yellow pigment “Pariotol Yellow K0961HD” (trade name) manufactured by BASF Corporation was used.

2-9. Carbon black “Carbon black # 45” (trade name) manufactured by Mitsubishi Chemical Corporation was used.

2-10. Water vapor barrier layer forming film (R-1)
A transparent vapor deposition film “Tech Barrier AX” (trade name) manufactured by Mitsubishi Plastics, Inc. was used. It is a transparent film having a silica vapor deposition film on one side of a PET film, and has a thickness of 12 μm and a water vapor transmission rate (JIS K7129) of 0.15 g / (m ² · day).
2-11. Water vapor barrier layer forming film (R-2)
An inorganic binary vapor barrier film “Ecosia VE500” (trade name) manufactured by Toyobo Co., Ltd. was used. This is a transparent film obtained by vapor-depositing (silica / alumina) on one side of a PET film, and has a thickness of 12 μm and a water vapor permeability of 0.5 g / (m ² · day).

2-12. Fourth resin layer film (IV-1)
A PET film “Melinex 238” (trade name) manufactured by Teijin DuPont was used. The thickness is 75 μm.
2-13. Fourth resin layer film (IV-2)
SKC PET film “SR55” (trade name) was used. The thickness is 75 μm.
2-14. Fourth resin layer film (IV-3)
A PET film “Lumirror X10P” (trade name) manufactured by Toray Industries, Inc. was used. The thickness is 50 μm.

3. Preparation of first thermoplastic resin composition Production Example 1-1
The thermoplastic resin and the colorant were mixed by a Henschel mixer at the ratio shown in Table 1. Then, it melt-kneaded at the barrel temperature of 270 degreeC using the Nippon Steel Works twin screw extruder "TEX44" (model name), and obtained the pellet-shaped 1st thermoplastic resin composition (I-1) (Table | Table) 1).

Production Examples 1-2 to 1-7
Except having used a thermoplastic resin and a coloring agent in the ratio shown in Table 1, it is the same as that of manufacture example 1-1, and the pellet-shaped 1st thermoplastic resin composition (I-2)-(I- 7) was obtained (see Table 1).

4). Preparation of second thermoplastic resin composition Production Example 2-1
The thermoplastic resin and the colorant were mixed by a Henschel mixer at the ratio shown in Table 2. Then, it melt-kneaded at the barrel temperature of 270 degreeC using the Nippon Steel Works twin screw extruder "TEX44" (model name), and obtained the pellet-shaped 1st thermoplastic resin composition (II-1) (Table | Table) 2).

Production Examples 2-2 to 2-8
Except having used a thermoplastic resin and a coloring agent in the ratio shown in Table 2, it is the same as that of manufacture example 2-1, and the pellet-shaped 1st thermoplastic resin composition (II-2)-(II-). 8) was obtained (see Table 2).

5). Preparation of third thermoplastic resin composition Production Example 3-1
The thermoplastic resin and the colorant were mixed at a ratio shown in Table 3 using a Henschel mixer. Then, it melt-kneaded at the barrel temperature of 270 degreeC using the Nippon Steel Works twin screw extruder "TEX44" (model name), and obtained the pellet-shaped 1st thermoplastic resin composition (III-1) (Table | Table) 3).

Production Examples 3-2 to 3-8
Except having used a thermoplastic resin and a coloring agent in the ratio shown in Table 3, it is the same as that of manufacture example 3-1, 1st thermoplastic resin composition (III-2)-(III-) of pellet form. 8) was obtained (see Table 3).

6). Manufacture and evaluation of back sheets for solar cells (1)
Example 1
Using a multilayer film molding machine having a T-die having a die width of 1,400 mm and a lip interval of 1.5 mm and having three extruders with a screw diameter of 65 mm, each extruder is provided with a first thermoplastic resin composition (I- 1) The 2nd thermoplastic resin composition (II-1) and the 3rd thermoplastic resin composition (III-1) were supplied. Then, each resin composition melted at a temperature of 270 ° C. was discharged from the T die to obtain a three-layer soft film. Thereafter, this three-layer soft film was brought into surface contact with a cast roll whose surface temperature was controlled to 95 ° C. with an air knife and cooled and solidified to obtain a laminated film having a thickness of 75 μm. The thicknesses of the first resin layer, the second resin layer, and the third resin layer are as shown in Table 4. Thickness gauge "ID-C1112C" (model name) manufactured by Mitutoyo Co., Ltd. is used to cut the film after 1 hour from the start of film production. Then, the thickness was measured at intervals of 10 mm (n = 107), and the average value was obtained. Measurement point values in the range of 20 mm from the edge of the film were removed from the average calculation.
Next, the film for 4th resin layers of Table 4 was adhere | attached on the outer surface of the 3rd resin layer in the said laminated | multilayer film using the polyurethane-type adhesive agent, and the solar cell backsheet was obtained. And about this solar cell backsheet, various evaluation was performed and the result was written together in Table 4.

Examples 2 to 10 and Comparative Examples 1 to 8
Using the first thermoplastic resin composition, the second thermoplastic resin composition, and the third thermoplastic resin composition shown in Tables 4 to 8, a solar cell backsheet was obtained in the same manner as in Example 1. It was. And about this solar cell backsheet, various evaluation was performed and the result was written together in Table 4-Table 8. FIG.

4). Manufacture and evaluation of solar cell backsheet (2)
Example 11
Using a multilayer film molding machine having a T-die having a die width of 1,400 mm and a lip interval of 1.5 mm and having three extruders with a screw diameter of 65 mm, each extruder is provided with a first thermoplastic resin composition (I- 2) The 2nd thermoplastic resin composition (II-2) and the 3rd thermoplastic resin composition (III-2) were supplied. Then, each resin composition melted at a temperature of 270 ° C. was discharged from the T die to obtain a three-layer soft film. Thereafter, this three-layer soft film was brought into surface contact with a cast roll whose surface temperature was controlled at 95 ° C. with an air knife and cooled and solidified to obtain a laminated film having a thickness of 170 μm. The thicknesses of the first resin layer, the second resin layer, and the third resin layer are as shown in Table 9. Thickness gauge "ID-C1112C" (model name) manufactured by Mitutoyo Co., Ltd. is used to cut the film after 1 hour from the start of film production. Then, the thickness was measured at intervals of 10 mm (n = 107), and the average value was obtained. Measurement point values in the range of 20 mm from the edge of the film were removed from the average calculation.
Next, the water vapor barrier layer-forming film was adhered to the outer surface of the third resin layer in the laminated film using a polyurethane-based adhesive so that the vapor deposition film became the outer surface. Furthermore, the film for 4th resin layers of Table 9 was adhere | attached on the surface of the vapor deposition film in a water vapor | steam barrier layer using the polyurethane-type adhesive agent, and the solar cell backsheet was obtained. And about this solar cell backsheet, various evaluation was performed and the result was written together in Table 9. FIG.

Example 12
Using the first thermoplastic resin composition, the second thermoplastic resin composition, the third thermoplastic resin composition, and the water vapor barrier layer forming film shown in Table 9, as in Example 11, for solar cells A backsheet was obtained. And about this solar cell backsheet, various evaluation was performed and the result was written together in Table 9. FIG.

In the present invention, the solar cell backsheet comprising the first resin layer, the second resin layer, the third resin layer, and the fourth resin layer in sequence can improve the power generation efficiency of the solar cell, Excellent heat resistance, flexibility, dimensional stability and weather resistance, and also excellent scratch resistance, punching resistance, chemical resistance and flame resistance. Therefore, it is suitable for outdoor use exposed to sunlight or wind and rain for a long period of time, and not only the solar cell module constituting the solar cell used for the roof of a house, but also a flexible solar cell module. Useful as a sheet.
Moreover, in this invention, the solar cell backsheet which comprises a 1st resin layer, a 2nd resin layer, a 3rd resin layer, a water vapor | steam barrier layer, and a 4th resin layer sequentially improves the power generation efficiency of a solar cell. Excellent design, heat resistance, flexibility, water vapor barrier properties, scratch resistance, hydrolysis resistance, dimensional stability and weather resistance, as well as punching resistance, chemical resistance and flame resistance Excellent. Therefore, it is suitable for outdoor use exposed to sunlight or wind and rain for a long period of time, and not only the solar cell module constituting the solar cell used for the roof of a house, but also a flexible solar cell module. Useful as a sheet.

1 and 1 ′: solar cell backsheet 11: first resin layer 12: second resin layer 13: third resin layer 14: water vapor barrier layer 15: fourth resin layer 2: solar cell module 21: surface side transparent protection Member 23: Front side sealing film 25: Solar cell element 27: Back side sealing film

Claims (10)

In the solar cell backsheet comprising a first resin layer, a second resin layer, a third resin layer, and a fourth resin layer in order, of the first resin layer, the second resin layer, and the third resin layer. At least one layer is an infrared transparent colored resin layer, the fourth resin layer is a back surface protective layer, the thickness of the first resin layer (H _A ), the thickness of the second resin layer (H _B ) and thickness of the third resin layer _{(H C)} satisfies the following formula (1) and 2, and the light of wavelength 800～1,400Nm, above the backsheet for the solar cell the The solar cell backsheet, wherein when reflected on the surface of one resin layer, the reflectance with respect to the light is less than 50%.
_{0.4 ≦ (H A + H C} ) / H B ≦ 2.4 (1)
_{0.7 ≦ H A / H C ≦} 1.3 (2)   The solar cell backsheet according to claim 1, wherein when light having a wavelength of 400 to 700 nm is radiated to the surface of the first resin layer in the solar cell backsheet, the light absorption rate is 60% or more.   The back sheet for solar cell according to claim 1 or 2, wherein a dimensional change rate when left at 150 ° C for 30 minutes is ± 1% or less.   The thermoplastic resin that constitutes the first resin layer, the thermoplastic resin that constitutes the second resin layer, and the thermoplastic resin that constitutes the third resin layer are all thermoplastic resins containing an aromatic vinyl resin. The solar cell backsheet according to any one of claims 1 to 3.   The glass transition temperature of the thermoplastic resin constituting the first resin layer and the glass transition temperature of the thermoplastic resin constituting the third resin layer are both glass of the thermoplastic resin constituting the second resin layer. The solar cell backsheet according to any one of claims 1 to 4, which is lower than a transition temperature.   The solar cell backsheet according to any one of claims 1 to 5, wherein the fourth resin layer is a resin layer having flame retardancy.   The solar cell backsheet according to any one of claims 1 to 6, further comprising a water vapor barrier layer between the third resin layer and the fourth resin layer.   The solar cell backsheet according to claim 7, wherein the water vapor barrier layer is formed of a vapor deposition film in which a film containing a metal and / or a metal oxide is formed on a surface thereof.   The back sheet for solar cells according to claim 1, wherein the back sheet for solar cells has a thickness of 50 to 1,000 μm.   A solar cell module comprising the solar cell backsheet according to any one of claims 1 to 9.

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