JP5542547B2 - Solar cell module, composition for solar cell sealing material, and solar cell sealing material comprising the same - Google Patents

Description

  The present invention relates to a solar cell module capable of increasing the wavelength conversion efficiency of sunlight, a composition for a solar cell encapsulant and a solar cell encapsulant used therefor, and more specifically, the sun capable of enhancing the wavelength conversion efficiency of sunlight. Eliminates the drawbacks of battery modules and the ethylene-vinyl acetate copolymer (EVA) type that occupies the mainstream of conventional encapsulants, making it easy to form solar cell modules, eliminating deacetic acid, water vapor barrier properties, and moisture absorption resistance The present invention relates to a composition for a solar cell encapsulant that is excellent in properties, crosslinkability, and the like, and a solar cell encapsulant that retains transparency, heat resistance, flexibility, and the like.

In recent years, global environmental issues have been actively promoted. As part of these efforts, in order to control global warming, reductions in greenhouse gases have been screamed, and carbon dioxide has been reduced, particularly with the aim of a low-carbon society. However, the use of natural energy such as hydroelectric power generation, wind power generation, geothermal power generation, and solar power generation is being promoted as an alternative to fossil fuels that emit significant amounts of carbon dioxide.
Among these, because solar power generation has significantly improved performance such as power generation efficiency of solar cell modules, the price has declined, and the national and local governments have promoted the introduction of residential solar power generation systems, In recent years, the spread has progressed remarkably.

Photovoltaic power generation generally protects solar cell elements such as silicon, gallium-arsenic, copper-indium-selenium with an upper transparent protective material and a lower substrate protective material, and the solar cell element and protective material are sealed with resin. It uses solar cell modules fixed with materials and packaged, and although it is smaller in scale than hydroelectric power generation, wind power generation, etc., it can be distributed and placed in places where power is required, so it improves performance such as power generation efficiency Research and development aimed at lowering prices is being promoted.
However, further cost reduction is necessary for further diffusion. Therefore, not only the development of solar cell elements using new materials, such as conventional silicon and gallium arsenide, but also the manufacturing cost of solar cell modules Efforts to further reduce this are continuing.

Sunlight has a wide wavelength region including ultraviolet light, visible light, and infrared light. However, the light energy of incident solar light depends on the cell (power generation element) in the solar cell, and is in a region that can be absorbed by the cell. Only the wavelength is converted.
Therefore, in order to improve the conversion efficiency of these light energies in the solar cell, a solar cell module in which a wavelength conversion material that converts ultraviolet light into visible light is arranged between the transparent glass substrate of the solar cell module and the solar cell. It has been proposed (see, for example, Patent Document 1).
Moreover, it has the structure which has arrange | positioned the photovoltaic cell in this which provided the sealing material layer which consists of an ethylene-vinyl acetate copolymer between a protective transparent plate and a board | substrate, Until incident light reaches a photovoltaic cell A solar cell module having a light transmittance of 40% to 70% at a wavelength of 360 nm has been proposed (for example, see Patent Document 2).

Moreover, a rare earth complex emitting fluorescence of 500 to 1000 nm is applied to a sealing material of a solar cell module in which a large number of units having a crystalline silicon cell sealed with a sealing material between the front cover, the back cover, and the cover are incorporated. The solar module to contain is proposed (for example, refer patent document 3).
However, these sealing materials used in Patent Document 2 or Patent Document 3 are all EVA, and have drawbacks such as deacetic acid resistance, water vapor barrier properties, moisture absorption resistance, as will be described later. It has problems in terms of the manufacturing process and performance of solar cell modules.

  On the other hand, the solar cell encapsulant constituting the solar cell module is required to have good transparency in order to secure the incident amount of sunlight so as not to reduce the power generation efficiency of the solar cell. Yes. Moreover, since a solar cell module is normally installed outdoors, it is exposed to sunlight for a long period of time and the temperature rises. Therefore, in order to avoid troubles in which the resin sealing material flows and the module is deformed, it must have heat resistance. Furthermore, in order to reduce the material cost of the solar cell element year after year, the thickness has been reduced, and a sealing material with further flexibility is also required.

Currently, a resin sealing material for a solar cell element in a solar cell module has an ethylene-vinyl acetate copolymer having a high vinyl acetate content (hereinafter sometimes referred to as EVA) from the viewpoints of flexibility and transparency. Is used together with an organic peroxide as a crosslinking agent (see, for example, Patent Document 4).
And in the sealing operation of the solar cell element, after the solar cell element is covered with a resin sealing material, the solar cell element is heated for several minutes to tens of minutes and temporarily bonded, and the organic peroxide is decomposed in the oven. Then, heat treatment is performed for several minutes to 1 hour to bond them (for example, see Patent Document 5).
However, these EVAs have disadvantages such as deacetication occurring at high temperatures, poor water vapor barrier properties, moisture absorption resistance, and the like.

In addition, in order to reduce the manufacturing cost of the solar cell module, further shortening of the time required for the sealing work is demanded. A solar cell encapsulant made of an amorphous or low crystalline α-olefin copolymer of 40% or less has been proposed (see, for example, Patent Document 6).
In this Patent Document 6, it is exemplified that an amorphous or low crystalline ethylene-butene-1 copolymer is mixed with an organic peroxide and a sheet is produced at a processing temperature of 100 ° C. using a profile extruder. However, since the processing temperature is low, there is a problem that sufficient productivity is low. In particular, an α-olefin polymer produced with a single site catalyst has a narrow molecular weight distribution, poor processability, an increased torque of an extruder or the like, and a further reduction in productivity. In addition, in order to mold such a resin with a narrow molecular weight distribution at high speed, it is necessary to mold at a higher temperature, which is not only a cause of increased generation of burnt resin and eyes, but also about the conversion efficiency of solar energy There is no suggestion of disclosure, and improvements are required to eliminate the various drawbacks of the conventional solar modules.

  Under such circumstances, it is easy to form a solar cell module that eliminates the drawbacks of the EVA type resin that occupies the mainstream of conventional sealing materials, has no deacetic acid, and has excellent water vapor barrier properties, moisture absorption resistance, crosslinkability, etc. Development of a resin composition for a solar cell encapsulant for the purpose of improving the wavelength conversion efficiency of sunlight, and further development of a solar cell module capable of increasing the wavelength conversion efficiency of sunlight using the same is desired. .

JP 2007-27271 A JP 2008-235610 A JP 2006-303033 A JP-A-9-116182 JP 2003-204073 A JP 2006-210906 A

  An object of the present invention is to provide a solar cell module capable of improving the wavelength conversion efficiency of sunlight, and a solar cell module, in view of the above-mentioned problems of the prior art, easy to form, no deacetic acid, water vapor barrier property, moisture absorption resistance , A resin composition for a solar cell encapsulant that is excellent in crosslinkability and the like, in particular for the purpose of improving the wavelength conversion efficiency of sunlight, and a solar cell encapsulant that retains transparency, heat resistance, flexibility, etc. To provide materials.

  As a result of intensive research in order to solve the above problems, the present inventors have selected a specific α-olefin polymer as a resin component used for a solar cell encapsulant, and then selected the specific α- By combining olefin polymers and wavelength conversion agents, or other polyolefin resins and functional group-containing polyolefin resins in addition to them, the wavelength conversion efficiency of sunlight is improved, productivity is high, and there is no deacetic acid. In addition, a resin composition for a solar cell encapsulant that is excellent in water vapor barrier properties, moisture absorption resistance, crosslinkability, and the like is obtained, and when the resin composition is used, sealing for solar cells such as heat resistance, transparency, and flexibility is achieved. A solar cell encapsulant that maintains various performances required for a stopper is manufactured, and by using the solar cell encapsulant, it has been found that the productivity of solar cell modules is greatly improved. Knowledge Thus, the present invention has been completed.

That is, according to the first invention of the present invention, in the solar cell module provided with the surface protective material layer, the sealing material layer, the back surface protective material layer, and optionally the base material layer,
The sealing material layer is composed of 5 to 100% by weight of an α-olefin polymer (A) and another polyolefin resin (B) and / or functional group-containing polyolefin other than the α-olefin polymer (A). A resin material (X) comprising 0 to 95% by weight of a resin based resin (C), and at least one of the surface protective material layer, the sealing material layer and the back surface protective material layer includes a wavelength conversion layer , Moreover , the solar cell module is characterized in that the α-olefin polymer (A) is an ethylene-α-olefin copolymer (A1) satisfying the following characteristics (a1) to (a5). The
(A1) Density is 0.86-0.92 g / cm ³
(A2) Melt flow rate (MFR) measured under a load of 190 ° C. and 21.18 N is 0.05 to 50 g / 10 min.
( A3 ) The melt viscosity (η ^* ₁ ) at a shear rate of 2.43 × 10 s ⁻¹ measured at 100 ° C. is 9.0 × 10 ⁴ poise or less
( A4 ) The melt viscosity (η ^* ₂ ) at a shear rate of 2.43 × 10 ² s ⁻¹ measured at 100 ° C. is 1.8 × 10 ⁴ poise or less.
(A5) The number of branches (N) due to the comonomer in the polymer and the tensile modulus (E) satisfy the following formula (a).
Formula (a): N ≧ −0.67 × E + 53
(However, N is the number of branches per 1000 carbon atoms in total of the main chain and side chain measured by NMR, and E is the tensile modulus of the sheet measured in accordance with ISO 1184-1983.) )

According to the second invention of the present invention, in the first invention, the α-olefin polymer (A) is an ethylene-α-olefin copolymer (A1) satisfying the following property (a6): The solar cell module is provided.
(A6) Flow ratio (FR): Ratio of I10, which is an MFR measurement value at 190 ° C. under a ₁₀ kg load, to I _2.16 , which is an MFR measurement value at 190 ° C. under a 2.16 kg load (I ₁₀ / I _2.16 ) is less than 7.0
According to the third invention of the present invention, in the first or second invention, the sealing material layer comprises 5 to 100% by weight of the α-olefin polymer (A) and the α-olefin polymer weight. A resin material (X) comprising 0 to 95% by weight of a polyolefin resin (B) and / or a functional group-containing polyolefin resin (C) other than the coalescence (A) and a wavelength conversion agent (D). A featured solar cell module is provided.

According to a fourth invention of the present invention, in the third invention, the wavelength conversion layer and / or the wavelength conversion agent (D) is a rare earth element, an ion thereof or an organometallic complex thereof and / or an organic fluorescent dye. There is provided a solar cell module characterized by being at least one fluorescent material.

  According to a fifth invention of the present invention, in any one of the first to fourth inventions, the α-olefin polymer (A) is produced with a single site catalyst. A solar cell module is provided.

  Furthermore, according to the sixth invention of the present invention, there is provided a resin composition for a solar cell encapsulant used in the solar cell module according to any one of the first to fifth inventions, which is an α-olefin polymer. (A) 5 to 100% by weight and other polyolefin resin (B) and / or functional group-containing polyolefin resin (C) other than the α-olefin polymer (A) and 0 to 95% by weight. A resin composition for a solar cell encapsulant is provided, which comprises 0.001 to 5 parts by weight of a wavelength conversion agent (D) in 100 parts by weight of a resin material (X).

  According to a seventh aspect of the present invention, in the sixth aspect, the wavelength converting agent (D) is a rare earth element, an ion thereof, an organometallic complex thereof, and / or an organic fluorescent dye. A resin composition for a solar cell encapsulant, which is a substance, is provided.

Furthermore, according to the eighth invention of the present invention, the α-olefin polymer (A) of the sixth or seventh invention is produced by a single site catalyst, and the solar cell is characterized in that A resin composition for a sealing material is provided.

According to a ninth invention of the present invention, in any of the sixth to eighth inventions, the resin material (X) is an ethylene-α-olefin having a density of 0.86 to 0.92 g / cm ^3. Copolymer (A1) 95-5% by weight, high pressure radical process low density polyethylene (B1), ethylene-vinyl ester copolymer (B2), ultra low with a density less than 0.86-0.91 g / cm ³ density polyethylene resin (B3), density 0.91~0.94g / cm ³ less than the linear low density polyethylene resin (B4), density 0.94~0.97g / cm ³ of high density polyethylene resin ( B5), at least one polyolefin resin (B) selected from the group consisting of ethylene-α-olefin copolymer rubber (B6), and polypropylene resin (B7) and / or functional group-containing polyolefin Emissions-based resin (C) a solar cell encapsulant resin composition characterized by consisting of 5 to 95% by weight is provided.

According to the tenth aspect of the present invention, a solar cell encapsulating comprising a single layer film or a multilayer film formed from the resin composition for a solar cell encapsulating material according to any of the sixth to ninth aspects of the invention. A solar cell encapsulant comprising a material, or a multilayer sheet obtained by laminating the single layer film or the multilayer film and at least the front surface and / or the back surface protective film with another base material and / or adhesive film interposed as desired. A stop is provided.

Furthermore, according to the 11th invention of this invention, the sealing for solar cells which consists of a single layer film or a multilayer film formed from the resin composition for solar cell sealing materials which concerns on any invention of 6th- 10th A solar cell encapsulant comprising a material, or a multilayer sheet obtained by laminating the single layer film or the multilayer film and at least the front surface and / or the back surface protective film with another base material and / or adhesive film interposed as desired. A stop is provided.

The solar cell module of the present invention is a solar cell module comprising a surface protective material layer, a sealing material layer, a back surface protective material layer, and optionally a base material layer, wherein the sealing material layer is an α-olefin polymer. (A) 5 to 100% by weight and other polyolefin resin (B) and / or functional group-containing polyolefin resin (C) other than the α-olefin polymer (A) and 0 to 95% by weight. Since it is formed from the resin material (X) and at least one of the surface protective material layer, the sealing material layer, and the back surface protective material layer includes a wavelength conversion layer, the wavelength conversion efficiency can be improved, and the molding processability is improved. Rich, highly productive, excellent in water vapor barrier properties, moisture absorption resistance, crosslinkability, etc., and has no deacetic acid compared to conventional EVA.
The resin composition used for the encapsulant layer of the solar cell module is an α-olefin polymer (A) of 100 to 5% by weight, and other polyolefin resins other than the α-olefin polymer (A). (B) and / or a functional group-containing polyolefin resin (C) A resin composition containing 0 to 95% by weight of a resin material (X) and a wavelength conversion agent (D), thereby further providing the solar cell module. As a result, the solar cell module can be converted into a wavelength, and it is difficult to remove acetic acid even when exposed to a high temperature as compared with conventional EVA, has high productivity, and is excellent in water vapor barrier properties, moisture absorption resistance, and the like.

In particular, when an α-olefin polymer having a narrow molecular weight distribution produced with a single site catalyst is used as a resin component used for a solar cell encapsulant, there is a remarkable effect. In particular, as the α-olefin polymer (A), (a1) a density is 0.86 to 0.92 g / cm ³ , (a2) a melt flow rate (MFR) measured under a load of 190 ° C. and 21.18 N. 0.05 to 50 g / 10 min, (a3) The melt viscosity (η ^* ₁ ) at a shear rate of 2.43 × 10 s ⁻¹ measured at 100 ° C. is 9.0 × 10 ⁴ poise or less, (a4) 100 ° C. When an ethylene-α-olefin copolymer satisfying a melt viscosity (η ^* ₂ ) of 1.8 × 10 ⁴ poise or less at a shear rate of 2.43 × 10 ² s ⁻¹ measured in ¹ is used at low speed molding The effect on the surface of the product at the time of high-speed molding is small, and similar products can be obtained in each molding speed region, and a remarkable effect is exhibited in providing a product with good workability and surface appearance.
Further, by using a composition layer of an α-olefin polymer and a functional group-containing polyolefin resin (C), it is possible to improve the adhesion to a surface protective material such as glass.
Furthermore, the resin composition for solar cell encapsulant is at least one selected from the group consisting of a crosslinking agent, a crosslinking aid, a silane coupling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, and a processing aid. By adding additives, a solar cell encapsulant that retains various performances required for solar cell encapsulants such as heat resistance, transparency, flexibility, and adhesiveness is produced, producing solar cell modules. It is possible to greatly improve the performance.

The solar cell module of the present invention is a solar cell module comprising a surface protective material layer, a sealing material layer, a back surface protective material layer, and optionally a base material layer, wherein the sealing material layer is an α-olefin polymer. (A) 5 to 100% by weight and other polyolefin resin (B) and / or functional group-containing polyolefin resin (C) other than the α-olefin polymer (A) and 0 to 95% by weight. It is formed from the resin material (X), and at least one of the surface protective material layer, the sealing material layer, and the back surface protective material layer includes a wavelength conversion layer.
In the solar cell module of the present invention, it is most effective to provide a sealing material layer formed from a resin composition for a solar cell sealing material containing a wavelength converting agent (D) as the wavelength conversion layer. The α-olefin polymer (A) is 5 to 100% by weight, and other polyolefin resin (B) and / or functional group-containing polyolefin resin (C) other than the α-olefin polymer (A). ) 0.001 to 5 parts by weight of the wavelength converting agent (D) is added to 100 parts by weight of the resin material (X) consisting of 0 to 95% by weight.
Hereinafter, the present invention will be described in detail for each item.

I. 1. Resin composition for solar cell encapsulant α-olefin polymer (A)
The α-olefin polymer (A) according to the present invention (hereinafter sometimes simply referred to as “component (A)”) is (1) an unmodified α-olefin polymer (A _α ). (2) Functional group-modified α-olefin polymer (A _β ), (3) Unmodified α-olefin polymer (A _α ) and functional group-modified α-olefin polymer (A _β ) A mixture is included.

(1) Unmodified α-olefin polymer (A _α )
The unmodified α-olefin polymer (A _α ) according to the present invention is a copolymer with another α-olefin having ethylene as a main component, and another α-olefin having propylene as a main component. Examples of the copolymer include a copolymer in which one or more of other α-olefins are used as accessory components, and a small amount of a diene monomer is optionally copolymerized. An α-olefin polymer having a crystallinity of 40% or less by wire, particularly an ethylene-α-olefin copolymer having a density of 0.86 to 0.92 g / cm ³ is preferable.

The ethylene / α-olefin copolymer used in the present invention has an α-olefin content of 5 to 40% by weight, preferably 10 to 35% by weight, and more preferably 15 to 30% by weight. A diene monomer may be included as necessary, and these α-olefins may be used alone or in combination of two or more. If it is said range, a softness | flexibility and heat resistance are favorable.
Here, the content of α-olefin is a value measured by ¹³ C-NMR method under the following conditions.
Device: JEOL-GSX270 manufactured by JEOL
Concentration: 300 mg / 2 mL
Solvent: Orthodichlorobenzene

Examples of such ethylene copolymers include ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / 4-methyl-1-pentene copolymers, ethylene / 1-hexene copolymers, ethylene Binary copolymers such as 1-octene copolymer, ethylene / propylene / 1-hexene copolymer, ethylene / propylene / 1-octene copolymer, ethylene / 1-butene / 1-hexene copolymer, ethylene -1-butene / 1-octene copolymer terpolymer, etc. are mentioned.
Examples of the copolymer obtained by copolymerizing a small amount of diene monomer include ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / 1,6- A hexadiene copolymer etc. can be illustrated.

  Among these, ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / 1-hexene copolymers, binary copolymers such as ethylene / 1-octene copolymers, ethylene / propylene, etc. A terpolymer such as a 1-hexene copolymer, an ethylene / propylene / 1-octene copolymer, and an ethylene / propylene / diene copolymer is preferable.

Among the _α -olefin polymers (A _α ) according to the present invention, an ethylene / α-olefin copolymer (A1) is preferable, and ethylene / α satisfying the following characteristics (a1) to (a4) is particularly preferable. -An olefin copolymer (A1) is preferable.
(A1) Density is 0.86-0.92 g / cm ³
(A2) Melt flow rate (MFR) measured under a load of 190 ° C. and 21.18 N is 0.05 to 50 g / 10 min. (A3) Melt viscosity at a shear rate of 2.43 × 10 s ⁻¹ measured at 100 ° C. (Η ^* ₁ ) is 9.0 × 10 ⁴ poise [Poise (P)] or less (a4) The melt viscosity (η ^* ₂ ) at a shear rate of 2.43 × 10 ² s ⁻¹ measured at 100 ° C. is 1 .8 × 10 ⁴ poise [Poise (P)] or less

The (a1) density of the ethylene / α-olefin copolymer (A1) according to the present invention is 0.86 to 0.92 g / cm ³ , preferably 0.87 to 0.91 g / cm ³ , more preferably 0. The range is from .88 to 0.908 g / cm ³ . When the density is within this range, it is possible to easily provide a solar cell sealing material having transparency, flexibility, heat resistance, and the like.
On the other hand, if the density is less than 0.86 g / cm ³ , the sheet is too soft, the handling workability is lowered, and the heat resistance is inferior. On the other hand, if the density exceeds 0.92 g / cm ³ , the flexibility of the sheet may be impaired, and the transparency may be deteriorated.

  The (a2) melt flow rate (MFR) of the ethylene / α-olefin copolymer (A1) according to the present invention has an MFR measured under a load of 190 ° C. and 21.18 N of 0.05 to 50 g / 10 min. It is preferable to use a 0.1-45 g / 10 minute thing. When the MFR is less than 0.05 g / 10 min, there is a concern that the moldability at high speed is deteriorated and the productivity is lowered. On the other hand, when the MFR exceeds 50 g / 10 min, there is a concern that the mechanical strength is lowered and the sheet cannot be thinned.

Regarding the (a3) melt viscosity (η ^* ₁ ) and (a4) melt viscosity (η ^* ₂ ) of the ethylene / α-olefin copolymer (A1) according to the present invention, the ethylene / α-olefin copolymer used in the present invention is used. The coalescence should have a specific range of melt viscosity at a specific shear rate measured at 100 ° C. The reason for focusing on the melt viscosity at a specific shear rate measured at 100 ° C. is to estimate the influence on the product when the composition at that temperature is commercialized.
That is, (a3) The melt viscosity (η ^* ₁ ) at a shear rate of 2.43 × 10 s ⁻¹ measured at 100 ° C. is 9.0 × 10 ⁴ poise or less, preferably 8.0 × 10 ⁴ poise or less, Preferably it is 7.0 × 10 ⁴ poise or less, more preferably 5.5 × 10 ⁴ poise or less, still more preferably 5.0 × 10 ⁴ poise or less, particularly preferably 3.0 × 10 ⁴ poise or less, most preferably Is 2.5 × 10 ⁴ poise or less. On the other hand, the lower limit of the melt viscosity (η ^* ₁ ) is preferably 1.0 × 10 ⁴ poise or more, and more preferably 1.5 × 10 ⁴ poise or more.

If the melt viscosity (η ^* ₁ ) is within this range, productivity at low speed and low speed molding is good, and there is no problem in processing into products. Further, when the melt viscosity (η ^* ₁ ) exceeds the upper limit, the productivity during low-speed molding at low temperatures is inferior. On the other hand, when the melt viscosity (η ^* ₁ ) exceeds the lower limit, processing into a product becomes difficult.
The melt viscosity (η ^* ₁ ) can be adjusted by the melt flow rate (MFR) or molecular weight distribution of the ethylene / α-olefin copolymer. When the value of the melt flow rate (MFR) is increased, the melt viscosity (η ^* ₁ ) tends to decrease. If other properties such as molecular weight distribution are different, the magnitude relationship may be reversed. By setting the time to 10 minutes, more preferably from 10 to 40 g / 10 minutes, and even more preferably from 15 to 35 g / 10 minutes, the melt viscosity (η ^* ₁ ) can be easily kept within a predetermined range.

Further, the ethylene / α-olefin copolymer (A1) used in the present invention has (a4) a melt viscosity (η ^* ₂ ) at a shear rate of 2.43 × 10 ² s ⁻¹ measured at 100 ° C. of 1. 8 × 10 ⁴ poise or less, preferably 1.7 × 10 ⁴ poise or less, more preferably 1.5 × 10 ⁴ poise or less, further preferably 1.4 × 10 ⁴ poise or less, most preferably 1.3 × 10 ⁴ poise or less. On the other hand, the lower limit of (a4) melt viscosity (η ^* ₂ ) is preferably 5.0 × 10 ³ poise or more, more preferably 8.0 × 10 ³ poise or more. When the melt viscosity (η ^* ₂ ) is within this range, the productivity at high speed molding at a low temperature is good, and there is no problem in processing the product. Further, (a4) If the melt viscosity (η ^* ₂ ) exceeds the upper limit, it becomes difficult to increase the productivity at high speed molding at low temperature, while if it exceeds the lower limit, it becomes difficult to process the product. .
Here, (a3) melt viscosity (η ^* ₁ ) and (a4) melt viscosity (η ^* ₂ ) are measured values obtained using a capillary rheometer having a capillary with a diameter of 1.0 mm and L / D = 10. It is.
The two types of shear rates are provided in order to obtain a similar product in each molding speed region with little influence on the surface of the product during low speed molding and high speed molding.

Further, the ethylene / α-olefin copolymer (A1) used in the present invention has a ratio (η ^* ₁ / η ^* ₂ ) of melt viscosity (η ^* ₁ ) and melt viscosity (η ^* ₂ ) having different shear rates. However, it is preferably 4.5 or less, more preferably 4.2 or less, still more preferably 4.0 or less, and most preferably 3.0 or less. The lower limit of the ratio of η ^* ₁ to η ^* ₂ (η ^* ₁ / η ^* ₂ ) is preferably 1.1 or more, and more preferably 1.5 or more. If the ratio (η ^* ₁ / η ^* ₂ ) is within the above range, it is preferable because there is little influence on the sheet surface during low speed molding and high speed molding.

In the ethylene / α-olefin copolymer (A1), the number of branches (N) by the comonomer in the polymer (a5) and the tensile modulus (E) preferably satisfy the following formula (a): .
Formula (a): N ≧ −0.67 × E + 53
(However, N is the number of branches per 1000 carbon atoms in total of the main chain and side chain measured by NMR, and E is the tensile modulus of the sheet measured according to ISO 1184-1983.) )
Here, the number of branches (N) due to the comonomer in the polymer is, for example, E.I. W. Hansen, R .; Blom, and O.M. M.M. It can be calculated from a ¹³ C-NMR spectrum with reference to Bade, Polymer, 36, 4295 (1997).

In the solar cell module, the solar cell encapsulant tends to become thinner as the solar cell element becomes thinner. In the solar cell encapsulating material having a reduced thickness, when an impact is applied from the cover film side, the wiring is easily disconnected, and thus it is required to increase the rigidity of the encapsulating material. A copolymer having a low degree of branching of the polymer chain is useful as a highly rigid sealing material because the rigidity of the copolymer after crosslinking is increased. However, if the rigidity is increased, the crosslinking efficiency becomes worse. Therefore, a copolymer having a high degree of branching of the polymer chain is used to improve the fluidity of the copolymer before crosslinking, and as a material excellent in moldability. Need to use.
In the present invention, since the number of branches (N) by the comonomer of the ethylene / α-olefin copolymer has a polymer structure satisfying the formula (a), the balance between rigidity and crosslinking efficiency is good.

Furthermore, in the present invention, the relational expression of the characteristic (a5) is preferably represented by the following expression (a ′). The relational expression of the characteristic (a5) is more preferably the following expression (a ″).
Formula (a ′): −0.67 × E + 80 ≧ N ≧ −0.67 × E + 53
Formula (a ″): −0.67 × E + 75 ≧ N ≧ −0.67 × E + 54

The ethylene / α-olefin copolymer according to the present invention can be produced by a copolymerization reaction using a catalyst as described above, but the composition ratio of raw material monomers to be copolymerized and the type of catalyst to be used are selected. Thus, the degree of branching in the polymer chain can be easily adjusted.
In order for the ethylene / α-olefin copolymer used in the present invention to satisfy the formula (a), the comonomer in the ethylene / α-olefin copolymer is selected from propylene, 1-butene, or 1-hexene. Is preferred. Moreover, it is preferable to produce using a vapor phase method or a high pressure method, and it is more preferable to select a high pressure method.
More specifically, in order to fix the tensile modulus E of the sheet and increase / decrease N in the number of branches, it is possible to mainly change the number of carbons of the comonomer copolymerized with ethylene. Ethylene / α-olefin copolymer is mixed with ethylene so that the amount of 1-butene or 1-hexene is 60 to 80 wt%, and is reacted at a polymerization temperature of 130 to 200 ° C. using a metallocene catalyst. It is preferable to produce a coalescence.
Thereby, the number of branches N of the ethylene / α-olefin copolymer can be adjusted appropriately, and the resulting sheet has a tensile elastic modulus E of 40 MPa or less, and the ethylene / α-olefin within the range represented by the formula (a). A copolymer can be obtained.

The ethylene / α-olefin copolymer (A1) used in the present invention further has (a6) a flow ratio (FR), that is, I ₁₀ which is an MFR measurement value at 190 ° C. under a 10 kg load, and 2. It is preferable that a ratio (I ₁₀ / I _2.16 ) with I _2.16 which is an MFR measurement value at a load of 16 kg is less than 7.0. The melt flow rate (MFR) is a value measured according to JIS K7210-1999.

It is known that FR has a strong correlation with the molecular weight distribution of ethylene / α-olefin copolymer and the amount of long chain branching.
In the present invention, among polymers satisfying the above conditions (a1) to (a4), the MFR measurement value (I ₁₀ ) at 190 ° C. under a 10 kg load and the MFR measurement value (I ₁₀ ) at 190 ° C. under a 2.16 kg load (I _2.16 ) and a ratio (I ₁₀ / I _2.16 ) of less than 7.0 are used. By using a copolymer having a polymer structure characterized by such long-chain branching, the balance between rigidity and crosslinking efficiency is good. On the other hand, when FR is 7.0 or more, the crosslinking efficiency at the time of crosslinking tends to deteriorate as a solar cell encapsulant.
The FR of the ethylene / α-olefin copolymer used in the present invention is less than 7.0, preferably less than 6.5, and more preferably less than 6.3. However, if the FR is less than 5.0, it may be difficult to obtain sufficient rigidity as a solar cell encapsulant. The flow ratio (FR) of the characteristic (a6) is most preferably 5.0 to 6.2.

The ethylene-α-olefin copolymer according to the present invention further comprises (a7) the ratio (Mz / Mn) of the Z average molecular weight (Mz) and the number average molecular weight (Mn) determined by gel permeation chromatography (GPC). ) Is preferably 8.0 or less, more preferably 5.0 or less, and even more preferably 4.0 or less.
Further, Mz / Mn is preferably 2.0 or more, more preferably 2.5 or more, and further preferably 3.0 or more. However, when Mz / Mn exceeds 8.0, transparency deteriorates. In order to adjust (Mz / Mn) to a predetermined range, a method of selecting an appropriate catalyst system can be used.

In addition, the measurement of Mz / Mn is performed by gel permeation chromatography (GPC), and the measurement conditions are as follows.
Apparatus: GPC 150C type manufactured by Waters Inc. Detector: 1A infrared spectrophotometer manufactured by MIRAN (measurement wavelength: 3.42 μm)
Column: Showa Denko 3 AD806M / S (column calibration is Tosoh monodispersed polystyrene (0.5 mg / ml solution of each of A500, A2500, F1, F2, F4, F10, F20, F40, and F288) The logarithm of the elution volume and the molecular weight was approximated by a quadratic equation, and the molecular weight of the sample was converted to polyethylene using the viscosity equation of polystyrene and polyethylene, where the coefficient of the viscosity equation of polystyrene is α = 0.723, log K = −3.767, and polyethylene has α = 0.733 and log K = −3.407.)
Measurement temperature: 140 ° C
Concentration: 20 mg / 10 mL
Injection volume: 0.2ml
Solvent: Orthodichlorobenzene Flow rate: 1.0 ml / min

  Since the Z average molecular weight (Mz) greatly contributes to the average molecular weight of the high molecular weight component, Mz / Mn is easier to confirm the presence of the high molecular weight component than Mw / Mn. The high molecular weight component is a factor that affects the transparency. When the high molecular weight component is large, the transparency is deteriorated. Moreover, the tendency for a crosslinking efficiency to deteriorate is seen. Therefore, the smaller Mz / Mn is preferable.

  The propylene-based polymer such as a copolymer with other α-olefins mainly composed of propylene may be a propylene homopolymer, but preferably has a propylene polymer unit of 70 to 95 mol%, preferably 72. Examples thereof include those containing ˜90 mol% and α-olefin polymerization units other than propylene of 5 to 30 mol%, preferably 10 to 28 mol%. Examples of such propylene copolymers include propylene / ethylene copolymers and propylene / 1-butene copolymers.

In addition, a propylene polymer having a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg is 0.05 to 50 g / 10 minutes, particularly 0.1 to 20 g / 10 minutes. Is preferred.
When the MFR is less than 0.05 g / 10 min, there is a concern that the moldability at high speed is deteriorated and the productivity is lowered. Further, when the MFR exceeds 50 g / 10 min, there is a concern that the mechanical strength is lowered and the sheet cannot be thinned.

  Among the α-olefin polymers, in the case of a copolymer with an α-olefin mainly composed of ethylene, a Ziegler catalyst, a vanadium catalyst or a metallocene catalyst, preferably a vanadium catalyst or a metallocene catalyst, more preferably a metallocene. It can be produced using a catalyst. Examples of the production method include a high-pressure ion polymerization method, a gas phase method, a solution method, and a slurry method. In particular, an ethylene-α-olefin copolymer produced by a high-pressure ion polymerization method using a metallocene catalyst is preferred.

The metallocene catalyst which is a single site catalyst is not particularly limited, but preferably a catalyst comprising a metallocene compound such as a zirconium compound coordinated with a group having a cyclopentadienyl skeleton and the like and a promoter as catalyst components. Is mentioned.
Commercially available products of ethylene-based α-olefin copolymers include Harmolex (registered trademark) series, Kernel (registered trademark) series manufactured by Nippon Polyethylene, and Evolue (registered trademark) manufactured by Prime Polymer. Series, Exelen (registered trademark) GMH series manufactured by Sumitomo Chemical Co., Ltd., Excellen (registered trademark) FX series, and the like.
Examples of the vanadium catalyst include a catalyst having a soluble vanadium compound and an organic aluminum halide as catalyst components.

  In the case of a copolymer mainly composed of propylene, a steric rule containing a transition metal compound component such as a highly active titanium catalyst component or a metallocene catalyst component, an organoaluminum component, and an electron donor, a carrier, etc. as necessary Can be produced by copolymerizing propylene and other α-olefins in the presence of a hydrophilic olefin polymerization catalyst.

(2) Functional group-modified α-olefin polymer ( _Aβ )
The functional group-modified α-olefin polymer (A _β ) according to the present invention is obtained by grafting the α-olefin polymer (A _α ) with functional group-containing compounds (a) to (f) described later. The functional group-modified α-olefin polymer ( _Aβ ).

Specific examples of the functional group-modified α-olefin polymer ( _Aβ ) include maleic anhydride-modified ethylene / α-olefin copolymer, (meth) acrylic acid-modified ethylene-α-olefin copolymer, (meth). Examples thereof include a glycidyl acrylate modified ethylene copolymer and a silane modified ethylene-α-olefin copolymer.
The functional group-modified α-olefin polymer (A _β ) is obtained by converting the α-olefin polymer (A _α ) to a radical initiator as described in detail in the functional group-containing polyolefin resin (C) described later. It can be produced by modifying with the functional group-containing compound capable of undergoing a grafting reaction in the presence. The prescription such as the modification method is performed in the same manner as the functional group-containing polyolefin resin (C) described later.

(3) Mixture of unmodified α-olefin polymer (A _α ) and functional group-modified α-olefin polymer (A _β ) The unmodified α-olefin polymer (A _α ) and functional group The blending ratio with the modified α-olefin polymer (A _β ) is arbitrary, but when considering the adhesiveness to the surface material with glass as a solar cell encapsulant and the economic efficiency, the weight Ratio of unmodified polymer (A _α ) / modified polymer (A _β ) = 50 to 95/50 to 5, preferably unmodified polymer (A _α ) / modified polymer (A _β ) = 60 to 90 It is selected in the range of / 40-10.

2. Other polyolefin resin (B)
The other polyolefin-based resin (B) in the present invention (hereinafter sometimes simply referred to as “component (B)”) is a low-density polyethylene (B1) obtained by high-pressure radical polymerization and an ethylene-vinyl ester copolymer. Super low density polyethylene (B3) having a density of less than 0.86 to 0.91 g / cm ³ by ion polymerization such as a coalescence (B2), Ziegler catalyst, vanadium catalyst, Phillips catalyst, metallocene catalyst, 0.91 to 0.94 g / cm ³ less than the linear low density polyethylene (B4), high density polyethylene 0.94~0.97g / cm ³ (B5), ethylene -α- olefin copolymer rubber (B6), and propylene alone It includes at least one resin selected from the group consisting of a polymer or propylene and another α-olefin copolymer (B7).

(1) Low density polyethylene (LDPE) (B1)
The low density polyethylene (LDPE) (B1) produced by the high pressure radical polymerization method has a melt flow rate (MFR) measured at 190 ° C. under a load of 21.18 N of 0.05 to 100 g / 10 minutes, preferably 0.1 to 0.1%. 70 g / 10 min, more preferably 0.5 to 50 g / 10 min. Within this range, the melt tension of the composition is in an appropriate range, and sheet molding is easy.
The density is 0.905 to 0.940 g / cm ³ , preferably 0.910 to 0.938 g / cm ³ , and more preferably 0.912 to 0.935 g / cm ³ .
The melt tension is 1.5 to 25 g, preferably 3 to 20 g, more preferably 3 to 15 g.
Moreover, Mw / Mn is 3.0-15, Preferably it is 4.0-10. Melt tension, Mw / Mn is an elastic item of the resin, and sheet molding is easy within the above range. In addition, Mw / Mn here is weight average molecular weight (Mw) / number average molecular weight (Mn) by GPC analysis.

(2) Ethylene-vinyl ester copolymer (B2)
The ethylene-vinyl ester copolymer (B2) according to the present invention is a vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate based on ethylene produced by a high-pressure radical polymerization method, It is a copolymer with vinyl ester monomers such as vinyl stearate and vinyl trifluoroacetate. Among these, vinyl acetate is particularly preferable. That is, a copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of vinyl ester, and 0 to 49.5% by weight of other copolymerizable unsaturated monomers is preferable. The vinyl ester content is in the range of 3 to 30% by weight, preferably 5 to 20% by weight. The MFR of these copolymers is 0.01 to 50 g / 10 minutes, preferably 0.1 to 40 g / 10 minutes, and the melt tension is 2.0 to 25 g, preferably 3 to 20 g.

(3) Linear polyethylene by ion polymerization (B3) (B4) (B5)
The linear polyethylene by ionic polymerization according to the present invention is an ethylene homopolymer or ethylene-α-olefin copolymer having a density of 0.86 to 0.97 g / cm ³ (B3) 0.86 to 0.8. 91g / cm ³ less than the very low density polyethylene ^{(VLDPE), (B4) 0.91g} / cm 3 ~0.94g / cm 3 less than the linear low density polyethylene (LLDPE), (B5) 0.94g / cm ³ or more linear medium / high density polyethylene (MDPE / HDPE) and the like can be mentioned.

(B3) linear low density polyethylene (VLDPE), (B4) linear low density polyethylene (LLDPE), (B5) linear medium / high density polyethylene (MDPE / HDPE) Has a density of 0.86 to 0.97 g / cm ³ , a melt flow rate (MFR) measured under a load of 190 ° C. and 21.18 N of 0.05 to 50 g / 10 minutes, preferably 0.1 to 45 g / It is selected in the range of 10 minutes, more preferably 0.5 to 40 g / 10 minutes.
Among these, very low density polyethylene (VLDPE) and low density polyethylene (LLDPE) are particularly preferable in terms of flexibility, transparency, and the like.
The molecular weight distribution (Mw / Mn) of very low density polyethylene (VLDPE) and low density polyethylene (LLDPE) is 2.0 to 6.0, preferably 2.5 to 5.0, more preferably 2.8 to 4. .0 range. Within this range, it is possible to provide a sheet having a good balance between flexibility and transparency.

  The α-olefin of the ethylene-α-olefin copolymer according to the present invention has 3 to 12 carbon atoms, preferably 3 to 10 carbon atoms, specifically, propylene, butene-1, 4-methylpentene-1. Hexene-1, octene-1, decene-1, dodecene-1, and the like. The content of these α-olefins is preferably selected in the range of 3 to 40 mol%.

(4) Ethylene-α-olefin copolymer rubber (B6)
Examples of the ethylene-α-olefin copolymer rubber (B6) according to the present invention include ethylene-propylene copolymer rubber (EPR), ethylene-propylene-diene copolymer rubber (EPDM), and ethylene-1-butene copolymer. Examples include coalesced rubber.

(5) Propylene homopolymer or propylene and other α-olefin copolymer (B7)
The propylene-based polymer (B7) according to the present invention is a propylene homopolymer or propylene and another α-olefin copolymer, an isotactic propylene homopolymer, a syndiotactic propylene polymer, propylene, and Examples thereof include random polymers and block polymers with α-olefins such as ethylene and butene-1. Among these, a random polymer is preferable from the viewpoint of flexibility and transparency.

3. Functional group-containing polyolefin resin (C)
The functional group-containing polyolefin resin (C) according to the present invention (hereinafter sometimes simply referred to as “component (C)”) refers to the following functional group-containing compounds (a) to (f), an olefin, Copolymer (C1) or a functional group-modified polyolefin resin (C2) obtained by modified grafting of functional group-containing compounds (a) to (f) in the presence of a radical generator to a polyolefin resin It is.
The functional group-containing polyolefin resin (C) may be a single type or a combination of two or more types.

(1) Functional group-containing compound The functional group-containing compound of the functional group-containing polyolefin resin (C) according to the present invention includes an epoxy group-containing compound (a), an unsaturated carboxylic acid group-containing compound or a derivative thereof (b), and an ester. It is at least one compound selected from the group consisting of a group-containing compound (c), a hydroxyl group-containing compound (d), an amino group-containing compound (e), and a silane group-containing compound (f), and an epoxy group-containing compound ( a), or an unsaturated carboxylic acid group-containing compound or a derivative thereof (b) is preferred.

(A) Epoxy group-containing compound Examples of the epoxy group-containing compound include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, adipic acid diglycidyl ester, methacrylic acid glycidyl ester, and trimethylolpropane triglycidyl ether. , Polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, butanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, phenol novolac polyglycidyl ether, epoxidized vegetable oil, and the like.

  Among these epoxy group-containing compounds, polyvalent epoxy compounds having a molecular weight of 3000 or less and containing at least two epoxy groups (oxirane groups) in the molecule are preferable. Since this epoxy compound contains two or more epoxy groups in the molecule, the adhesive strength is remarkably improved as compared with the case where there is one epoxy group in the molecule. The molecular weight of the epoxy compound is preferably 3000 or less, and particularly preferably 1500 or less. When the molecular weight exceeds 3000, there is a possibility that sufficient adhesive strength cannot be obtained when the composition is formed.

As the epoxy group-containing compound, an epoxidized vegetable oil can be selected from the viewpoint of ease of handling and safety. Epoxidized vegetable oil is an epoxidized unsaturated double bond of natural vegetable oil with peracid, for example, epoxidized soybean oil, epoxidized linseed oil, epoxidized olive oil, epoxidized safflower oil, epoxidized Examples include corn oil.
These epoxidized vegetable oils are commercially available as, for example, O-130P (epoxidized soybean oil), O-180A (epoxidized linseed oil), manufactured by Asahi Denka Kogyo Co., Ltd.
It should be noted that an oil component that is not epoxidized or is insufficiently epoxidized as a by-product when epoxidizing vegetable oil does not hinder the effects of the present invention even if it is present.

  In this invention, content of an epoxy-group containing compound is 0.01-5 weight% in a functional group containing polyolefin-type resin (C), 0.01-3 weight% is preferable, 0.01-1 Weight percent is more preferred. If the content of the epoxy group-containing compound is within this range, the adhesive strength with the solar cell element or the protective material will not be sufficient, and the laminated solar cell module will not cause blocking due to stickiness or smell. No problem occurs.

(B) Unsaturated carboxylic acid group-containing compound or derivative thereof The unsaturated carboxylic acid or derivative thereof used in the present invention is at least one compound selected from a carboxylic acid group or an acid anhydride group-containing compound. preferable.
Examples include monobasic unsaturated carboxylic acids, dibasic unsaturated carboxylic acids, and their metal salts, amides, imides, esters and anhydrides. The number of carbon atoms of the monobasic unsaturated carboxylic acid is 20 or less, preferably 15 or less, and the number of carbon atoms of the dibasic unsaturated carboxylic acid is 30 or less, preferably 25 or less. 30 or less, preferably 25 or less. Among these unsaturated carboxylic acid group-containing compounds and derivatives thereof, acrylic acid, methacrylic acid, maleic acid and its anhydride, 5-norbornene-2,3-dicarboxylic acid and its anhydride, and glycidyl methacrylate are particularly preferable. Maleic anhydride and 5-norbornene anhydride are preferred because of excellent adhesion performance of the resin composition.

  Preferred copolymers include ethylene / (meth) acrylic acid glycidyl copolymer, ethylene / (meth) acrylic acid copolymer, ethylene / maleic anhydride copolymer, ethylene / maleic anhydride / vinyl acetate copolymer. Examples thereof include a binary or ternary copolymer such as a polymer, an ethylene / maleic anhydride / methyl acrylate copolymer, and an ethylene / maleic anhydride / ethyl acrylate copolymer.

  The content of the unsaturated carboxylic acid group-containing compound or derivative thereof is preferably 0.05 to 5.0% by weight, more preferably 0.1 to 3% by weight in the functional group-containing polyolefin resin (C). Especially preferably, it is 0.2 to 2 weight%. If it is the range of this content, sufficient adhesive performance can be provided, without an unreacted monomer increasing.

(C) Ester group-containing compound Examples of the ester group-containing compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and the like. And ethyl acrylate.

Specific examples of the above products include ethylene-methyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., ACLIFT (registered trademark) CM502), ethylene-ethyl acrylate copolymer (manufactured by Nihon Unicar, NUC (registered trademark)) 6570) is commercially available.
The content of the ester group-containing compound is preferably 5.0 to 40.0% by weight, more preferably 10 to 30.0% by weight, and particularly preferably 15.0% in the functional group-containing polyolefin resin (C). ˜25.0% by weight. If it is content of this range, the softness | flexibility and adhesiveness of a functional group containing polyolefin resin (C) will express.

The above ester group-containing compound and ethylene copolymer include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-octene, as other unsaturated monomers in addition to ethylene. olefins having 3 to 10 carbon atoms, such as _decene, C 2 -C ₃ vinyl esters of alkanecarboxylic acids, (meth) acrylate, (meth) acrylate, (meth) acrylate, propyl glycidyl (meth) At least one selected from the group of (meth) acrylic acid esters such as acrylate, ethylenically unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid and maleic anhydride, or anhydrides thereof. It is possible to use.

The ethylene copolymer is preferably a copolymer comprising 65 to 99.5% by weight of ethylene, 0.5 to 35% by weight of an unsaturated carboxylic acid or ester thereof, and 0 to 25% by weight of other unsaturated monomers. .
The MFR of these ethylene copolymers is selected in the range of 0.05 to 50 g / 10 minutes, preferably 0.1 to 45 g / 10 minutes.

(D) Hydroxyl group-containing compound Examples of the hydroxyl group-containing compound include hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
The content of the hydroxyl group-containing compound is preferably 0.05 to 5.0% by weight, more preferably 0.1 to 3% by weight, and particularly preferably 0.2% in the functional group-containing polyolefin resin (C). ~ 2% by weight. If it is content of this range, sufficient adhesive performance can be provided, without an unreacted monomer increasing.

(E) Amino group-containing compound Examples of the amino group-containing compound include aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meth) acrylate, and the like.
The content of the amino group-containing compound is preferably 0.05 to 5.0% by weight, more preferably 0.1 to 3% by weight, and particularly preferably 0.2% in the functional group-containing polyolefin resin (C). ~ 2% by weight. If it is content of this range, sufficient adhesive performance can be provided, without an unreacted monomer increasing.

(F) Silane group-containing compound Examples of the silane group-containing compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane, vinyltrichlorosilane, vinyltriisopropoxysilane, vinyltrismethylethylketoximesilane, and vinyltriisopropenoxy. Vinyl silanes such as silane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, acryloxymethylmethyldimethoxysilane, acryloxymethyldimethylmethoxysilane, γ-acryloxypropyltri Methoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldi Acrylic silanes such as toxisilane, γ-acryloxypropyldimethylmethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethylmethyldimethoxysilane, methacryloxymethyldimethylmethoxysilane, γ-methacryloxypropyltri Methoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, methacrylsilanes such as γ-methacryloxypropyldimethylmethoxysilane, styryltrimethoxysilane, Styryltriethoxysilane, styrylmethyldimethoxysilane, N-vinylbenzyl-γ-aminopropyltrimethoxysilane, N-vinyl And unsaturated silane compounds such as styrylsilanes such as benzyl-γ-aminopropylmethyldimethoxysilane.
In addition, these unsaturated silane compounds can be used individually or in mixture of 2 or more types.
In the present invention, the content of the silane group-containing compound is 0.01 to 5% by weight in the functional group-containing polyolefin resin (C). Preferably, it is 0.01 to 3 weight%, More preferably, it is 0.01 to 1 weight%. When the content is in this range, sufficient adhesion with a protective material such as glass can be obtained, and a decrease in the volume resistivity can be suppressed.

(2) Production of Functional Group-Containing Polyolefin Resin (C) The functional group-containing polyolefin resin (C) is a copolymer of a functional group-containing compound and an olefin, or the polyolefin resin (B) is used as a radical initiator. It can be produced by carrying out a grafting reaction with the functional group-containing compound capable of undergoing a grafting reaction in the presence.
In addition, the above functional group-modified α-olefin polymer ( _Aβ ) can also be modified and produced by the same method.

The functional group-containing polyolefin polymer (C1) is a copolymer of the functional group-containing compound and olefin which can be copolymerized.
Preferred copolymers include ethylene / (meth) acrylic acid glycidyl group-containing compound copolymers, ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, ethylene / maleic anhydride copolymers, ethylene / anhydrous copolymers. Examples thereof include binary or ternary copolymers such as a maleic acid / vinyl acetate copolymer, an ethylene / maleic anhydride / methyl acrylate copolymer, and an ethylene / maleic anhydride / ethyl acrylate copolymer. The amount of copolymerization varies depending on the type of functional group-containing compound, but the functional group-containing compound unit is contained in 0.5 to 30% by weight in 100% by weight of the copolymer.

The functional group-modified polyolefin polymer (C2) is a functional group-modified polyolefin resin (C2) obtained by grafting a polyolefin resin with a functional group-containing compound, and specific examples thereof include maleic anhydride-modified ethylene α-olefin copolymer, (meth) acrylic acid modified ethylene-α-olefin copolymer, (meth) acrylic acid glycidyl modified ethylene-α-olefin copolymer, silane group modified ethylene-α-olefin copolymer, etc. Can be mentioned.
As described in detail below, the functional group-modified polyolefin polymer (C2) is produced by modifying a polyolefin polymer with the functional group-containing compound capable of undergoing a grafting reaction in the presence of a radical initiator. It is.

(I) Radical initiator As the radical initiator used in the grafting reaction in the present invention, dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t-butylperoxy) hexane, lauroyl Peroxide, t-butylperoxybenzoate, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, t-butylcumyl peroxide, α, α'-bis (t-butylperoxy -M-isopropyl) benzene, di-t-butyldiperoxyisophthalate, n-butyl-4, - bis (t-butylperoxy) valerate, t- butyl peroxybenzoate, t- butyl peroxy acetate, cyclohexanone peroxide, t- butyl peroxy laurate, include organic peroxides such as acetyl peroxide.
Among these, a decomposition temperature for obtaining a half-life of 1 minute is preferably 160 to 200 ° C. If the decomposition temperature is too low, since the decomposition reaction starts before the raw α-olefin polymer is sufficiently plasticized in the extruder, the reaction rate becomes low. Conversely, if the decomposition temperature is too high, the inside of the extruder, etc. Thus, the reaction is not completed, and the amount of the unreacted functional group-containing compound increases.

  The blending amount of the radical initiator is preferably 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.3 parts by weight with respect to 100 parts by weight of the resin component. If the radical initiator is less than 0.005 parts by weight, the grafting reaction is not sufficiently performed, and unreacted monomers increase, which is not preferable. On the other hand, when the amount is more than 0.5 parts by weight, gels and fish eyes frequently occur, which is not preferable.

(Ii) Modification Method Hereinafter, the modification of the polyolefin resin of the component (C) will be described in detail, but the modification of the component ( _Aβ ) can be performed in the same manner.
A functional group-containing compound 0.05 to 20 parts by weight and a radical initiator 0.005 to 0.5 parts by weight are added to 100 parts by weight of a polyolefin-based resin, and a single-screw extruder and / or a twin-screw extruder are used. Using a reactor or the like and melt-kneading or modifying in a solvent.
Specifically, a melt kneading method using an extruder, a Banbury mixer, a kneader, etc., a solution method dissolved in an appropriate solvent, a slurry method suspended in an appropriate solvent, or a so-called gas phase grafting method can be mentioned.
The treatment temperature is appropriately selected in consideration of the deterioration of the resin, the decomposition of the functional group-containing compound, the decomposition temperature of the radical initiator to be used, etc. It is 350 degreeC, and 200-300 degreeC is especially suitable.

In producing the functional group-modified polyolefin resin (C) according to the present invention, for the purpose of improving its performance, for example, during the grafting reaction or modification, as described in JP-A-62-1107 Later, a method of treating with an epoxy compound or a polyfunctional compound containing an amino group or a hydroxyl group, and a method of removing unreacted functional group-containing compounds and by-product components by heating, washing, etc. Can do.
The higher the graft amount, the better, but it is preferable that 0.001 to 5.0% by weight of the functional group-containing compound unit is contained in 100% by weight of the functional group-containing polyolefin resin (C).

In the reaction between the functional group-containing compound and the polyolefin resin using the above radical initiator, side reactions such as grafting reaction and micro-crosslinking and decomposition of the polyolefin resin occur simultaneously in parallel. By setting the temperature to 250 ° C. or higher, the grafting reaction occurs preferentially, and a high monomer addition rate is realized. On the other hand, when the resin temperature is less than 250 ° C., micro-crosslinking of the polyolefin resin preferentially occurs, whereby gel and resin burn increase and the quality of the resulting functional group-containing polyolefin resin is lowered. Further, when the resin temperature exceeds 310 ° C., the deterioration of the polyolefin resin is accelerated, so that gels and resin burns increase drastically, which also deteriorates the quality.
In addition, since the reaction is carried out at such a high temperature, it is necessary to suppress the mixing of air into the extruder or the reactor as much as possible. In melt-kneading, it is necessary to avoid the resin from staying in the extruder for a long time. I must. For this reason, it is extremely preferable to perform nitrogen feed in the vicinity of the raw material resin inlet.

In addition, in producing the functional group-containing polyolefin resin (C) or the functional group-containing α-olefin polymer (A _β ) according to the present invention, in order to give priority to the grafting reaction to olefin while suppressing unnecessary side reactions. It is not preferable to add additives such as antioxidants that are generally used. For example, the addition of an antioxidant for polyolefin may increase the number of unreacted functional group-containing compounds due to antagonistic action between the antioxidant and the radical initiator. Moreover, the addition of metal soaps may cause the metal soaps and unsaturated carboxylic acids or their derivatives to react, and the adhesion performance of the resulting functional group-modified polyolefin resin (C2) may be reduced.

In the production of the functional group-containing polyolefin-based resin (C2), it is preferable to modify the polyolefin resin over a plurality of orders, thereby being a relatively expensive monomer, such as an unsaturated carboxylic acid and its derivative, an epoxy group-containing compound, etc. The modification rate of the modified monomer is sufficiently increased to improve economic efficiency, and even with a relatively small amount of modified monomer, the adhesion performance is very excellent, no unreacted modified monomer remains, and no gel or resin burns occur. A high-quality functional group-modified polyolefin resin can be produced.
The grafting reaction rate (functional group content) obtained by such a modification method by melt kneading is generally in the range of about 0.2 to 2.5% by weight. The grafting reaction rate of the final functional group-containing polyolefin resin (C2) is generally in the range of 0.55 to 2.5% by weight. However, it is not particularly limited to this range, and a higher modification rate is desirable.

4). Blending ratio of α-olefin polymer (A) and polyolefin resin (B) and / or functional group-containing polyolefin polymer (C) In the present invention, component (A), component (B) and / or component The blending ratio with (C) is preferably 0 to 95% by weight of component (B) and / or component (C) with respect to 100 to 5% by weight of component (A).
These components (B) and (C) are optional components, but in order to improve the performance of the sealing material such as adhesiveness and workability, the component (B) and / or the component (C) ) Is preferably blended.
The blending ratio is 5 to 10% by weight of component (B) / component (C) with respect to 90 to 95% by weight of component (A), preferably component (A) with respect to 80 to 90% by weight of component (A). B) Component (C) is 10 to 20% by weight, more preferably 70% to 90% by weight of Component (A), and Component (B) and Component (C) are in the range of 10 to 30% by weight. desirable.

A preferred combination of the resin materials (X) is that the component (A) is an ethylene-α-olefin copolymer (A1) having a density of 0.86 to 0.92 g / cm ³ and 5 to 95% by weight, and the component (B). Is a high-pressure radical method low-density polyethylene (B1), an ethylene-vinyl ester copolymer (B2), an ultra-low-density polyethylene resin (B3) having a density of 0.86 g / cm ^{3 to} less than 0.91 g / cm ³ , a density of 0. 91g ^/ cm ³ ~0.94g ^/ cm 3 less than the linear low density polyethylene resin (B4), density 0.94g ^/ cm ³ ~0.97g ^/ cm 3 density polyethylene resin (B5), ethylene -α -At least one polyolefin resin (B) selected from olefin copolymer rubber (B6) and polypropylene resin (B7) and / or a functional group-containing polyethylene resin ( ) It is preferably made 5 to 95 wt%.

In particular, as the α-olefin polymer (A), the ethylene-α-olefin copolymer (A1) has (a1) a density of 0.86 to 0.92 g / cm ³ and (a2) a melt flow rate (MFR). Is a melt flow rate (MFR) measured at 190 ° C. under a load of 21.18 N of 0.05 to 50 g / 10 min, (a3) melt viscosity at a shear rate of 2.43 × 10 s ⁻¹ measured at 100 ° C. (Η ^* ₁ ) is 9 × 10 ⁴ poise or less, (a4) The melt viscosity (η ^* ₂ ) at a shear rate of 2.43 × 10 ² s ⁻¹ measured at 100 ° C. is 1.8 × 10 ⁴ poise or less. 10 to 95% by weight of ethylene-α-olefin copolymer having a density of 0.86 to less than 0.92 g / cm ³ produced by a single site catalyst, A resin material (X) comprising 5 to 90% by weight of a steal copolymer (B2), a copolymer (C1) with an ethylene-unsaturated carboxylic acid or a derivative thereof is required for a sealing material for solar cells. Various properties such as transparency, flexibility, reduction of deacetic acid at high temperature, water vapor barrier property, moisture absorption resistance and the like are adjusted in a well-balanced manner.

5. Wavelength converting agent (D)
The wavelength converting agent (D) of the present invention is not particularly limited, and is used for converting and utilizing wavelengths in the ultraviolet flow region and / or infrared region other than the visible region in sunlight. An organic / inorganic hybrid material that can be absorbed over the entire wavelength range of light (300 nm to 10 μm) has also been developed, but it is important to include at least a rare earth metal complex and a fluorescent material.

  Examples of the rare earth metal of the rare earth metal complex include scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Of these, europium and samarium are preferable.

Examples of the organic compound that forms the rare earth metal complex include carboxylic acids, β-diketones, and nitrogen-containing organic compounds.
Examples of the carboxylic acid include aliphatic carboxylic acids such as butyric acid, stearic acid, oleic acid, coconut oil fatty acid, t-butyl carboxylic acid, and succinic acid, aromatic carboxylic acids such as benzoic acid, naphthoic acid, and quinoline carboxylic acid. Can be mentioned.

  β-diketones include 1,3-diphenyl-1,3-propanedione, acetylacetone, benzoylacetone, dibenzoylacetone diisobutyromethane, dibiparoylmethane, 3-methylpentane-2,4dione, 2,2- Dimethylpentane-3,5-dione, 2-methyl-1,3-butanedione, 1,3-butanedione, 3-phenyl-2.4-pentanedione, 1,1,1-trifluoro2,4-pentanedione, 1,1, 1-trifluoro 5,5-dimethyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 3-methyl-2,4-pentanedione, 2-acetylcyclopentanone, 2- Acetylcyclohexanone, 1-heptafluoropropyl-3-t-butyl-1,3-propanedione, , 3-diphenyl-2-methyl-1,3-propane dione (diphenyl acetylacetone), and 1-Etokishi 1,3-butanedione can be exemplified. Among these, 1,3-diphenyl-1,3-propanedione, acetylacetone, and benzoylacetone are preferable.

  Examples of the nitrogen-containing organic compound include aromatic amines such as alkylamines and anilines, nitrogen-containing aromatic heterocyclic compounds, and the like, specifically 1,10-phenanthroline or bipyridyl. In addition, imidazole, triazole, pyrimidine, pyrazine, aminopyridine, pyridine and derivatives thereof, nucleobases such as adenine, thymine, guanine and cytosine and derivatives thereof can also be used.

  The addition amount of the wavelength converting agent (D) is not particularly limited, but is usually 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, more preferably 100 parts by weight of the resin material (X). Preferably it is used in the range of 0.05 to 2 parts by weight. When the addition amount of the wavelength conversion agent is less than 0.001 part by weight, the wavelength conversion effect is not exhibited. On the other hand, even when an amount exceeding 5 parts by weight is added, the wavelength conversion efficiency is not improved, and the transparency may be impaired. Occurs.

6). Additives In the composition for solar cell encapsulant of the present invention, a crosslinking agent (E), a crosslinking aid (F), a silane coupling agent (G), an antioxidant (H), an ultraviolet absorber ( It is preferable to add at least one additive selected from the group consisting of I), a light stabilizer (J), and a processing aid (K).

6-1. Cross-linking agent (E)
As the crosslinking agent (E) of the present invention, an organic or inorganic radical generator can be used, and among them, an organic peroxide is preferable.
As the organic peroxide, an organic peroxide having a decomposition temperature (temperature at which the half-life is 1 hour) is 70 to 180 ° C., particularly 90 to 160 ° C. can be used.
Examples of such organic peroxides include t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, t-butyl peroxyacetate, t-butyl peroxybenzoate, dicumyl peroxide, 2 , 5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1 , 1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5- Diperoxybenzoate, t-butyl hydroperoxide, p-menthane hydroperoxy Id, benzoyl peroxide, p- chlorobenzoyl peroxide, t- butyl peroxy isobutyrate, hydroxyheptyl peroxide, and di cyclohexanone peroxide.

  The blending ratio of the crosslinking agent (E) is 0.2 to 5 parts by weight, preferably 0.5 to 3 parts by weight, more preferably 1 to 1 part by weight of the resin material (X) being 100 parts by weight. 2 parts by weight. When the blending ratio of the crosslinking agent is less than the above range, crosslinking is not performed or it takes time for crosslinking. Moreover, when larger than the said range, dispersion | distribution will become inadequate and it will be easy to become non-uniform | crosslinked.

6-2. Crosslinking aid (F)
Moreover, a crosslinking adjuvant (F) can be mix | blended with the resin composition of this invention. The crosslinking aid (F) is effective in promoting the crosslinking reaction and increasing the degree of crosslinking of the α-olefin copolymer. Specific examples thereof include polyallyl compounds and poly (meth) acryloxy compounds. Unsaturated compounds can be exemplified.

  More specifically, polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, etc. Examples include poly (meth) acryloxy compounds and divinylbenzene. The crosslinking aid (F) can be blended at a ratio of about 0 to 5 parts by weight with respect to 100 parts by weight of the resin material (X).

6-3. Silane coupling agent (G)
Examples of the silane coupling agent (G) in the present invention include γ-chloropropyltrimethoxysilane; vinyltrichlorosilane; vinyltriethoxysilane; vinyltrimethoxysilane; vinyl-tris- (β-methoxyethoxy) silane; -Methacryloxypropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-glycidoxypropyltrimethoxysilane; vinyltriacetoxysilane; γ-mercaptopropyltrimethoxysilane; γ-aminopropyl Examples include trimethoxysilane; N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, and the like. Vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane are preferable.
These silane coupling agents (G) are 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, more preferably 0.5 to 1 part by weight, based on 100 parts by weight of the resin material (X). Used in.

6-4. Antioxidant (H)
As the antioxidant (H) used in the present invention, various types such as (h1) hindered phenol antioxidants, (h2) phosphorus antioxidants, (h3) sulfur antioxidants, etc. Although it can be used, it is particularly preferable to use a hindered phenolic antioxidant.

6-4-1. Hindered phenolic antioxidant (h1)
Specific examples of the hindered phenol antioxidant (h1) include 2,6-di-t-butyl-p-cresol, 2-t-butyl-4-methoxyphenol, and 3-t-butyl-4-methoxy. Phenol, 2,6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-) Butylphenol), 4,4′-methylenebis (2,6-di-t-butylphenol), 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol], bis [3,3-bis ( 4-hydroxy-3-t-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-t-butyl-m-cresol), 2,2′-ethylidenebis ( -Sec-butyl-6-t-butylphenol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t) -Butylphenyl) butane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2,6-diphenyl-4-octadecyloxy Phenol, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate, 4,4′-thiobis (6-t-butyl-m-cresol), tocopherol, 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydride) Xyl-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, 2,4,6-tris (3,5-di-t-butyl-4- And hydroxybenzylthio) -1,3,5-triazine.

6-4-2. Phosphorous antioxidant (h2)
Examples of phosphorus antioxidants (h2) include 3,5-di-t-butyl-4-hydroxybenzyl phosphonate dimethyl ester and bis (3,5-di-t-butyl-4-hydroxybenzylphosphonic acid ethyl ester. , Tris (2,4-di-t-butylphenyl) phosphate, and the like.

6-4-3. Sulfur-based antioxidant (h3)
As the sulfur-based antioxidant (h3), 2,4-bis-n-octylthio-6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2 -Thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl] -o-cresol and the like can be mentioned.

6-5. UV absorber (I)
An ultraviolet absorber can be blended in the resin composition of the present invention. Examples of the ultraviolet absorber (I) include various types such as benzophenone, benzotriazole, triazine, and salicylic acid ester.

6-5-1. Benzophenone-based UV absorbers Examples of benzophenone-based UV absorbers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2- Hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-octadecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-5 -Chlorobenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxy Ben Examples include zophenone.

6-5-2. Benzotriazole-based UV absorber The benzotriazole-based UV absorber is a hydroxyphenyl-substituted benzotriazole compound, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5) -T-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-dimethylphenyl) benzotriazole, 2- (2-methyl-4-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3- Methyl-5-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-amylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) ) Benzotriazole, and the like. Examples of triazine ultraviolet absorbers include 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2- ( And 4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyloxy) phenol. Examples of salicylic acid esters include phenyl salicylate and p-octylphenyl salicylate. These ultraviolet absorbers are preferably blended in an amount of 0 to 2.0 parts by weight with respect to 100 parts by weight of the resin material (X).

6-6. Light stabilizer (J)
A light stabilizer can be blended in the resin composition of the present invention. Examples of the light stabilizer (J) include a hindered amine light stabilizer (J1).

6-6-1. Hindered amine light stabilizer (J1)
In the present invention, it is preferable to blend a hindered amine light stabilizer (J1) in the resin composition. The hindered amine light stabilizer captures radical species harmful to the polymer and prevents generation of new radicals. There are many types of hindered amine light stabilizers ranging from low molecular weight compounds to high molecular weight compounds, but any conventionally known compounds can be used without particular limitation.

1) Low molecular weight hindered amine light stabilizer Low molecular weight hindered amine light stabilizer
70% by weight of a reaction product of bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide and octane (molecular weight 737) And 30% by weight polypropylene;
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate (molecular weight 685);
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate mixture (molecular weight 509);
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (molecular weight 481); Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane Tetracarboxylate (molecular weight 791);
Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate (molecular weight 847);
A mixture of 2,2,6,6-tetramethyl-4-piperidyl-1,2,3,4-butanetetracarboxylate and tridecyl-1,2,3,4-butanetetracarboxylate (molecular weight 900);
A mixture of 1,2,2,6,6-pentamethyl-4-piperidyl-1,2,3,4-butanetetracarboxylate and tridecyl-1,2,3,4-butanetetracarboxylate (molecular weight 900), etc. Is mentioned.

2) High molecular weight hindered amine light stabilizers As high molecular weight hindered amine light stabilizers,
Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl ) Imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] (molecular weight 2,000-3,100);
Polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (molecular weight 3,100 to 4,000);
N, N ′, N ″, N ″ ′-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazine- 2-yl) -4,7-diazadecane-1,10-diamine (molecular weight 2,286), dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol A mixture of
Dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6, 6-tetramethyl-4-piperidyl) butylamine polycondensate (molecular weight 2,600-3,400), and
4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-acryloyloxy-1-ethyl-2,2,6 , 6-tetramethylpiperidine, 4-acryloyloxy-1-propyl-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1-butyl-2,2,6,6-tetramethylpiperidine, 4 -Methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylperidine, 4-methacryloyloxy-1-ethyl-2,2,6 , 6-tetramethylpiperidine, 4-methacryloyloxy-1-butyl-2,2,6,6-tetramethylpiperidine, 4-crotonoy Copolymers of cyclic aminovinyl compounds such as oxy-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-1-propyl-2,2,6,6-tetramethylpiperidine and ethylene and the like. Can be mentioned. The above-mentioned hindered amine light stabilizers may be used alone or in combination of two or more.

Among these, as a hindered amine light stabilizer,
Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl ) Imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] (molecular weight 2,000-3,100);
Polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (molecular weight 3,100 to 4,000);
N, N ′, N ″, N ″ ′-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazine- 2-yl) -4,7-diazadecane-1,10-diamine (molecular weight 2,286), dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol A mixture of
Dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6, It is preferable to use a copolymer of 6-tetramethyl-4-piperidyl) butylamine polycondensate (molecular weight 2,600 to 3,400) cyclic aminovinyl compound and ethylene, hindered amine light over time when the product is used. It is preferable that a hindered amine light stabilizer having a melting point of 60 ° C. or higher is used from the viewpoint of easy preparation of the composition.

  In the present invention, the content of the hindered amine light stabilizer is 0.1 to 2.5 parts by weight, preferably 0.1 to 1.0 parts by weight, relative to 100 parts by weight of the resin material (X). It is good to do. When the content is 0.1 parts by weight or more, the effect of stabilization is sufficiently obtained, and when the content is 2.5 parts by weight or less, the resin is discolored due to excessive addition of a hindered amine light stabilizer. Can be suppressed.

6-7. Processing aid (K)
The processing aid (K) according to the present invention includes (k1) at least one lubricant processing aid selected from (k1) fatty acids, fatty acid metal salts, fatty acid amides, and aliphatic hydrocarbon processing aids, (k2) C9-C40 saturated or unsaturated fatty acid ester processing aid, (k3) epoxidized animal and vegetable oil processing aid, (k4) fluorine elastomer processing aid, (k5) silicone processing aid, And (k6) at least one processing aid selected from the group consisting of polyester processing aids.
The amount of the processing aid (K) is selected in the range of 0.05 to 20 parts by weight with respect to 100 parts by weight of the resin material (X). If the blending amount of the processing aid is less than 0.05 parts by weight, the effect is not exhibited, and if it exceeds 20 parts by weight, there is a concern that the screw slips and the extrusion is not smoothly performed. Moreover, there is a risk that the transparency of the solar cell encapsulant and the strength of the sheet may be reduced.

  In the present invention, the weight ratio of the crosslinking agent (organic peroxide) (E) to the hindered amine light stabilizer (J) is E: J = 1: 0.01 to 1:10, Preferably, E: J = 1: 0.02 to 1: 6.5. Thereby, it becomes possible to remarkably suppress yellowing of the resin.

7). Other additive components In the resin composition of the present invention, other optional additional components can be blended within a range that does not significantly impair the object of the present invention. Examples of such optional components include colorants, dispersants, fillers, fluorescent whitening agents, and the like used in ordinary polyolefin resin materials.

  In addition, in order to impart flexibility and the like to the resin composition of the present invention, other thermoplastic resins and / or styrene-based elastomers such as hydrogenated styrene block copolymers, etc. within a range not impairing the object of the present invention 3 to 75 parts by weight of the rubber compound can be blended.

II. Solar cell encapsulant The solar cell encapsulant of the present invention (hereinafter also simply referred to as encapsulant) is obtained by pelletizing the resin composition and forming it into a film or sheet by extrusion molding, calendar molding, or the like. is there.
That is, the solar cell encapsulant of the present invention is a film for solar cell encapsulant comprising a single layer film or a multilayer film formed by extrusion molding the above-described resin composition for solar cell encapsulant, or the solar cell encapsulant. It is a multilayer sheet formed by laminating a film for battery sealing material and at least a protective film on the front surface and / or the back surface with an adhesive film interposed as desired.

(1) Solar cell encapsulating material comprising a single layer film Examples of preferred embodiments of the solar cell encapsulating material comprising the single layer film of the present invention include those using the following compositions.
(I) A predetermined amount of a wavelength converting agent is added to 100 parts by weight of an ethylene-α-olefin copolymer (A1) having a density of 0.86 to 0.92 g / cm ³ produced with a single site catalyst as an α-olefin polymer. In addition, a solar cell encapsulant (ii) single site formed by forming a composition containing a processing aid, a crosslinking agent, a silane coupling agent, an ultraviolet absorber and a hindered amine stabilizer into a film or a sheet as necessary. 95 to 40% by weight of ethylene-α-olefin copolymer (A1) having a density of 0.86 to 0.92 g / cm ³ produced by a catalyst and other polyolefin resin (B) such as ethylene-vinyl acetate copolymer A predetermined amount of a wavelength converting agent is added to 5 to 60% by weight of an ethylene copolymer such as a polymer (B) and / or an ethylene-alkyl acrylate copolymer (C), A solar cell encapsulant formed by forming a film or sheet of a composition containing a processing aid, a crosslinking agent, a silane coupling agent, an ultraviolet absorber, and a high molecular weight hindered amine stabilizer as necessary. In combination, a balanced solar cell encapsulant that achieves the objects of the present invention such as flexibility, transparency, heat resistance, and productivity improvement is provided.

(2) Solar cell encapsulating material comprising a multilayer film As a preferred embodiment of the solar cell encapsulating material comprising the multilayer film of the present invention, for example, the above-mentioned (A1) single-layer film (i) or (A1 + B and / or A solar cell comprising a single-layer film (ii) comprising the composition of C) and a two-layer film of other polyolefin-based resin (B) such as ultra-low density polyethylene (B3) and linear low density polyethylene (B4) Sealing material, three-layer film of the single-layer film (i) / ultra-low-density polyethylene (B3) / linear low-density polyethylene film (B4), the single-layer film (ii) / ultra-low-density polyethylene (B3) ) / Multilayer films such as a three-layer film with a linear low density polyethylene film (B4). In these films, a predetermined amount of wavelength conversion agent is appropriately added to each layer, and further additives such as a crosslinking agent, a silane coupling agent, an ultraviolet absorber, a high molecular weight hindered amine stabilizer, and a processing aid as necessary. Can be added to give the function of the sealing material or to improve the performance.

(3) Solar cell encapsulating material comprising a multilayer sheet The solar cell encapsulating material comprising the multilayer sheet of the present invention includes at least a protective film on the front surface and / or the back surface, and another substrate with an adhesive film as desired. A solar cell encapsulant comprising a multilayer sheet obtained by laminating the single-layer or multilayer solar cell encapsulant film.
The protective film for the front and / or back is selected from polyethylene resin, polypropylene resin, polyester resin, polyamide resin, saponified ethylene-vinyl acetate copolymer, polyvinylidene chloride resin, and fluorine resin. Examples thereof include a film of one kind of resin, a stretched film of those resins, a film obtained by depositing an inorganic oxide on the surface of these resins, and the like.
Examples of the substrate include polypropylene-based or polyester-based non-woven fabric, inorganic or organic non-woven fabric or woven fabric, and metal foil.
Production methods of these laminates are generally known, such as conventionally known extrusion laminating, sand laminating for laminating films in advance, dry laminating, or laminating by coextrusion laminating these resins. A laminating method is adopted.
Moreover, you may use the adhesive film or the said functional group containing polyolefin resin (C) of this invention at the time of extrusion lamination as needed at the time of manufacture of the said laminated body. Further, the molten film may be fused by performing corona discharge treatment, ozone treatment, plasma treatment, flame treatment, anchor treatment or the like.

  The solar cell encapsulant of the present invention may be a single layer sheet as described above, but glass, acrylic resin, polycarbonate, polyester, fluorine on one or both sides of the sheet made of the composition of the present invention by multilayer extrusion molding. Film having adhesiveness with upper (surface) protective material and / or lower (back surface) protective material such as containing resin, for example, copolymer of ethylene and unsaturated carboxylic acid or derivative thereof, maleic anhydride modified polyethylene, anhydrous A multilayered sheet provided with maleic acid-modified polypropylene resin or the like, or a sheet made of the composition of the present invention was provided with a water vapor barrier substrate, a metal oxide vapor deposition film, etc. via an adhesive resin on one or both sides. It can also be a multilayer sheet.

  The sheet-like solar cell encapsulant can be produced by a known sheet molding method using a T-die extruder, a calendar molding machine, or the like. For example, ethylene / α-olefin copolymer, a predetermined amount of wavelength converting agent, and further, if necessary, a crosslinking agent, a hindered amine light stabilizer, a crosslinking aid, a silane coupling agent, an ultraviolet absorber, an oxidation agent. It can be obtained by dry blending additives such as an inhibitor and a light stabilizer in advance and supplying them from a hopper of a T-die extruder and extruding into a sheet at an extrusion temperature of 80 to 150 ° C. In these dry blends, some or all of the additives can be used in the form of a masterbatch. In addition, in T-die extrusion and calendering, some or all of the additive is previously melt-mixed into the amorphous α-olefin copolymer using a single screw extruder, twin screw extruder, Banbury mixer, kneader, etc. Thus obtained resin composition can also be used.

The solar cell encapsulant of the present invention may be used as a pellet, but the thickness as a single layer film is usually used after being formed into a film or sheet having a thickness of about 0.1 to 1 mm.
If the thickness is less than 0.1 mm, the strength is small and the adhesion is insufficient. If the thickness is more than 1 mm, the transparency may be lowered, which may be a problem. A preferred thickness is 0.1 to 0.8 mm.

III. Solar cell module In general, a solar cell module includes a surface protective material layer, a sealing material layer, a back surface protective material layer, and, if desired, a base material layer in addition to the solar cell element.
In the solar cell module of the present invention, the encapsulant layer is composed of 5 to 100% by weight of the α-olefin polymer (A) and other polyolefin resin (B) other than the α-olefin polymer (A). And / or a functional group-containing polyolefin resin (C) is formed from a resin material (X) comprising 0 to 95% by weight, and at least one of a surface protective material layer, a sealing material layer and a back surface protective material layer. Needs to be a wavelength conversion layer. Among these, the wavelength conversion layer in which the wavelength conversion agent (D) is added to the sealing material layer is particularly effective.
If this solar cell sealing material is used, it can be manufactured by fixing the solar cell element together with upper and lower protective materials. Examples of such solar cell modules include various types.
For example, an upper transparent protective material / encapsulating material / solar cell element / encapsulating material / lower protective material that is sandwiched between both sides of the solar cell element by an encapsulating material, on the inner peripheral surface of the lower substrate protective material A structure in which a sealing material and an upper transparent protective material are formed on the formed solar cell element, a solar cell element formed on the inner peripheral surface of the upper transparent protective material, for example, a fluororesin-based transparent protective material In addition, a structure in which an encapsulant and a lower protective material are formed on an amorphous solar cell element formed by sputtering or the like can be used.

  The solar cell element is not particularly limited, and is based on silicon such as single crystal silicon, polycrystalline silicon, amorphous silicon, III-V group or II-VI group such as gallium-arsenic, copper-indium-selenium, cadmium-tellurium. Various solar cell elements such as compound semiconductors can be used.

Examples of the surface (upper) protective material constituting the solar cell module include an inorganic material such as glass, a resin sheet such as an acrylic resin, a polycarbonate, a polyester resin, and a fluorine-containing resin.
The back (lower) protective material is a single or multilayer sheet such as a metal or various thermoplastic resin films, for example, a metal such as tin, aluminum or stainless steel, an inorganic material such as glass, polyester, an inorganic substance, etc. Examples of the protective material include one layer or multiple layers such as vapor-deposited polyester, fluorine-containing resin, and polyolefin-based resin. Such a protective material for the front surface (upper part) and / or the back surface (lower part) can be subjected to a primer treatment, an adhesive, an adhesive film, or the like in order to enhance the adhesion to the sealing material.

  Examples of the water vapor barrier film include polyester resin, polyamide resin, saponified ethylene-vinyl acetate copolymer, polyvinylidene chloride resin, fluorine resin, and polypropylene resin, or a resin film thereof. Examples thereof include a stretched film of the above-mentioned resin, and a film in which an inorganic oxide is vapor-deposited on the surface of the resin. In particular, a film in which an inorganic oxide is vapor-deposited is preferable because it has excellent water vapor barrier properties and transparency.

  As an inorganic oxide vapor deposition film constituting a solar cell module, for example, a physical vapor deposition method, a chemical vapor deposition method, or a combination of both, A multilayer film composed of one layer or two or more layers can be formed and manufactured. For example, an inorganic oxide vapor-deposited thin film can be formed using a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, or an ion plating method.

  Examples of the metal oxide according to the present invention include silicon oxide, aluminum oxide, and magnesium oxide. The film thickness of the inorganic oxide thin film varies depending on the type of metal or metal oxide used, but is, for example, about 50 to 2000 mm (5 to 200 nm), preferably 100 to 1000 mm (10 to 100 nm). It is desirable to select and form arbitrarily within the range. In the present invention, the inorganic oxide vapor-deposited thin film is not limited to a single layer of inorganic oxide vapor-deposited thin film, but may be a laminate of two or more layers. Or as a metal oxide, it can also be used by the 1 type, or 2 or more types of mixture, and can also comprise the thin film of the inorganic oxide mixed by the dissimilar material.

  In manufacturing the solar cell module, the sheet of the sealing material of the present invention is prepared in advance, and the above-described method is performed by pressure bonding at a temperature at which the resin composition of the sealing material melts, for example, 150 to 200 ° C. A module having a simple structure can be formed. Moreover, if the method of laminating with the solar cell element, the front surface (upper) protective material or the back surface (lower) protective material by extrusion coating the sealing material of the present invention is adopted, the solar cell can be made in one step without bothering to form a sheet. Modules can be manufactured. Therefore, if the sealing material of this invention is used, the productivity of a module can be improved markedly.

On the other hand, when the solar cell module is manufactured, the sealing material is temporarily applied to the solar cell element or the protective material at a temperature at which the organic peroxide is not substantially decomposed and the sealing material of the present invention is melted. Adhesion is then carried out to raise the temperature, and sufficient adhesion and crosslinking of the ethylene / α-olefin copolymer can be carried out. In this case, the gel in the encapsulant layer is used in order to obtain a solar cell module with good heat resistance having a melting point (DSC method) of the encapsulant layer of 85 ° C. or higher and a storage elastic modulus of 150 ° C. of 10 ³ Pa or higher. Fraction (1 g of sample is immersed in 100 ml of xylene, heated at 110 ° C. for 24 hours, then filtered through a 20 mesh wire net and the mass fraction of unmelted portion is measured) is 50 to 98%, preferably about 70 to 95% It is better to crosslink so that

  In Patent Document 3, 100 parts by weight of an amorphous or low crystalline ethylene / butene copolymer is added to 2,5-dimethyl-2,5-di (t-butylperoxy) hexane as an organic peroxide. A mixture of 1.5 parts by weight and 2 parts by weight of triallyl isocyanurate as a crosslinking aid was produced using a profile extruder at a processing temperature of 100 ° C. and a thickness of 0.5 mm (Example 3). ). However, when such a composition is selected, sufficient productivity cannot be obtained because the processing temperature is low.

  In the sealing operation of the solar cell element, after covering the solar cell element with the sealing material of the present invention, the solar cell element is temporarily bonded by heating to a temperature at which the organic peroxide is not decomposed for several minutes to 10 minutes, In addition, there is a method in which the organic peroxide is decomposed in the oven at a high temperature of about 150 to 200 ° C. for 5 to 30 minutes to be bonded.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The evaluation methods and resins used in the examples and comparative examples are as follows.

1. Evaluation method of resin physical properties (1) Melt flow rate (MFR): MFR of ethylene / α-olefin copolymer is measured according to JIS-K6922-2: 1997 appendix (190 ° C., 21.18 N load). did.
(2) Density: The density of the ethylene / α-olefin copolymer was measured according to JIS-K6922-2: 1997 appendix (in the case of 23 ° C., low density polyethylene).
(3) Mz / Mn: Measured by GPC as described above.
(4) Melt viscosity: In accordance with JIS-K-7199-1999, using Capillograph 1-B manufactured by Toyo Seiki Seisakusho, using a capillary with set temperature: 100 ° C., D = 1 mm, L / D = 10, melt viscosity at a shear rate of _{^{2.43 × 10sec -1 (η * 1}} ), to measure the melt viscosity at a shear rate of ^{2.43 × 10 2 sec -1 (η} * 2).

2. Extrudate at creating conditions for pellets 160 ℃ -0kg / cm ² obtained by melt kneading (sheet), 3 minutes after preheating, 160 ° C. 100 kg / cm conditions 27 minutes pressurization of ² (160 The sheet was then pressed at 30 ° C. for 30 minutes, and then cooled to a cooling press set at 30 ° C. under a pressure of 100 kg / cm ² for 10 minutes to produce a sheet having a thickness of 0.7 mm.

3. Method for evaluating extruded product (sheet) (1) HAZE
It measured based on JIS-K7136-2000.
(2) Tensile modulus (MD)
Based on ISO1184-1983, the tensile elastic modulus in the MD direction (sheet take-up direction) was measured. It shows that it is excellent in the softness, so that this value is small.

(3) Heat resistance It evaluated by the gel fraction of the sheet | seat bridge | crosslinked for 30 minutes at 160 degreeC. It can be evaluated that the higher the gel fraction, the more the crosslinking proceeds and the higher the heat resistance. A gel with a gel fraction of 70 wt% was designated as a heat resistance evaluation “◯”. As for the gel fraction, about 1 g of the sheet is cut out and weighed accurately, immersed in 100 cc of xylene, treated at 110 ° C. for 24 hours, the residue after filtration is dried and weighed, and divided by the weight before treatment. Calculate the gel fraction.

(4) Adhesiveness with glass A slide glass having a length of 7.6 cm, a width of 2.6 cm, and a thickness of 1 mm was used.
The resin composition and the slide glass were brought into contact with each other and heated using a press machine at 150 ° C. for 15 minutes. The evaluation was made with “x” when the resin could be peeled off from the glass by hand in a 23 ° C. atmosphere for 24 hours, and “◯” when it could not be peeled off.

(5) Workability (i) Proper extrusion The pellets could be produced at an extrusion rate (17 kg / hour) or more without any increase in resin temperature due to resin pressure or shear heat generation during melt kneading using a 40 mmφ single screw extruder. "○", those that could produce pellets at an extrusion rate (9-17 kg / hour) "△", those that could produce pellets at an extrusion rate (9 kg / hour) or less, or those that could not produce pellets Was marked “x”.
(Ii) Sheet Appearance Using the pellets prepared above, 2. The appearance of a 0.7 mm thick sheet produced by the method for producing an extruded product (sheet) was visually confirmed.
The sheet in which the resin temperature did not increase due to the resin pressure or shearing heat generation during melt kneading was judged to be a good sheet with no gel generated by the progress of crosslinking, and was judged as “good”. When the decomposition of the organic oxide due to the increase in the resin temperature progressed, a gel formed by the progress of cross-linking was seen in the sheet, and it was judged that the sheet was not uniform and was not a good sheet, and was set as “x”. .

(6) Wavelength conversion efficiency Except for not adding a wavelength conversion substance (fluorescent rare earth metal complex / fluorescent dye), the power generation amount of a solar cell module using a sealing material manufactured in the same manner as a resin to which a wavelength conversion substance is added is 1 The power generation rate ratio (average value of 5 samples each) of the solar cell module using the sealing material to which the wavelength converting substance was added was shown.

4). Used Raw Material (1) Component (A1): Ethylene / α-Olefin Copolymer Ethylene / hexene-1 copolymer (PE-1) polymerized in the following <Production Example 1>, polymerized in <Production Example 2> The copolymer of ethylene and butene-1 (PE-2), and a commercially available ethylene / 1-butene copolymer, Tuffmer A4085S (PE-3) manufactured by Mitsui Chemicals, Inc. were used. The physical properties are shown in Table 1.
(2) Silane coupling agent: γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM503)
(3) Organic peroxide: Arupema Yoshitomi Corp., Luperox 101 (2,5-dimethyl-2,5-di (t-butylperoxy) hexane)
(4) Hindered amine light stabilizer: dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine And N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate

<Production Example 1>
(I) Preparation of catalyst A catalyst for producing a copolymer of ethylene and hexene-1 was prepared by the method described in JP-T-7-508545. That is, to the complex dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) hafnium dimethyl 2.0 mmol, tripentafluorophenyl boron is added in an equimolar amount to the complex, and diluted to 10 liters with toluene. A catalyst solution was prepared.

(Ii) Polymerization Using a stirred autoclave type continuous reactor having an internal volume of 1.5 liters, maintaining the pressure in the reactor at 130 MPa, a mixture of ethylene and 1-hexene has a composition of 1-hexene of 75% by weight. The raw material gas was continuously supplied at a rate of 40 kg / hour. Further, the catalyst solution was continuously supplied, and the supply amount was adjusted so that the polymerization temperature was maintained at 150 ° C. The polymer production per hour was about 4.3 kg. After completion of the reaction, an ethylene / 1-hexene copolymer (PE-) having a 1-hexene content of 24% by weight, an MFR of 35 g / 10 min, a density of 0.880 g / cm ³ , and Mz / Mn of 3.7. 1) was obtained. The characteristics of this ethylene / 1-hexene copolymer (PE-1) are shown in Table 1.

<Production Example 2>
Polymerization was carried out by changing the monomer composition and polymerization temperature during polymerization in Production Example 1 so that the composition, density, and melt viscosity shown in Table 1 were obtained. After completion of the reaction, an ethylene / 1-butene copolymer (PE-) having 1-butene content = 35 wt%, MFR = 33 g / 10 min, density = 0.870 g / cm ³ , and Mz / Mn = 3.5. 2) was obtained. The characteristics of this ethylene / 1-butene copolymer (PE-2) are shown in Table 1.

Example 1
1 part by weight of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM503) as a silane coupling agent with respect to 100 parts by weight of ethylene and 1-hexene copolymer (PE-1) As an oxide, 0.5 part by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (manufactured by Arkema Yoshitomi Co., Ltd., Luperox 101) and as a hindered amine light stabilizer, dibutylamine 1,3,5-triazine N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6- Tetramethyl-4-piperidyl) butylamine polycondensate (Ciba Specialty Chemicals, CHIMASSORB 2020FDL) 0.2 parts by weight and a wavelength conversion agent Then, 0.2 parts by weight of tris (2,2,6,6-tetramethyl-3,5-heptanedionato) europium (III) (manufactured by J & K SCIENTIFIC LTD.) Was mixed. Using a shaft extruder, pelletization was performed under conditions of a set temperature of 130 ° C. and an extrusion rate (17 kg / hour).
The obtained pellets were then press-formed at 160 ° C. for 30 minutes to produce a sheet having a thickness of 2 mm. The sheet was measured for HAZE, tensile modulus (MD), heat resistance, and adhesion. The power generation amount ratio was set to 1 in (Comparative Example 1).
The evaluation results are shown in Table 2.

(Example 2)
In Example 1, a sheet was produced in the same manner as in Example 1 except that ethylene and 1-butene copolymer (PE-2) were used instead of ethylene and 1-hexene copolymer (PE-1). did. The sheet was evaluated for HAZE, tensile modulus (MD), heat resistance, and adhesion. The power generation ratio was set to 1 in (Comparative Example 2). The evaluation results are shown in Table 2.

(Example 3)
In Example 2, a sheet was prepared in the same manner except that Coumarin 153 was used as the fluorescent dye-based wavelength converting agent. The sheet was evaluated for HAZE, tensile modulus (MD), heat resistance, and adhesion. The power generation ratio was set to 1 in (Comparative Example 3). The evaluation results are shown in Table 2.

Example 4
In Example 3, instead of ethylene and 1-butene copolymer (PE-2), Tafmer A4085S (PE-3) was used and a 40 mmφ single-screw extruder was used to set the temperature at 100 ° C. and the extrusion rate (9.7 kg). The sheet was formed in the same manner except that it was pelletized under the conditions of (/ hour). The sheet was evaluated for HAZE, tensile modulus, heat resistance, and adhesion. The power generation ratio was set to 1 in (Comparative Example 4). The evaluation results are shown in Table 2. This Example 4 is a reference example.

(Comparative Example 1)
A sheet was prepared in the same manner as in Example 1 except that the wavelength converting agent was not added. The sheet was evaluated for HAZE, tensile modulus, heat resistance, and adhesion. The power generation ratio was set to 1 and compared with Example 1. The evaluation results are shown in Table 2.

(Comparative Example 2)
A sheet was prepared in the same manner as in Example 2 except that the wavelength converting agent was not added. The sheet was evaluated for HAZE, tensile modulus, heat resistance, and adhesion. The power generation ratio was set to 1 and compared with Example 2. The evaluation results are shown in Table 2.

(Comparative Example 3)
A sheet was prepared in the same manner as in Example 3 except that the wavelength converting agent was not added. The sheet was evaluated for HAZE, tensile modulus, heat resistance, and adhesion. The power generation ratio was set to 1 and compared with Example 3. The evaluation results are shown in Table 2.

(Comparative Example 4)
A sheet was prepared in the same manner as in Example 4 except that the wavelength converting agent was not added. The sheet was evaluated for HAZE, tensile modulus (MD), heat resistance, and adhesion. The power generation ratio was set to 1 and compared with Example 4. The evaluation results are shown in Table 2.

As a result, as is apparent from Table 2, in Examples 1 to 4 (however, Example 4 is a reference example) , since the resin composition of the present invention is used, it is obtained by extrusion molding. The sheet has excellent workability, small HAZE, high tensile elastic modulus, excellent heat resistance and adhesion to glass, and in addition, in terms of power generation ratio, it is significant compared to the comparative example in which no wavelength conversion agent is added. There was a difference.
On the other hand, in Comparative Examples 1 to 4, there was almost no difference from the examples in terms of workability, HAZE, tensile elastic modulus, heat resistance, and adhesiveness, but clearly inferior in terms of power generation ratio. It was.

  Since the solar cell module of the present invention can increase the wavelength conversion efficiency of sunlight, its industrial applicability is very large. In addition, the composition for solar cell encapsulant used for it is easy to form a solar cell module, has no deacetic acid, has excellent water vapor barrier properties, moisture absorption resistance, crosslinkability, etc., and has transparency and heat resistance. Since it is suitable for a solar cell sealing material that retains flexibility and the like, its industrial applicability is also very large.

Claims (11)

In the solar cell module provided with a surface protective material layer, a sealing material layer, a back surface protective material layer, and a base material layer as desired,
The sealing material layer is composed of 5 to 100% by weight of an α-olefin polymer (A) and another polyolefin resin (B) and / or functional group-containing polyolefin other than the α-olefin polymer (A). A resin material (X) composed of 0 to 95% by weight of a resin (C), and
At least one of the surface protective material layer, the sealing material layer, and the back surface protective material layer includes a wavelength conversion layer , and the α-olefin polymer (A) has the following characteristics (a1) to (a5): A resin composition for a solar cell encapsulant, which is a satisfactory ethylene-α-olefin copolymer (A1) .
(A1) Density is 0.86-0.92 g / cm ³
(A2) Melt flow rate (MFR) measured under a load of 190 ° C. and 21.18 N is 0.05 to 50 g / 10 min.
( A3 ) The melt viscosity (η ^* ₁ ) at a shear rate of 2.43 × 10 s ⁻¹ measured at 100 ° C. is 9.0 × 10 ⁴ poise or less
( A4 ) The melt viscosity (η ^* ₂ ) at a shear rate of 2.43 × 10 ² s ⁻¹ measured at 100 ° C. is 1.8 × 10 ⁴ poise or less.
(A5) The number of branches (N) due to the comonomer in the polymer and the tensile modulus (E) satisfy the following formula (a).
Formula (a): N ≧ −0.67 × E + 53
(However, N is the number of branches per 1000 carbon atoms in total of the main chain and side chain measured by NMR, and E is the tensile modulus of the sheet measured in accordance with ISO 1184-1983.) ) The solar cell encapsulant according to claim 1, wherein the α-olefin polymer (A) is an ethylene-α-olefin copolymer (A1) that satisfies the following property (a6). Resin composition.
(A6) Flow ratio (FR): Ratio of I10, which is an MFR measurement value at 190 ° C. under a ₁₀ kg load, to I _2.16 , which is an MFR measurement value at 190 ° C. under a 2.16 kg load (I ₁₀ / I _2.16 ) is less than 7.0 The sealing material layer is composed of 5 to 100% by weight of an α-olefin polymer (A) and another polyolefin resin (B) and / or functional group-containing polyolefin other than the α-olefin polymer (A). The solar cell module according to claim 1 or 2, comprising a resin material (X) composed of 0 to 95% by weight of a resin based resin (C) and a wavelength conversion agent (D). The wavelength conversion layer and / or the wavelength conversion agent (D) is according to claim 3, wherein the rare earth element is its ion or at least one fluorescent substance of the organic metal complexes and / or organic fluorescent dye Solar cell module.   The solar cell module according to any one of claims 1 to 4, wherein the α-olefin polymer (A) is produced with a single site catalyst. It is a resin composition for solar cell sealing materials used for the solar cell module of any one of Claims 1-5,
α-olefin polymer (A) 5 to 100% by weight and other polyolefin resin (B) and / or functional group-containing polyolefin resin (C) 0 to other than α-olefin polymer (A) A resin composition for a solar cell encapsulant, comprising 0.001 to 5 parts by weight of a wavelength converting agent (D) in 100 parts by weight of a resin material (X) comprising 95% by weight.   The solar cell sealing material according to claim 6, wherein the wavelength conversion agent (D) is at least one fluorescent material of rare earth elements, ions thereof, organometallic complexes thereof, and / or organic fluorescent dyes. Resin composition. The resin composition for solar cell encapsulant according to claim 6 or 7 , wherein the α-olefin polymer (A) is produced with a single site catalyst. The resin material (X) is composed of 95 to 5% by weight of ethylene-α-olefin copolymer (A1) having a density of 0.86 to 0.92 g / cm ³ , high-pressure radical method low-density polyethylene (B1), ethylene - vinyl ester copolymer (B2), density 0.86~0.91g / cm ³ less than the very low-density polyethylene resin (B3), a density of less than 0.91~0.94g / cm ³ linear From low density polyethylene resin (B4), high density polyethylene resin (B5) having a density of 0.94 to 0.97 g / cm ³ , ethylene-α-olefin copolymer rubber (B6), and polypropylene resin (B7) claim 6-8, characterized in that it consists of at least one polyolefin-based resin (B) and / or functional group-containing polyolefin-based resin (C) 5 to 95 wt% selected from the group consisting Solar cell encapsulant resin composition according to any one. The composition further comprises a crosslinking agent (E), a crosslinking aid (F), a silane coupling agent (G), an antioxidant (H), an ultraviolet absorber (I), a light stabilizer (J), and The resin composition for a solar cell encapsulant according to any one of claims 6 to 9 , comprising at least one additive selected from the group consisting of processing aids (K). Monolayer film or a multilayer film for a solar cell sealing material is formed from the solar cell encapsulant resin composition according to any one of claims 6-10, or a monolayer film or a multilayer film A solar cell encapsulant comprising a multilayer sheet obtained by laminating at least a protective film on the front surface and / or the back surface with another base material and / or an adhesive film interposed as desired.