JP2011012243A - Ethylene-based resin composition, solar cell sealing material and solar cell module using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ethylene-based resin composition that comprises a modified product obtained by modifying an ethylene-based resin (A) satisfying specific requirements with a radically polymerizable unsaturated compound (B1) and a radically polymerizable unsaturated compound (B2), which has excellent adhesiveness to glass, back sheets and thin film electrodes, electric insulation, transparency, moldability and process stability; and a solar cell sealing material using the same.SOLUTION: The ethylene-based resin composition comprises a modified product obtained by modifying an ethylene-based polymer (A) with a radically polymerizable unsaturated compound (B1) and a radically polymerizable unsaturated compound (B2). The ethylene-based polymer (A) simultaneously satisfies the following requirements: (a) a density of 900-940 kg/m; (b) a melting peak based on DSC of 90-125°C; (c) melt flow rate (MFR 2) measured at 190°C and 2.16 kg load of 0.1-100 g/10 minutes based on JIS K-6721; (d) Mw/Mn of 1.2-3.5; and (e) metal residue of 0.1-50 ppm.

Description

The present invention relates to an ethylene resin composition excellent in adhesion to glass, a back sheet, and a thin film electrode, electrical insulation, transparency, moldability and process stability, and further relates to a solar cell encapsulant using the same.
The present invention further relates to a solar cell sealing sheet using such an ethylene-based resin composition, and a solar cell module using the sealing material and / or the sealing sheet.

  As global environmental problems, energy problems, and the like become more serious, solar cells are attracting attention as an energy source that is clean and free from depletion. When a solar cell is used outdoors such as a roof portion of a building, it is generally used in the form of a solar cell module.

  The above solar cell module is roughly divided into two types: a crystalline solar cell module and a thin film solar cell module. A crystalline solar cell module is a solar cell module protective sheet (surface protective sheet) / solar cell sealing sheet / crystalline solar cell formed of polycrystalline silicon, single crystal silicon, or the like. / Sheet cell sealing sheet / solar cell module protective sheet (back surface protective sheet) are laminated in this order, and then manufactured using a lamination method or the like in which these are vacuum-sucked and thermocompression bonded.

  The thin film solar cell module is a thin film solar cell / solar cell made by forming a very thin film of several μm on a substrate such as glass with amorphous silicon or crystalline silicon. The battery sealing sheet / solar cell module protective sheet (back surface protective sheet) are laminated in this order, and then manufactured using a lamination method or the like in which these are vacuum-sucked and heat-pressed.

  The solar cell module obtained in this way has weather resistance and is suitable for outdoor use such as a roof portion of a building.

  Conventionally, as a material constituting a solar cell sealing sheet (solar cell sealing material), ethylene-vinyl acetate copolymer (EVA) has been widely used from the viewpoint of requirements such as transparency and flexibility. (For example, refer to Patent Document 1). When EVA is used for a solar cell encapsulant, it is common to perform a crosslinking treatment in order to impart sufficient heat resistance, but the crosslinking treatment requires a relatively long time of about 0.2 to 2 hours. Therefore, it has been a cause of lowering the production speed and production efficiency of the solar cell module. In addition, there is a concern that components such as acetic acid gas generated by the decomposition of EVA may affect the solar cell element.

  One of the measures for solving the above technical problem is to use an ethylene / α-olefin copolymer for at least a part of the solar cell encapsulant, and also for ethylene / α- There is also a proposal for a solar cell encapsulant using an olefin copolymer (see Patent Document 2). However, Patent Document 2 discloses some types of usage of ethylene / α-olefin copolymer for obtaining preferable characteristics (heat resistance, transparency, flexibility, resistance to process stability, etc.) as a sealing material. No specific guidance is disclosed. This is presumably because the technique disclosed in Patent Document 2 is premised on the crosslinking treatment, and is intended to achieve desired physical properties together with the crosslinking treatment.

  Furthermore, there is also a proposal for a solar cell encapsulant using a metallocene linear low density polyethylene having a specific density range (see Patent Document 3). However, Patent Document 3 also does not disclose any specific guidelines other than the density for the usage form of the ethylene / α-olefin copolymer. This is presumably because the technique disclosed in Patent Document 3 is premised on the crosslinking treatment, and is intended to achieve desired physical properties together with the crosslinking treatment.

  There is also a proposal of a filling sheet made of a resin film made of a resin composition containing maleic anhydride-modified polyolefin (see Patent Document 4). However, in the solar cell module-filled sheet disclosed in Patent Document 4, free maleic anhydride remaining in the resin composition penetrated into the sheet under severe conditions exceeding the accelerated test conditions described in the document. There is a problem in that it is hydrolyzed with water to become maleic acid, which corrodes an electrode such as a silver electrode and lowers the photovoltaic power. Furthermore, there is no disclosure of the gel fraction, and there is also a problem that the dielectric breakdown voltage decreases when the gel is generated.

JP-A-8-283696 JP 2000-091611 A Japanese Patent Laid-Open No. 2007-150069 JP 2004-214641 A

  In view of the above-mentioned background, the object of the present invention is to clarify guidelines for obtaining desired physical properties (not necessarily accompanied by cross-linking) in a solar cell encapsulant using an ethylene-based resin composition. It is excellent in various properties such as adhesion to sheets and thin film electrodes, electrical insulation, transparency, moldability and process stability, and it is possible to improve productivity by omitting crosslinking as necessary. It is in providing a battery sealing material.

  The present invention further provides a solar cell sealing sheet using such an ethylene-based resin composition, and a solar cell module using the sealing material and / or the sealing sheet.

  As a result of intensive studies to solve the above problems, the present inventors have radically polymerized an ethylene polymer (A) in a specific density range, melting point range, melt flow rate range, molecular weight distribution range, and metal residue range. By using an ethylene-based resin composition containing a modified product obtained by modification with a polymerizable unsaturated compound (B1) and a radically polymerizable unsaturated compound (B2), adhesion, electrical insulation, transparency, moldability And it discovered that the solar cell sealing material which was excellent in process stability and was able to improve productivity by omitting bridge | crosslinking as needed was obtained, and resulted in this invention.

That is, the present invention
(1) An ethylene polymer (A) that simultaneously satisfies the following requirements a) to e):
A radically polymerizable unsaturated compound (B1) comprising an ethylenically unsaturated silane compound;
Selected from hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or their derivatives, vinyl ester compounds, vinyl chloride and carbodiimide compounds A radically polymerizable unsaturated compound (B2) comprising at least one compound
An ethylene-based resin composition containing a modified product obtained by modification.
a) Density is 900-940 kg / m ³
b) 90-125 ° C melting peak based on DSC
c) Melt flow rate (MFR2) measured at 190 ° C. and 2.16 kg load in accordance with JIS K-6721 is 0.1 to 100 g / 10 minutes d) Mw / Mn is 1.2 to 3.5
e) 0.1-50 ppm of metal residue
(2) (i) Modified product (1) obtained by modifying ethylene polymer (A) with radically polymerizable unsaturated compound (B1), or ethylene polymer (A) and ethylene / α-olefin Modified product (3) obtained by modifying a mixture of copolymer (C) with radically polymerizable unsaturated compound (B1)
A modified body selected from
(Ii) A modified product (2) obtained by modifying an ethylene polymer (A) with a radically polymerizable unsaturated compound (B2), or an ethylene polymer (A) and an ethylene / α-olefin copolymer. Modified product (4) obtained by modifying the mixture of (C) with the radical polymerizable unsaturated compound (B2)
A modified body selected from
The ethylene-based resin composition according to (1), which contains
(3) (i) Modified product (5) obtained by modifying ethylene polymer (A) with radical polymerizable unsaturated compound (B1) and radical polymerizable unsaturated compound (B2), or ethylene heavy A modified product (6) obtained by modifying a mixture of the compound (A) and the ethylene / α-olefin copolymer (C) with a radical polymerizable unsaturated compound (B1) and a radical polymerizable unsaturated compound (B2).
A modified body selected from
(Ii) A modified product (1) obtained by modifying an ethylene polymer (A) with a radically polymerizable unsaturated compound (B1), or an ethylene polymer (A) and an ethylene / α-olefin copolymer Modified product (3) obtained by modifying the mixture of (C) with the radical polymerizable unsaturated compound (B1)
A modified body selected from
The ethylene-based resin composition according to (1), which contains
(4) (i) Modified product (5) obtained by modifying ethylene polymer (A) with radical polymerizable unsaturated compound (B1) and radical polymerizable unsaturated compound (B2), or ethylene heavy A modified product (6) obtained by modifying a mixture of the compound (A) and the ethylene / α-olefin copolymer (C) with a radical polymerizable unsaturated compound (B1) and a radical polymerizable unsaturated compound (B2).
A modified body selected from
(Ii) A modified product (2) obtained by modifying an ethylene polymer (A) with a radically polymerizable unsaturated compound (B2), or an ethylene polymer (A) and an ethylene / α-olefin copolymer. Modified product (4) obtained by modifying the mixture of (C) with the radical polymerizable unsaturated compound (B2)
A modified body selected from
The ethylene-based resin composition according to (1), which contains
(5) The ethylene resin composition according to any one of (2) to (4), wherein the ethylene / α-olefin copolymer (C) satisfies the following requirement f).
f) density of 850 kg / m ³ or more, 895kg / m less than ³ (6) reaction for obtaining the modified product is ethylene polymer (A) or the ethylene-based polymer (A) and the ethylene · alpha-olefin copolymer A mixture of (C);
A radically polymerizable unsaturated compound (B1) and / or a radically polymerizable unsaturated compound (B2);
Organic peroxides,
The ethylene-based resin composition according to any one of (2) to (5), wherein the ethylene-based resin composition is formed by extrusion-melt modification.
(7) The ethylene resin composition according to (6), wherein the ethylene polymer (A) used in the reaction for obtaining the modified product is a powder of the ethylene polymer (A).
(8) The ethylene-based resin composition according to (6), wherein the ethylene-based polymer (A) used in the reaction for obtaining the modified body is a mixture of powder and pellets of the ethylene-based polymer (A). object.
(9) The reaction for obtaining the modified product is performed by impregnating the ethylene polymer (A) powder in advance with the radical polymerizable unsaturated compound (B1) and / or the radical polymerizable unsaturated compound (B2) and the organic peroxide. The ethylene resin composition according to (6), wherein the ethylene resin composition is formed in the presence of a mixture of the pellets of the ethylene polymer (A).
(10) Graft group concentration derived from the radical polymerizable unsaturated compound (B2) measured by infrared absorption spectrum of the ethylene resin composition is in the range of 0.05 to 5.0% by weight, and free radical polymerization The ethylene-based resin composition according to any one of (1) to (9), wherein the amount of the functional compound (B2) is 500 ppm or less and the gel fraction is 30% or less.
(11) The ethylene-based resin composition according to any one of (1) to (10), wherein the radical polymerizable unsaturated compound (B2) is an unsaturated carboxylic acid or a derivative thereof.
(12) Any one of claims (1) to (11), further comprising at least one additive selected from an ultraviolet absorber (D), a radical scavenger (E), and a heat stabilizer (F). The ethylene-based resin composition described in 1.
(13) A solar cell encapsulant comprising the ethylene-based resin composition according to any one of (1) to (12).
(14) The solar cell encapsulant according to any one of (1) to (13), wherein the ethylene-based resin composition is in a sheet form.
(15) The solar cell sealing material according to (13) or (14), which is integrated with a back surface sealing material for a solar cell module.
(16) A solar cell module obtained by using the solar cell sealing material according to (13) to (15).
(17) A thin film solar cell module obtained by using the solar cell encapsulating material according to (13) to (15).
(18) A crystalline solar cell module obtained by using the solar cell encapsulant described in (13) to (15) as a solar cell encapsulant on the back surface side.

  ADVANTAGE OF THE INVENTION According to this invention, the ethylene-type resin composition excellent in adhesiveness with glass, a back sheet | seat, and a thin film electrode, electrical insulation, transparency, a moldability, and process stability can be obtained. Furthermore, by using the ethylene-based resin composition, it has excellent adhesion to glass, backsheet, and thin film electrode, electrical insulation, transparency, and process stability, and also eliminates cross-linking as necessary. It is possible to obtain a solar cell encapsulant that can improve the above.

  The present invention further provides a solar cell sealing sheet using such an ethylene-based resin composition, and the sealing material and / or the sealing sheet, in addition to the excellent characteristics described above. Thus, it is possible to obtain a solar cell module excellent in cost and other economical efficiency.

  Moreover, the solar cell sealing material of this invention can also obtain a thin film solar cell with high moisture permeability resistance and a small fall of conversion efficiency.

  In the ethylene resin composition of the present invention, an ethylene polymer (A) that simultaneously satisfies the following requirements a) to e) is modified with a radically polymerizable unsaturated compound (B1) and a radically polymerizable unsaturated compound (B2). It contains a modified product obtained as described above.

  The ethylene resin composition of the present invention is a modified product obtained by modifying an ethylene polymer (A) that simultaneously satisfies the following requirements a) to e) with a radically polymerizable unsaturated compound (B1) ( 1) a modified product (2) obtained by modifying the ethylene polymer (A) with a radically polymerizable unsaturated compound (B2), the ethylene polymer (A) and an ethylene / α-olefin copolymer A modified product (3) obtained by modifying a mixture (C) with a radically polymerizable unsaturated compound (B1), a mixture of the ethylene polymer (A) and an ethylene / α-olefin copolymer (C) Modified with a radically polymerizable unsaturated compound (B2) (4), the ethylene polymer (A) is a radically polymerizable unsaturated compound (B1) and a radically polymerizable unsaturated compound (B2) Modified product obtained by modification with (5) and a mixture of the ethylene polymer (A) and the ethylene / α-olefin copolymer (C) is modified with a radical polymerizable unsaturated compound (B1) and a radical polymerizable unsaturated compound (B2). It is also a preferred embodiment that the modified product (6) obtained in this manner is contained in the combinations shown in Table 1 below (containing modified product a and modified product b in Table 1 below).

Hereinafter, the present invention will be described in detail.
Ethylene polymer (A)
The ethylene polymer (A) is not particularly limited as long as it satisfies the requirements of a) to e) and has a structural unit derived from ethylene.

  The ethylene polymer (A) used in the ethylene resin composition of the present invention is, for example, an ethylene homopolymer or a copolymer of ethylene and at least one α-olefin having 3 to 20 carbon atoms other than ethylene. A polymer can be mentioned. Here, as the α-olefin having 3 to 20 carbon atoms other than ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, Examples include 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like, and α-olefins having 4 to 10 carbon atoms are preferable.

Furthermore, the copolymer of ethylene and a cyclic olefin can also be mentioned. Here, as the cyclic olefin, a norbornene derivative, a tricyclo-3-decene derivative, a tricyclo-3-undecene derivative, a tetracyclo-3-dodecene derivative, a pentacyclo-4-pentadecene derivative, a pentacyclopentadecadiene derivative, a pentacyclo-3- Pentadecene derivatives, pentacyclo-4-hexadecene derivatives, pentacyclo-3-hexadecene derivatives, hexacyclo-4-heptadecene derivatives, heptacyclo-5-eicosene derivatives, heptacyclo-4-eicosene derivatives, heptacyclo-5-heneicosene derivatives, octacyclo-5-docosene Derivatives, nonacyclo-5-pentacocene derivatives, nonacyclo-6-hexacocene derivatives, cyclopentadiene-acenaphthylene adducts, 1,4-methano-1,4,4a, a- tetrahydrofluorene derivatives, 1,4-methano -1,4,4a, 5,10,10a hexa hydro anthracene derivatives, and the like cycloalkylene derivative having 3 to 20 carbon atoms. Among these, tetracyclo [4.4.0. ^12,5 . 1 ^7,10 ] -3-dodecene derivative and hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . ^09,14 ] -4-heptadecene derivatives, particularly tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene is preferred.

  These α-olefins and cyclic olefins may be used alone or in combination of two or more of α-olefin and cyclic olefin. These α-olefins and cyclic olefins may form a random copolymer with ethylene or a block copolymer.

Next, requirements a) to e) will be sequentially described.
[Requirement a)]
The density of the ethylene polymer (A) used in the ethylene resin composition of the present invention is 900 to 940 kg / m ³ , preferably 900 to 935 kg / m ³ , more preferably 900 to 930 kg / m ³ , Preferably it is 900-925 kg / m < ³ >, More preferably, it is 905-925 kg / m < ³ >, Most preferably, it is 905-923 kg / m < ³ >.

When the density is less than 900 kg / m ³ , the heat resistance of the sealing material is lowered, and when power is generated by sunlight with the module tilted, the glass and the electrodes gradually slide and the glass slides down. When the density exceeds 940 kg / m ³ , the flexibility of the sealing material is lowered, and cracking of the crystal cell and peeling of the silver electrode occur when the module is laminated. Moreover, it is necessary to increase the temperature at the time of laminate molding.

  The density depends on the comonomer content such as α-olefin of the ethylene polymer (A). The smaller the comonomer content, the higher the density, and the higher the comonomer content, the lower the density. Further, it is known that the comonomer content in the ethylene polymer (A) is determined by the composition ratio (comonomer / ethylene) of the comonomer and ethylene in the polymerization system (for example, Walter Kaminsky, Makromol. Chem. 193, p.606 (1992)).

  For this reason, it is possible to increase / decrease the density of an ethylene polymer (A) by increasing / decreasing comonomer / ethylene.

[Requirement b)]
The melting peak temperature based on DSC of the ethylene polymer (A) used in the ethylene resin composition of the present invention is 90 to 125 ° C, preferably 90 to 120 ° C, more preferably 90 to 115 ° C. When the temperature is lower than 90 ° C., the heat resistance of the sealing material is lowered, and when the module is tilted and power is generated by sunlight, the glass and the electrode gradually slide down. When the temperature exceeds 125 ° C., the flexibility of the sealing material decreases, and cracking of the crystal cell and peeling of the silver electrode occur when the module is laminated. Moreover, it is necessary to increase the temperature at the time of laminate molding.
Similarly to the density, the melting peak temperature depends on the comonomer content such as the α-olefin of the ethylene polymer (A). The lower the comonomer content, the higher the melting peak, and the higher the comonomer content, the lower the melting peak. Further, it is known that the comonomer content in the ethylene polymer (A) is determined by the composition ratio (comonomer / ethylene) of the comonomer and ethylene in the polymerization system (for example, Walter Kaminsky, Makromol. Chem. 193, p.606 (1992)).

  For this reason, it is possible to increase or decrease the melting peak of the ethylene polymer (A) by increasing or decreasing comonomer / ethylene.

[Requirement c)]
The melt flow rate (MFR2) measured at 190 ° C. under a 2.16 kg load in accordance with JIS K-6721 of the ethylene polymer (A) used in the ethylene resin composition of the present invention is 0.1 to 0.1. The amount is 100 g / 10 minutes, preferably 0.5 to 50 g / 10 minutes, and more preferably 0.5 to 20 g / 10 minutes. When the MFR2 is less than 0.1 g / 10 minutes, the fluidity of the composition is lowered, and the productivity at the time of sheet extrusion molding is lowered. On the other hand, if it exceeds 100 g / 10 minutes, the fluidity is too high and sheet molding is difficult. Further, mechanical properties such as the tensile strength of the sheet are lowered.

  The melt flow rate (MFR2) strongly depends on the molecular weight. The smaller the melt flow rate (MFR2), the larger the molecular weight, and the larger the melt flow rate (MFR2), the smaller the molecular weight. Further, it is known that the molecular weight of the ethylene-based polymer (A) is determined by the composition ratio (hydrogen / ethylene) of hydrogen and ethylene in the polymerization system (for example, Kazuo Soga, KODASHASHA “CATARYTIC OLEFIN POLYMERISATION”). ", 376 (1990)). For this reason, by increasing / decreasing hydrogen / ethylene, it is possible to produce an ethylene polymer (A) having a melt flow rate (MFR2) that is the upper limit or the lower limit of the requirement c) of the present invention.

[Requirement d)]
The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC of the ethylene polymer (A) used in the ethylene resin composition of the present invention is 1.2-3. 0.5, preferably 1.2 to 3.2, more preferably 1.2 to 2.8. When Mw / Mn is less than 1.2, living polymerization occurs, the amount of catalyst per unit weight of the polymer increases, the production cost of the polymer increases, and this is industrially disadvantageous. When Mw / Mn is more than 3.5, the impact strength of the obtained ethylene-based resin composition is lowered, and the sheet is sticky, the sheet is blocked, and the sheet feeding property is deteriorated.

  The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is generally affected by the composition distribution. For example, in the case of batch slurry polymerization, the comonomer conversion rate is kept low. Mw / Mn decreases, and Mw / Mn tends to increase with increasing comonomer conversion. In addition, by shortening the polymerization time, the comonomer conversion rate is low, the alteration of the active species of the polymerization catalyst can be suppressed, the composition distribution is narrow, and Mw / Mn tends to be small. However, by increasing the polymerization time, the comonomer conversion rate is also high, the polymerization catalyst is altered, the composition distribution is widened, and Mw / Mn tends to increase. Further, in continuous gas phase or solution polymerization, by shortening the average residence time, the deterioration of the polymerization catalyst can be suppressed, the composition distribution is narrow, and Mw / Mn tends to be small. However, when the average residence time is increased, the active species of the polymerization catalyst are altered, the composition distribution is widened, and Mw / Mn tends to increase.

[Requirement e)]
The metal residue of the ethylene-based polymer (A) used in the ethylene-based resin composition of the present invention is 0.1 to 50 ppm, preferably 0.1 to 45 ppm, and more preferably 0.1 to 40 ppm. If the metal residue is less than 0.1 ppm, the decalcification operation of the polymerization catalyst is essential, the plant fixing cost, the utility cost, etc. become high, and the product cost increases, and further, a large amount of acid or alkali used for the deashing treatment It becomes necessary and the possibility that it will remain increases, and the remaining acid or alkali may cause corrosion of the electrode or the like. When the metal residue exceeds 50 ppm, the volume resistivity and dielectric breakdown resistance are reduced due to the metal residue.

  The metal residue depends on, for example, the polymerization activity of the transition metal of the metallocene compound that becomes an active species of the polymerization catalyst. If the polymerization catalyst has a high polymerization activity, the metal residue can be reduced naturally. Therefore, it becomes one of the suitable methods to use a polymerization catalyst with high polymerization activity. Polymerization at the optimum polymerization temperature of the polymerization catalyst used, or increasing the polymerization pressure as much as possible to increase the monomer concentration per polymerization catalyst is one of the preferred methods for increasing the polymerization activity and reducing the metal residue. It is. In addition, for example, the metallocene compound may be an organoaluminum oxy compound, a compound that reacts with the metallocene compound to form an ion pair, and an organoaluminum compound. This is one of the preferred methods for reducing the metal residue. In addition, improving the polymerization activity using various techniques can be a suitable technique for reducing the metal residue. However, there is a method of reducing the metal residue by decalcification using a chelating agent such as acid and alkali or methyl acetoacetate, but the acid and alkali or chelating agent remains in the ethylene polymer (A). Then, since corrosion of a thin film electrode is promoted, it is difficult to be one of suitable methods in the present invention.

Production Method of Ethylene Polymer (A) The ethylene polymer (A) of the present invention can be produced by using a conventionally known ethylene polymerization catalyst component. Examples thereof include Ziegler-Natta catalysts and metallocene compounds. Among these, a metallocene compound having a high polymerization activity per unit transition metal exhibiting a polymerization activity is preferable because an ethylene polymer (A) having a small amount of metal residue can be obtained without performing a deashing treatment. As the metallocene compound, for example, the metallocene compounds described in JP-A-2006-077261, JP-A-2008-231265, JP-A-2005-314680, and the like can be used. As long as the coalescence is satisfied, a metallocene compound having a structure different from that of the metallocene compound described in the above-mentioned patent document may be used, or two or more metallocene compounds selected from them may be blended and used. Furthermore, the preferable aspect at the time of using a metallocene compound is, for example,
(I) a conventionally known metallocene compound, and (II) (II-1) an organoaluminum oxy compound,
(II-2) at least one compound selected from (II-2) a compound that reacts with the metallocene compound (I) to form an ion pair, and (II-3) an organoaluminum compound (sometimes called a cocatalyst) In the presence of an olefin polymerization catalyst consisting of the above, it can be obtained by supplying one or more monomers selected from ethylene, α-olefin and the like.

  (II-1) Organoaluminum oxy compounds, (II-2) Compounds that react with the metallocene compound (I) to form ion pairs, and (II-3) Organoaluminum compounds are also disclosed, for example, in JP-A-2006. The metallocene compounds described in JP-0777261, JP 2008-231265, JP 2005-314680, and the like can be used, and the ethylene-based polymer is defined by the requirements a) to e) of the present application. As long as the above requirements are satisfied, a metallocene compound having a structure different from that of the metallocene compound described in the above-mentioned patent document may be used. These compounds may be introduced individually or in advance into the polymerization atmosphere. Further, for example, it may be supported on a particulate inorganic oxide carrier described in JP-A-2005-314680.

Polymerization The polymerization of the ethylene polymer (A) of the present invention can be carried out by any of the conventionally known gas phase polymerization methods, or liquid phase polymerization methods such as slurry polymerization methods and solution polymerization methods. Preferably, it is carried out by a gas phase polymerization method or slurry polymerization method which is highly active and reduces metal residues. Slurry polymerization and solution polymerization are propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene and other aliphatic hydrocarbons; cyclopentane, cyclohexane, methylcyclopentane and other alicyclic hydrocarbons; benzene, toluene Aromatic hydrocarbons such as xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane or mixtures thereof, or an inert hydrocarbon medium. Of these inert hydrocarbon solvents, aliphatic hydrocarbons and alicyclic hydrocarbons are preferred.

  The ethylene polymer (A) obtained by the polymerization method may be subjected to a conventionally known deashing treatment used for an olefin polymer to remove the catalyst component and the fine inorganic oxide support.

Radical polymerizable unsaturated compound (B1)
The radically polymerizable unsaturated compound (B1) used in the present invention is characterized by being an ethylenically unsaturated silane compound, and conventionally known ones can be used. Ethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxyethoxysilane), γ-glycidoxypropyltripyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethylethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethylmethoxysilane, 3 -Methacryloxypropylmethyl diet Sisilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Trimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N -Phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane and the like can be used. Preferably, γ-glycidoxypropyl-tripril methoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3- Acoxypropyltrimethoxysilane is mentioned. More preferably, vinyltriethoxysilane, vinyltrimethoxysilane, 3-acryloxypropyltrimethylsilane, vinyltrimethoxysilane, 3-acryloxypropyltrimethylsilane, which have good adhesiveness, can shorten the lamination time during lamination molding with each adherend, have low steric hindrance and high graft modification efficiency. Methoxysilane is mentioned.

  The blending amount of the radically polymerizable unsaturated compound (B1) is 100 parts by weight of the ethylene polymer (A) or a mixture of the ethylene polymer (A) and the ethylene / α-olefin copolymer (C). The radically polymerizable unsaturated compound (B1) is usually 0.1 to 5 parts by weight, preferably 0.1 to 4 parts by weight. When the blending amount of the radical polymerizable unsaturated compound (B1) is within the above range, the adhesiveness of the ethylene resin composition is sufficiently improved, and the transparency and flexibility of the ethylene resin composition are adversely affected. It is preferable because it is not.

Radical polymerizable unsaturated compound (B2)
The radical polymerizable unsaturated compound (B2) used in the present invention is a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group ethylenically unsaturated compound, an aromatic vinyl compound, or an unsaturated carboxylic acid. Alternatively, derivatives thereof, vinyl ester compounds, vinyl chloride, carbodiimide compounds and the like can be mentioned.

  As the radically polymerizable unsaturated compound (B2), an unsaturated carboxylic acid or a derivative thereof is particularly preferable. Examples of unsaturated carboxylic acids or derivatives thereof include unsaturated compounds having at least one carboxylic acid group, esters of a compound having a carboxylic acid group and an alkyl alcohol, and unsaturated compounds having at least one carboxylic anhydride. Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group.

  Specific examples of the compound include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid [trademark] (endocis-bicyclo [2.2. 1) unsaturated carboxylic acids such as hept-5-ene-2,3-dicarboxylic acid); or derivatives thereof such as acid halides, amides, imides, anhydrides, esters and the like.

  Specific examples of such derivatives include, for example, maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, 2-methylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dimethylmaleic anhydride, 4- Methyl-4-cyclohexene-1,2-dicarboxylic anhydride monomethyl maleate, dimethyl maleate, glycidyl malate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. Is mentioned.

  These unsaturated carboxylic acids and / or derivatives thereof can be used singly or in combination of two or more. Of these, unsaturated dicarboxylic acids or their anhydrides are preferred, and maleic acid, nadic acid or their acid anhydrides are particularly preferred.

  The hydrolyzable unsaturated silane is a compound having a radical polymerizable unsaturated group and an alkoxysilyl group or silyl group in the molecule, and a hydrolyzable silyl group bonded to a vinyl group by an alkylene group in some cases. Or a compound having a hydrolyzable silyl group bonded with an ester amide such as acrylic acid or methacrylic acid. Specific examples thereof include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, monovinylsilane, monoallylsilane and the like. Examples of the unsaturated halogenated hydrocarbon include vinyl chloride and vinylidene chloride.

  The blending amount of the radically polymerizable unsaturated compound (B2) is 100 parts by weight of the ethylene polymer (A) or a mixture of the ethylene polymer (A) and the ethylene / α-olefin copolymer (C). The radically polymerizable unsaturated compound (B2) is usually 0.1 to 5 parts by weight, preferably 0.1 to 4 parts by weight. If the blending amount of the radically polymerizable unsaturated compound (B2) is within the above range, the adhesiveness of the ethylene resin composition is sufficiently improved, and the transparency and flexibility of the ethylene resin composition are adversely affected. It is preferable because it is not.

Ethylene / α-olefin copolymer (C)
In the ethylene / α-olefin copolymer (C) used in the present invention, ethylene and an α-olefin having 3 to 20 carbon atoms can be used singly or in combination of two or more. Among the α-olefins having 3 to 20 carbon atoms, α-olefins having 4 or more carbon atoms are preferable, and those having 4 to 8 carbon atoms are particularly preferable. Examples of such α-olefins include 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, 4-methyl-1-pentene, and 1-octene. 1 type, or 2 or more types of these are used. Of these, 1-butene, 1-pentene, 1-hexene and 4-methyl-1-pentene are preferred because of their availability. Furthermore, the polymerization form of the ethylene / α-olefin copolymer (C) may be a random copolymer or a block copolymer.

The density of the ethylene / α-olefin copolymer (C) is 850 to less than 895 kg / m ³ . Preferably it is 850-890 kg / m < ³ >, More preferably, it is 850-880 kg / m < ³ >. When the density is more than 895 kg / m ³ , tackiness cannot be improved, and there is a tendency that adhesion is not improved. If the density is less than 850 kg / m ³ , the compatibility with the ethylene polymer (A) decreases, bleeding out to the sheet surface occurs, and the sheet feeding property tends to decrease. In addition, stickiness to the chill roll occurs during sheet forming, which tends to make sheet thickness control and sheet forming difficult.

  The structural unit derived from the α-olefin of the ethylene / α-olefin copolymer (C) is 9 to 22 mol%. Preferably, it is 10-22 mol%, More preferably, it is 11-17 mol%. When the structural unit derived from the α-olefin is less than 9 mol%, tackiness cannot be improved, and improvement in adhesiveness tends not to be observed. When the structural unit derived from the α-olefin exceeds 22 mol%, the compatibility with the ethylene polymer (A) is lowered, bleeding out to the sheet surface occurs, and the sheet feeding property tends to be lowered. In addition, stickiness to the chill roll occurs during sheet forming, which tends to make sheet thickness control and sheet forming difficult.

  The melting peak based on DSC of the ethylene / α-olefin copolymer (C) is 85 ° C. or less or in a range where it is not substantially observed. Preferably, it is 80 ° C. or lower or substantially not observed, more preferably 75 ° C. or lower or substantially unobserved. When the melting peak exceeds 85 ° C., tackiness cannot be improved, and no improvement in adhesiveness tends to be observed.

  The melt flow rate (MFR2) measured at 190 ° C. under a load of 2.16 kg in accordance with JIS K-6721 of the ethylene / α-olefin copolymer (C) is 0.1 to 100 g / 10 min. Range. Preferably, it is 0.1-80 g / 10 minutes, More preferably, it is 0.5-80 g / 10 minutes, More preferably, it is 1.0-50 g / 10 minutes. When the MFR2 is less than 0.1 g / 10 minutes, the fluidity of the resin composition is lowered, and the productivity at the time of sheet extrusion molding is lowered. In addition, the scorch property of the resin composition becomes high and gelation is likely to occur, and the torque of the extruder increases, which may make sheet molding difficult. Even if a sheet is obtained, unevenness may occur on the surface of the sheet due to the gel generated in the extruder, and the appearance may deteriorate. In addition, when a voltage is applied, cracks are generated around the gel within the sheet, and the dielectric breakdown resistance is reduced. Furthermore, moisture permeability at the gel object interface is likely to occur, and moisture permeability is reduced. Moreover, since unevenness | corrugation generate | occur | produces on the sheet | seat surface, at the time of the lamination process of a solar cell module, adhesiveness with glass, a thin film electrode, and a back sheet deteriorates, and since adhesion becomes inadequate, adhesiveness also falls. If the MFR2 exceeds 100 g / 10 min, the molecular weight is low, so adhesion to a roll surface such as a chill roll occurs, and peeling is required, making it difficult to form a sheet with a uniform thickness, and the resin composition is not stiff. , It tends to be difficult to form a thick sheet of 0.3 mm or more.

  Further, the MFR10 / MFR2 which is the ratio of the melt flow rate (MFR10) and MFR2 measured at 190 ° C. and 10 kg load according to JIS K-6721 of the ethylene / α-olefin copolymer (C) is 5 It is in the range of 0.0 to 8.0. Preferably, MFR10 / MFR2 is 5.5 to 8.0, and more preferably, MFR10 / MFR2 is 5.5 to 7.5. When MFR10 / MFR2 is less than 5, it is difficult to produce an ethylene / α-olefin copolymer. When MFR10 / MFR2 is more than 8, low temperature characteristics tend to deteriorate.

  The molecular weight distribution Mw / Mn, which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC of the ethylene / α-olefin copolymer (C), is in the range of 1.2 to 3.5. is there. Preferably, it is 1.5-3.5, More preferably, it is 1.7-3.2. In order to produce a product having an Mw / Mn of less than 1.2, the ethylene / α-olefin copolymer must be polymerized by living polymerization, and no catalytic activity is obtained, or a conventionally known polymerization method Since it is necessary to separate the low molecular weight component and the high molecular weight component of the ethylene / α-olefin copolymer obtained in (1), there is a problem that the production cost is high. In addition, since the temperature range in which molding can be performed is narrow and the amount discharged by the extruder is difficult to be uniformly produced, it tends to be difficult to form a sheet having a uniform thickness. If Mw / Mn is more than 3.5, the sheet has a low molecular weight component, so that the sheet is sticky, the sheet is blocked, and the sheet feeding property tends to deteriorate. In general, it is known that when the molecular weight distribution Mw / Mn is widened, the composition distribution is also widened. The sheet is sticky, the sheet is blocked, and the sheet feeding property tends to deteriorate. Further, since the low molecular weight bleeds to the surface of the sheet, the adhesion is hindered and the adhesiveness is lowered.

Production Method of Ethylene / α-Olefin Copolymer (C) The production method of the ethylene / α-olefin copolymer (C) of the present invention is not particularly limited, and various catalysts such as titanium compounds, vanadium compounds or metallocene compounds can be used. Can be used. Among these, it is preferable to use a metallocene compound that makes it easy to obtain an ethylene / α-olefin copolymer satisfying the above-described molecular weight distribution Mw / Mn and composition distribution. As the metallocene compound, for example, the metallocene compounds described in JP-A-2006-077261, JP-A-2008-231265, JP-A-2005-314680, and the like can be used. -As long as each characteristic of the olefin copolymer (A) is satisfied, a metallocene compound having a structure different from the metallocene compound described in the patent document may be used, or two or more kinds of metallocene compounds selected from them may be blended. May be used. Furthermore, the preferable aspect at the time of using a metallocene compound is, for example,
(I) a conventionally known metallocene compound, and (II) (II-1) an organoaluminum oxy compound,
(II-2) a compound that reacts with the metallocene compound (I) to form an ion pair,
And (II-3) 1 selected from ethylene, α-olefin, and the like in the presence of an olefin polymerization catalyst comprising at least one compound selected from organoaluminum compounds (sometimes referred to as a co-catalyst). More than one monomer can be supplied.

  Examples of (II-1) an organoaluminum oxy compound, (II-2) a compound that reacts with the metallocene compound (I) to form an ion pair, and (II-3) an organoaluminum compound include, for example, The metallocene compound described in Japanese Patent No. 077261, JP-A-2008-231265, JP-A-2005-314680 and the like can be used, and is different from the metallocene compound described in the above-mentioned patent document as long as the effects of the present invention are satisfied. An ethylene / α-olefin copolymer (C) may be produced using a metallocene compound having a structure. These compounds may be introduced individually or in advance into the polymerization atmosphere. Further, for example, it may be supported on a particulate inorganic oxide carrier described in JP-A-2005-314680.

Polymerization The ethylene / α-olefin copolymer (C) of the present invention can be polymerized by any of the conventionally known gas phase polymerization methods, or liquid phase polymerization methods such as slurry polymerization methods and solution polymerization methods. Preferably, it is performed by a liquid phase polymerization method such as a solution polymerization method.

When an ethylene / α-olefin copolymer is produced by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms using the metallocene compound as described above, the metallocene compound (I) The amount is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² mol per liter of volume.

  In the compound (II-1), the molar ratio [(II-1) / M] of the compound (II-1) and all transition metal atoms (M) in the compound (I) is usually 1 to 10,000, preferably It is used in such an amount that it becomes 10-5000. Compound (II-2) has a molar ratio [(II-2) / M] of all transition metals (M) in Compound (I) of usually 0.5 to 50, preferably 1 to 20. Used in various amounts. Compound (II-3) is generally used in an amount of 0 to 5 mmol, preferably about 0 to 2 mmol, per liter of polymerization volume.

  In the solution polymerization according to the present invention, by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of the metallocene compound as described above, the comonomer content is high, the composition distribution is narrow, and the molecular weight. An ethylene / α-olefin copolymer (C) having a narrow distribution can be produced efficiently. Here, the charged molar ratio of ethylene to the α-olefin having 3 to 20 carbon atoms is usually ethylene: α-olefin = 10: 90 to 99.9: 0.1, preferably ethylene: α-olefin = 30. : 70 to 99.9: 0.1, more preferably ethylene: α-olefin = 50: 50 to 99.9: 0.1.

  Examples of the α-olefin having 3 to 20 carbon atoms include linear or branched α-olefins such as propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned. The α-olefin that can be used in the solution polymerization of the present invention includes polar group-containing olefins. Examples of the polar group-containing olefin include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid and maleic anhydride, and metal salts such as sodium salts thereof; methyl acrylate, ethyl acrylate, Α, β-unsaturated carboxylic esters such as n-propyl acrylate, methyl methacrylate and ethyl methacrylate; vinyl esters such as vinyl acetate and vinyl propionate; unsaturated glycidyl such as glycidyl acrylate and glycidyl methacrylate And the like. Vinylcyclohexane, diene or polyene; aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, methoxystyrene, vinylbenzoic acid, methyl vinylbenzoate Styrenes such as vinyl benzyl acetate, hydroxystyrene, p-chlorostyrene, divinylbenzene; and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene, etc. may be allowed to coexist in the reaction system to proceed with high-temperature solution polymerization. Is possible. Among the α-olefins described above, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferably used. In the solution polymerization method according to the present invention, cyclic olefins having 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl- 2-norbornene or the like may be used in combination.

  “Solution polymerization” according to the present invention is a general term for a method of performing polymerization in a state where a polymer is dissolved in an inert hydrocarbon solvent described later. In the solution polymerization according to the present invention, the polymerization temperature is usually 0 to 200 ° C, preferably 20 to 190 ° C, more preferably 40 to 180 ° C.

In the solution polymerization according to the present invention, when the polymerization temperature is less than 0 ° C., the polymerization activity is extremely lowered, so that it is not practical in terms of productivity. Further, the molecular terminal of the ethylene / α-olefin copolymer The amount of double bonds decreases. In addition, in the polymerization temperature range of 0 ° C. or higher, as the temperature increases, the solution viscosity at the time of polymerization decreases, the heat of polymerization is easily removed, and the double molecular end of the ethylene / α-olefin copolymer is further reduced. Increases the amount of binding. However, when the polymerization temperature exceeds 200 ° C., the polymerization activity is extremely lowered, and therefore, it is not practical in terms of productivity. The polymerization pressure is usually under normal pressure to 10 MPa gauge pressure, preferably normal pressure to 8 MPa gauge pressure, and the copolymerization can be carried out in any of batch, semi-continuous and continuous methods. The reaction time (average residence time when the copolymerization reaction is carried out in a continuous manner) varies depending on conditions such as the catalyst concentration and polymerization temperature, and can be appropriately selected, but is usually 1 minute to 3 hours, preferably 10 minutes to 2.5 hours. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the obtained ethylene / α-olefin copolymer can also be adjusted by changing the hydrogen concentration or polymerization temperature in the polymerization system within the scope of the present invention. Furthermore, it can also adjust with the quantity of the compound (II) to be used. When hydrogen is added, the amount is suitably about 0.001 to 5,000 NL per kg of the ethylene / α-olefin copolymer to be produced. In addition, the vinyl group and vinylidene group present at the molecular ends of the obtained ethylene / α-olefin copolymer (C) can be adjusted by increasing the polymerization temperature and decreasing the amount of hydrogenation as much as possible. In the case of MFR10 / MFR2 of the obtained ethylene / α-olefin copolymer, the long-chain branched structure in the ethylene-based polymer is formed by β-hydrogen elimination reaction in the case of coordination polymerization as described in Examples below. It is considered that a molecular chain (macromonomer) having a generated terminal vinyl group is generated by reinsertion. Therefore, the MFR10 / MFR2 in the ethylene / α-olefin copolymer can be controlled by increasing or decreasing the ratio of the macromonomer concentration to the ethylene concentration ([macromonomer] / [ethylene]) in the solution. . Generally, when [macromonomer] / [ethylene] is high, the amount of long-chain branching in the ethylene / α-olefin copolymer increases, and when [macromonomer] / [ethylene] is low, the ethylene / α-olefin copolymer is high. The amount of long chain branching in the coalesce decreases. Specific methods for increasing / decreasing [macromonomer] / [ethylene] in the solution include the following methods. In particular,
[1] Polymerization temperature The lower the polymerization temperature, the less likely the β-hydrogen elimination reaction occurs. Therefore, if the polymerization temperature is lowered, [macromonomer] / [ethylene] is decreased, and MFR10 / MFR2 in the ethylene / α-olefin copolymer is decreased.
[2] Polymer concentration If the polymer concentration in the solution is lowered, the macromonomer concentration is also relatively lowered. Therefore, [macromonomer] / [ethylene] is reduced, and MFR10 / in the ethylene / α-olefin copolymer is reduced. MFR2 decreases.
[3] Ethylene conversion ratio If the ethylene conversion ratio is lowered, the ethylene concentration in the solution increases, so [macromonomer] / [ethylene] decreases, and MFR10 / MFR2 in the ethylene / α-olefin copolymer becomes descend.
[4] Solvent type When the polymerization solvent is a high-boiling solvent, the ethylene concentration in the solution increases, so [macromonomer] / [ethylene] decreases, and MFR10 / MFR2 in the ethylene / α-olefin copolymer. Will decline.

  In addition to controlling the β-hydrogen elimination reaction, the [macromonomer] / [ethylene]) can be increased or decreased by controlling the chain transfer reaction to Al, etc., in the ethylene / α-olefin copolymer. It is also possible to change MFR10 / MFR2.

  The solvent used in the solution polymerization according to the present invention is usually an inert hydrocarbon solvent, preferably a saturated hydrocarbon having a boiling point of 50 ° C. to 200 ° C. under normal pressure. Specific examples include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene; and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. Aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane are also included in the category of “inert hydrocarbon solvents” related to the high-temperature solution polymerization of the present invention. The use is not limited. As described above, in the solution polymerization according to the present invention, not only the conventionally used aromatic hydrocarbon-soluble organoaluminum oxy compounds, but also MMAO, which is dissolved in aliphatic hydrocarbons and alicyclic hydrocarbons, A modified methylaluminoxane such as TMAO-341 (manufactured by Tosoh Finechem Co., Ltd.) can be used. As a result, if aliphatic hydrocarbons or alicyclic hydrocarbons are used as the solvent for the solution polymerization, there is a possibility that aromatic hydrocarbons are mixed in the polymerization system or in the ethylene / α-olefin copolymer to be produced. It became possible to eliminate almost completely. That is, the solution polymerization method according to the present invention has a feature that the environmental load can be reduced and the influence on human health can be minimized.

  In order to suppress variations in physical property values, the ethylene / α-olefin copolymer obtained by the polymerization reaction and other components added as required are melted by any method and subjected to kneading, granulation, or the like. Is preferred.

  In particular, the blending amount of the ethylene / α-olefin copolymer (C) is a weight ratio with respect to a total of 100 parts by weight of the ethylene polymer (A) and the ethylene / α-olefin copolymer (C). Copolymer (A) / ethylene / α-olefin copolymer (C) = 100/0 to 10/90% by weight. Preferably, ethylene-based polymer (A) / ethylene / α-olefin copolymer = 100/0 to 20/80% by weight, more preferably ethylene-based polymer (A) / ethylene / α-olefin copolymer = 100/0 to 40/60% by weight, more preferably ethylene polymer (A) / ethylene / α-olefin copolymer = 100/0 to 60/40% by weight.

  When the weight ratio of the ethylene / α-olefin copolymer is more than 90% by weight, the heat resistance of the sealing material decreases, and when power is generated by sunlight with the module tilted, the glass and electrodes gradually slip. The glass tends to slide down. Further, stickiness to the chill roll during sheet forming occurs, and the sheet thickness control and sheet forming tend to be difficult. Furthermore, sheet blocking occurs, and the sheet feeding property tends to deteriorate. By blending an ethylene / α-olefin copolymer, the tackiness of the ethylene-based resin composition is improved, and the back surface protection for solar cell modules such as each adherend, particularly polyester resin, steel plate, plastic plate and FRP plate, etc. It tends to improve the adhesion to the sheet.

The total density of the resin components after blending the ethylene polymer (A) and the ethylene / α-olefin copolymer is 855 to 940 kg / m ³ .

Organic peroxide The organic peroxide used in the present invention comprises a radical polymerizable unsaturated compound (B1), a radical polymerizable unsaturated compound (B2), an ethylene polymer (A), an ethylene / α-olefin copolymer. It is used as a radical initiator when graft-modifying the compound (C).

  By graft-modifying the radically polymerizable unsaturated compound (B1) and the radically polymerizable unsaturated compound (B2) to the ethylene polymer (A) and the ethylene / α-olefin copolymer (C), glass, back A modified body of the ethylene polymer (A) having good adhesion to the sheet and electrode is obtained.

  The organic peroxide preferably used in the present invention is an ethylene polymer (A), an ethylene / α-olefin copolymer (C), a radical polymerizable unsaturated compound (B1) and a radical polymerizable unsaturated compound (B2). ) May be used as long as it can be graft-modified, and the type is not particularly limited, but preferred specific examples include dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy- 2-ethylhexanoate, dibenzoyl peroxide, cyclohexanone peroxide, di-t-butyl perphthalate, cumene hydroperoxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-amylperoxy 2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, 1,1-di (t-amylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-amylperoxy) cyclohexane, t-amylperoxyisononanoate, t-amylperoxynormal octoate, 1,1-di (t- Butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, 2,5 -Dimethyl-2,5-di (benzoylperoxy) hexane, t-amyl-peroxybenzoate T-butyl peroxyacetate, t-butyl peroxy isononanoate, t-butyl peroxybenzoate, 2,2-di (butyl peroxy) butane, n-butyl-4,4-di (t-butyl peroxy) -Oxy) petitate, methyl ethyl ketone peroxide, ethyl 3,3-di (t-butyl peroxy) butyrate, dicumyl peroxide, t-butyl cumyl peroxide, t-butyl peroxybenzoate, di-t-butyl peroxide, Examples include 1,1,3,3-tetralamethylbutyl hydroperoxide and acetylacetone peroxide. Preferably, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperoxy-2 -Ethyl hexyl carbonate, t-butyl peroxybenzoate, etc. are mentioned.

  The amount of the organic peroxide is 0.01 to 1 with respect to 100 parts by weight of the ethylene polymer (A) or the mixture of the ethylene polymer (A) and the ethylene / α-olefin copolymer (C). 0.0 part by weight, preferably 0.01 to 0.5 part by weight. If the amount of the organic peroxide is less than 0.01 parts by weight, a modified product with good adhesion cannot be obtained. When the blending amount of the organic peroxide is more than 1 part by weight, the gel fraction of the modified ethylene polymer obtained is increased, the surface of the resulting sheet or the like is uneven, and the appearance is deteriorated. Further, when a voltage is applied, cracks are generated around the gel inside the sheet or the like, and the dielectric breakdown resistance is lowered. Furthermore, when the gel fraction is high, moisture permeability at the gel interface is likely to occur, and moisture permeability is reduced.

Modified Polymer of Ethylene Polymer (A), Ethylene / α-Olefin Copolymer (C) The modified product constituting the ethylene resin composition according to the present invention is an ethylene that simultaneously satisfies the above requirements a) to e). The polymer (A) is a modified product obtained by modifying the radical polymerizable unsaturated compound (B1) and / or the radical polymerizable unsaturated compound (B2). The ethylene polymer ( What modified | denatured the mixture of A) and an ethylene-alpha-olefin copolymer (C) with the radically polymerizable unsaturated compound (B1) and / or the radically polymerizable unsaturated compound (B2) is preferable.

As a combination of the ethylene polymer (A), the radical polymerizable unsaturated compound (B1), the radical polymerizable unsaturated compound (B2) and the ethylene / α-olefin copolymer (C) used for the production of the modified product. The following <1> to <12> are preferable.
<1> A modified product (1) obtained by modifying an ethylene polymer (A) with a radically polymerizable unsaturated compound (B1) and an ethylene polymer (A) with a radically polymerizable unsaturated compound (B2). ) Modified product (2) obtained by modification with <2> a mixture of ethylene polymer (A) and ethylene / α-olefin copolymer (C) is a radically polymerizable unsaturated compound. A modified polymer (3) obtained by modification with (B1), a mixture of an ethylene polymer (A) and an ethylene / α-olefin copolymer (C) is modified with a radical polymerizable unsaturated compound (B2). A modified product (4) obtained by modifying a modified product <3> ethylene polymer (A) with a radical polymerizable unsaturated compound (B1), ethylene・ Radical polymerization of a mixture of α-olefin copolymer (C) Modified body containing modified body (4) obtained by modification with unsaturated compound (B2)
<4> A modified product (3) obtained by modifying a mixture of an ethylene polymer (A) and an ethylene / α-olefin copolymer (C) with a radically polymerizable unsaturated compound (B1); A modified product (2) obtained by modifying a polymer (A) with a radically polymerizable unsaturated compound (B2), a modified product <5> containing an ethylene-based polymer (A) as a radically polymerizable unsaturated compound ( B1) and a modified product (5) obtained by modifying with a radically polymerizable unsaturated compound (B2) and a modified product obtained by modifying an ethylene polymer (A) with a radically polymerizable unsaturated compound (B1). Modified body containing body (1) <6> A mixture of ethylene polymer (A) and ethylene / α-olefin copolymer (C) is prepared by radically polymerizable unsaturated compound (B1) and radically polymerizable Obtained by modification with saturated compound (B2) Modified product (6), a modified product (3) obtained by modifying a mixture of an ethylene polymer (A) and an ethylene / α-olefin copolymer (C) with a radically polymerizable unsaturated compound (B1). A modified product (5) obtained by modifying the ethylene polymer (A) with a radical polymerizable unsaturated compound (B1) and a radical polymerizable unsaturated compound (B2); A modified product containing a modified product (3) obtained by modifying a mixture of an ethylene polymer (A) and an ethylene / α-olefin copolymer (C) with a radical polymerizable unsaturated compound (B1) <8> Obtained by modifying a mixture of ethylene polymer (A) and ethylene / α-olefin copolymer (C) with radically polymerizable unsaturated compound (B1) and radically polymerizable unsaturated compound (B2). Modified product (6) and ethylene heavy The modified product (9) obtained by modifying the product (A) with the radically polymerizable unsaturated compound (B1) and the modified product <9> ethylene-based polymer (A) containing the radically polymerizable unsaturated compound ( B1) and a modified product (5) obtained by modifying with a radically polymerizable unsaturated compound (B2) and a modified product obtained by modifying an ethylene polymer (A) with a radically polymerizable unsaturated compound (B2). The modified body containing the body (2) <10> A mixture of the ethylene polymer (A) and the ethylene / α-olefin copolymer (C), the radical polymerizable unsaturated compound (B1) and the radical polymerizable unsaturated A modified product (6) obtained by modification with the compound (B2), and a mixture of the ethylene polymer (A) and the ethylene / α-olefin copolymer (C) with the radical polymerizable unsaturated compound (B2). Modified body obtained by modification (4) A modified product (5) obtained by modifying an ethylene polymer (A) with a radical polymerizable unsaturated compound (B1) and a radical polymerizable unsaturated compound (B2); Modified product <12> ethylene containing modified product (4) obtained by modifying a mixture of polymer (A) and ethylene / α-olefin copolymer (C) with radically polymerizable unsaturated compound (B2) Modified product (6) obtained by modifying a mixture of a polymer (A) and an ethylene / α-olefin copolymer (C) with a radical polymerizable unsaturated compound (B1) and a radical polymerizable unsaturated compound (B2) And a modified product (2) obtained by modifying the ethylene polymer (A) with a radically polymerizable unsaturated compound (B2). The modified products of the above <1> to <12> are: Denatured body constituting each (1) (6) can be obtained to mixing on which each separately produced. At this time, the ethylene-based polymer (A) that is a raw material of each modified body (modified body (1) to (6)) can satisfy the above requirements a) to e) at the same time. The physical properties of the polymer (A) may be the same or different.

  Moreover, about the combination of <5>-<12>, it can obtain also by the manufacturing method as shown next.

  For example, in the case of obtaining a modified product of <5>, the ethylene polymer (A) (modified material 1) is modified with the radical polymerizable unsaturated compound (B2) (radical polymerizable unsaturated compound 1). A mixture of the resulting modified product (2) (modification reaction 1) and the ethylene polymer (A) (modified product 2) is further converted into a radical polymerizable unsaturated compound (B1) (radical polymerizable unsaturated compound 2). ) (Modification reaction 2).

  That is, when the modification is represented by the symbol “•” and the mixture is represented by the symbol “+”, the modified product according to the combination <5> is represented by “A · B1 · B2 + A · B1”, whereas In the case of (A · B2 + A) · B1 → “A · B1 · B2 + A · B1”, it can be seen that an equivalent combination of denatured bodies can be obtained.

  About the said manufacturing method, it can be obtained by an equivalent method also about the modified body of the combination of <6>-<12>. The combinations are shown below (Table 2).

(A): Ethylene polymer (A)
(B1): radically polymerizable unsaturated compound (B1)
(B2): Radical polymerizable unsaturated compound (B2)
(C): Ethylene / α-olefin copolymer (C)

Manufacturing method of ethylene polymer (A), ethylene / α-olefin copolymer (C) modified product The ethylene polymer (A) of the present invention and, if necessary, ethylene / α-olefin copolymer (C ) Is modified with a radically polymerizable unsaturated compound (B1) and / or a radically polymerizable unsaturated compound (B2), and conventionally known methods such as extrusion melt modification and solution modification are known. However, the extrusion melt modification method is preferable because the production cost is low.

  The extrusion melt modification method used in the present invention includes (i) a powder of an ethylene polymer (A), a radical polymerizable unsaturated compound (B1), a radical polymerizable unsaturated compound (B2), and an organic peroxidation. (Ii) ethylene polymer (A) powder, ethylene polymer (A) pellets, radical polymerizable unsaturated compound (B1) and radical polymerizable unsaturated compound (B2) and extrusion melt modification in the presence of an organic peroxide, (iii) an ethylene system impregnated with a radically polymerizable unsaturated compound (B1), a radically polymerizable unsaturated compound (B2) and an organic peroxide in advance For example, the powder of the polymer (A) and the pellets of the ethylene polymer (A) are mixed to perform extrusion melting modification. In the above (i) to (iii), an ethylene / α-olefin copolymer (C) may be contained as necessary. At this time, the shape of the ethylene / α-olefin copolymer (C) may be either powder or pellet, but is preferably the same shape as the ethylene polymer (A). In the following matters, the description of the ethylene polymer (A) includes a mixture of the ethylene polymer (A) and the ethylene / α-olefin copolymer (C) as necessary.

  In the above (ii) and (iii), the weight ratio of the powder of the ethylene polymer (A) and the pellet of the ethylene polymer (A) is such that the powder / pellet ratio is 100/0 to 1/99% by weight. The powder / pellet ratio is preferably 100/0 to 5/95% by weight.

  In the present invention, the ethylene polymer (A) powder has a particle size of about 20 μm to 5 mm measured by optical microscope observation, laser diffraction scattering method, or the like. Preferably it is 0.05-4 mm. When the particle diameter is less than 20 μm, blocking between particles in the extruder hopper occurs, causing poor biting into the extruder screw, and tends to cause uneven thickness of the sheet. When the particle diameter exceeds 5 mm, the history of polymer particles remains on the sheet, and unevenness and uneven thickness on the sheet surface tend to occur.

  In the present invention, the pellets of the ethylene polymer (A) are prepared using a conventionally known single-screw extruder, twin-screw extruder, etc., and any pellets such as round pellets and square pellets can be used. Can do. The size also depends on the size of the extruder hopper opening, but in the case of a normal extruder, the longest diameter portion is preferably 5 cm or less. When the size of the pellet is more than 5 cm, the history of the pellet shape remains on the sheet, and unevenness and uneven thickness on the sheet surface tend to occur.

  When extrusion melting modification is carried out only with pellets of ethylene polymer (A), when blending various additives, organic peroxides, radical polymerizable unsaturated compounds (B1) and radical polymerizable unsaturated compounds (B2) The pellets are not impregnated with the liquid additive such as, and concentration unevenness occurs in the ethylene-based resin composition, the solar cell sealing material using the ethylene-based resin composition, and the solar cell sealing sheet. Moreover, during extrusion, various additives are localized, and a gel is generated in the ethylene resin composition, the solar cell sealing material using the ethylene resin composition, and the solar cell sealing sheet, This is not preferable because it causes a decrease in adhesiveness and a breakdown voltage.

  The blending amount of the organic peroxide, the radical polymerizable unsaturated compound (B1) and the radical polymerizable unsaturated compound (B2) with respect to a total of 100 parts by weight of the powder and pellets of the ethylene polymer (A) in the extrusion melt modification is as follows: The organic peroxide is 0.01 to 1 part by weight, the radical polymerizable unsaturated compound (B1) and the radical polymerizable unsaturated compound (B2) are 0.1 to 5 parts by weight, preferably the organic peroxide is 0 parts by weight. 0.01 to 0.5 parts by weight, 0.1 to 4 parts by weight of the radically polymerizable unsaturated compound (B1) and the radically polymerizable unsaturated compound (B2).

  Moreover, the ethylene-based resin composition of the present invention may contain a combination of the modified body (1) to the modified body (6) as represented by the combinations <1> to <12>. One.

  Here, the ethylene polymer (A) for obtaining the modified body (1) to the modified body (6) may satisfy the above requirements a) to e) at the same time, and the physical properties may be the same or different. Good. The physical properties of the ethylene / α-olefin copolymer (C) for obtaining the modified product (3), modified product (4), and modified product (6) may be the same or different.

  The production method of the modified product (1) includes (i) extrusion-melt modification in the presence of an ethylene polymer (A) powder, a radical polymerizable unsaturated compound (B1), and an organic peroxide. ii) Extrusion melt modification in the presence of ethylene polymer (A) powder, ethylene polymer (A) pellets, radical polymerizable unsaturated compound (B1), and organic peroxide, (iii) It is characterized by mixing an ethylene polymer (A) powder impregnated with a radically polymerizable unsaturated compound (B1) and an organic peroxide and an ethylene polymer (A) pellet, and subjecting the mixture to extrusion melt modification. Yes. The blending amount of the organic peroxide and the radical polymerizable unsaturated compound (B1) with respect to 100 parts by weight of the ethylene polymer (A) is 0.01 to 1 part by weight of the organic peroxide, radical polymerizable unsaturated compound ( B1) is 0.1 to 5 parts by weight, preferably 0.01 to 0.5 parts by weight of the organic peroxide and 0.1 to 4 parts by weight of the radical polymerizable unsaturated compound (B1).

  As the method for producing the modified product (2), (i) an ethylene polymer (A) powder, a radically polymerizable unsaturated compound (B2), and extrusion melt modification in the presence of an organic peroxide, ii) Extrusion melt modification in the presence of ethylene polymer (A) powder, ethylene polymer (A) pellets, radical polymerizable unsaturated compound (B2), and organic peroxide, (iii) It is characterized by mixing an ethylene polymer (A) powder impregnated with a radically polymerizable unsaturated compound (B2) and an organic peroxide and an ethylene polymer (A) pellet, and subjecting the mixture to extrusion melt modification. Yes. The blending amount of the organic peroxide and the radical polymerizable unsaturated compound (B2) with respect to 100 parts by weight of the ethylene polymer (A) is 0.01 to 1 part by weight of the organic peroxide, radical polymerizable unsaturated compound ( B2) is 0.1 to 5 parts by weight, preferably 0.01 to 0.5 parts by weight of the organic peroxide and 0.1 to 4 parts by weight of the radical polymerizable unsaturated compound (B2).

  As the method for producing the modified product (3), (i) a powder of ethylene polymer (A), a powder of ethylene / α-olefin copolymer (C), a radical polymerizable unsaturated compound (B1), , Extrusion melt modification in the presence of organic peroxide, (ii) ethylene polymer (A) powder, ethylene / α-olefin copolymer (C) powder, and ethylene polymer (A) pellets; An ethylene / α-olefin copolymer (C) pellet, a radically polymerizable unsaturated compound (B1), and extrusion melt modification in the presence of an organic peroxide; (iii) a radically polymerizable unsaturated compound (B1) ) And an organic peroxide-impregnated ethylene polymer powder (A), ethylene / α-olefin copolymer (C) powder, ethylene polymer (A) pellets and ethylene / α-olefin It is characterized by mixing with pellets of copolymer (C) and subjecting to extrusion melt modification. The amount of the organic peroxide and the radically polymerizable unsaturated compound (B1) to 100 parts by weight of the mixture of the ethylene polymer (A) and the ethylene / α-olefin copolymer (C) is 0 for the organic peroxide. 0.01 to 1 part by weight, 0.1 to 5 parts by weight of the radically polymerizable unsaturated compound (B1), preferably 0.01 to 0.5 part by weight of the organic peroxide, B1) is 0.1 to 4 parts by weight.

  The production method of the modified product (4) includes (i) a powder of an ethylene polymer (A), a powder of an ethylene / α-olefin copolymer (C), a radical polymerizable unsaturated compound (B2), , Extrusion melt modification in the presence of organic peroxide, (ii) ethylene polymer (A) powder, ethylene / α-olefin copolymer (C) powder, and ethylene polymer (A) pellets; Extrusion melt modification in the presence of an organic peroxide, pellets of ethylene / α-olefin copolymer (C), radical polymerizable unsaturated compound (B2), (iii) radical polymerizable unsaturated compound (B2 ) And an organic peroxide-impregnated ethylene polymer powder (A), ethylene / α-olefin copolymer (C) powder, ethylene polymer (A) pellets and ethylene / α-olefin It is characterized by mixing with pellets of copolymer (C) and subjecting to extrusion melt modification. The amount of the organic peroxide and the radically polymerizable unsaturated compound (B2) to 100 parts by weight of the mixture of the ethylene polymer (A) and the ethylene / α-olefin copolymer (C) is 0 for the organic peroxide. 0.01 to 1 part by weight, 0.1 to 5 parts by weight of the radically polymerizable unsaturated compound (B2), preferably 0.01 to 0.5 part by weight of the organic peroxide, B2) is 0.1 to 4 parts by weight.

  The modified product (5) can be produced by (i) a powder of an ethylene polymer (A), a radical polymerizable unsaturated compound (B1), a radical polymerizable unsaturated compound (B2), an organic peroxide. Extrusion melt modification in the presence of oxides, (ii) ethylene polymer (A) powder, ethylene polymer (A) pellets, radical polymerizable unsaturated compound (B1), radical polymerizable unsaturated Extrusion melt modification in the presence of compound (B2) and organic peroxide, (iii) ethylene impregnated with radically polymerizable unsaturated compound (B1), radically polymerizable unsaturated compound (B2) and organic peroxide in advance It is characterized in that the powder of the polymer polymer (A) and the pellets of the ethylene polymer (A) are mixed and subjected to extrusion melt modification. The organic peroxide, the radical polymerizable unsaturated compound (B1) and the radical polymerizable unsaturated compound (B2) are blended in an amount of 0.01 to 1 for the organic polymer (A) based on 100 parts by weight of the organic polymer (A). Parts by weight, 0.1 to 5 parts by weight of the radically polymerizable unsaturated compound (B1), 0.1 to 5 parts by weight of the radically polymerizable unsaturated compound (B2), preferably 0.01 to the organic peroxide -0.5 weight part, a radically polymerizable unsaturated compound (B1) is 0.1-4 weight part, and a radically polymerizable unsaturated compound (B2) is 0.1-4 weight part.

  As the method for producing the modified product (6), (i) a powder of ethylene polymer (A), a powder of ethylene / α-olefin copolymer (C), a radical polymerizable unsaturated compound (B1), , Radically polymerizable unsaturated compound (B2) and extrusion melt modification in the presence of organic peroxide, (ii) powder of ethylene polymer (A) and powder of ethylene / α-olefin copolymer (C) And ethylene polymer (A) pellets, ethylene / α-olefin copolymer (C) pellets, radical polymerizable unsaturated compound (B1), radical polymerizable unsaturated compound (B2), organic Extrusion melt modification in the presence of peroxide, (iii) of an ethylene polymer (A) impregnated with radically polymerizable unsaturated compound (B1), radically polymerizable unsaturated compound (B2) and organic peroxide in advance Pau -, Ethylene-α-olefin copolymer (C) powder, ethylene-based polymer (A) pellets and ethylene-α-olefin copolymer (C) pellets are mixed and extrusion-melt modified. It is characterized by that. The organic peroxide, the radical polymerizable unsaturated compound (B1) and the radical polymerizable unsaturated compound (B2) with respect to 100 parts by weight of the mixture of the ethylene polymer (A) and the ethylene / α-olefin copolymer (C). The compounding amount is 0.01 to 1 part by weight of the organic peroxide, 0.1 to 5 parts by weight of the radical polymerizable unsaturated compound (B1), and 0.1 to 5 parts of the radical polymerizable unsaturated compound (B2). Parts by weight, preferably 0.01 to 0.5 parts by weight of organic peroxide, 0.1 to 4 parts by weight of radical polymerizable unsaturated compound (B1), and 0 for radical polymerizable unsaturated compound (B2). .1 to 4 parts by weight.

  In addition, the ethylene-based resin composition of the present invention may employ a separate manufacturing method as described above in the combinations <5> to <12>.

  For example, in the case of obtaining a modified product of <5>, the ethylene polymer (A) (modified material 1) is modified with the radical polymerizable unsaturated compound (B2) (radical polymerizable unsaturated compound 1). A mixture of the resulting modified product (2) (modification reaction 1) and the ethylene polymer (A) (modified product 2) is further converted into a radical polymerizable unsaturated compound (B1) (radical polymerizable unsaturated compound 2). The production method obtained by modification with (Modification reaction 2) is also a preferred embodiment.

  Here, if the ethylene-based polymer (A) for obtaining the modified product (2) and the added ethylene-based polymer (A) satisfy the above-described requirements a) to e) at the same time, the ethylene-based polymer (A) The physical properties of the polymer (A) may be the same or different. Moreover, the manufacturing method of the modified body (2) mentioned above can preferably be used for the modified body (2). At this time, the resulting modified product is a modified product of the radically polymerizable unsaturated compound (B2) and the radically polymerizable unsaturated compound (B1) of the ethylene polymer (A), and the radical of the ethylene polymer (A). It becomes the mixture of the modified body by a polymerizable unsaturated compound (B1).

  As modification reaction 2, as an extrusion melt modification method, (i) modified body (2), ethylene polymer (A) powder, radical polymerizable unsaturated compound (B1), and presence of organic peroxide (Ii) modified polymer (2), ethylene polymer (A) powder, ethylene polymer (A) pellets, radical polymerizable unsaturated compound (B1), organic Extrusion melt modification in the presence of peroxide, (iii) modified body (2), powder of ethylene polymer (A) impregnated with radically polymerizable unsaturated compound (B1) and organic peroxide in advance, It is characterized by mixing with an ethylene polymer pellet (A) and subjecting it to extrusion melting modification. The amount of the organic peroxide and the radically polymerizable unsaturated compound (B1) to 100 parts by weight of the mixture of the modified product (2) and the added ethylene polymer (A) is 0.01 to 1 for the organic peroxide. Parts by weight, 0.1 to 5 parts by weight of the radically polymerizable unsaturated compound (B1), preferably 0.01 to 0.5 parts by weight of the organic peroxide, and 0 for the radically polymerizable unsaturated compound (B1). .1 to 4 parts by weight.

  In addition, although said description explained in full detail about the combination of said <5>, also about the ethylene-type resin composition concerning the combination of said <6>-<12>, it obtains with the manufacturing method and compounding amount similar to the above. Can do. Modified body (1) to modified body (6) obtained by the modification reaction 1 according to the above production method can be obtained by the above-described technique.

  Modified body (specifically modified body (2), modified body (4), modified body (5)) modified with radically polymerizable unsaturated compound (B2) contained in the ethylene-based resin composition of the present invention, The modified product (6) is characterized in that the graft group concentration derived from the radically polymerizable unsaturated compound (B2) measured by infrared absorption spectrum is in the range of 0.05 to 5.0% by weight. If the concentration is less than 0.2% by weight, the adhesion strength to glass, backsheet and thin film electrode is reduced, and if the graft group concentration is more than 5.0% by weight, organic peroxide is used to increase the graft group concentration. Since a large amount of the product is used, the gel is generated, and the adhesiveness to the adherend is reduced and the appearance of the solar cell sealing material sheet is deteriorated.

  Further, the modified body (2), modified body (4), modified body (5), and modified body (6) of the present invention are also characterized in that the amount of the free radical polymerizable compound (B2) is 1000 ppm or less. . When the amount of the free radical polymerizable compound (B2) exceeds 1000 ppm, electrode corrosion occurs during long-term use of the solar cell module.

  Furthermore, the modified body (2), the modified body (4), the modified body (5), and the modified body (6) of the present invention are characterized by having a gel fraction of 30% or less. When the gel fraction is more than 30%, the adhesiveness to the adherend is deteriorated and the appearance of the solar cell encapsulant sheet is deteriorated.

  In the extrusion melt modification method, an extrusion condition for obtaining a modified product by reacting an ethylene polymer (A), a radical polymerizable unsaturated compound (B1) and a radical polymerizable unsaturated compound (B2) is a conventionally known uniaxial. When using an extruder, a twin screw extruder or the like, usually when the ethylene polymer (A) has a melting point or higher, specifically, the ethylene polymer (A) is modified, for example, 100 to 300 ° C., preferably It is desirable to carry out at a temperature of 150 to 260 ° C. usually for 0.5 to 10 minutes.

  Further, when the radically polymerizable unsaturated compound (B1) and the radically polymerizable unsaturated compound (B2) are graft-modified to the ethylene polymer (A), a reducing substance may be used. When a reducing substance is used, the graft amount of the radically polymerizable unsaturated compound (B1) and the radically polymerizable unsaturated compound (B2)) can be improved.

UV absorber (D), light stabilizer (E), heat stabilizer (F)
The ethylene resin composition of the present invention is characterized in that it contains at least one additive selected from an ultraviolet absorber (D), a light stabilizer (E), and a heat stabilizer (F). It is preferable that the compounding quantity of the said additive is 0.005-5 weight part with respect to 100 weight part of ethylene-type polymer (A). Furthermore, it is preferable to contain at least two types of additives selected from the above three types. Most preferably, all three types are contained. When the blending amount of the above additive is in the above range, the effect of improving the weather resistance stability and heat resistance stability is sufficiently secured, and the transparency of the ethylene-based resin composition and the deterioration of the adhesion to glass are prevented. This is preferable.

  Specific examples of the ultraviolet absorber (D) include 2-hydroxy-4methoxybenzophenone, 2-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4-carboxybenzophenone, 2-hydroxy-4- Benzophenones such as N-octoxybenzophenone, benzotriazol such as 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole And salicylic acid ester type compounds such as phenyl salicylate and p-octylphenyl salicylate are used.

  Specific examples of the light stabilizer (E) include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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 Hindered amine compounds such as -piperidyl) imino}] and hindered piperidine compounds are preferably used.

  Specific examples of the heat stabilizer (F) include tris (2,4-di-tert-butylphenyl) phosphite and bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl. Ester phosphorous acid, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, and bis (2,4-di-tert-butyl) Phosphite heat stabilizers such as phenyl) pentaerythritol diphosphite, lactone heat resistance stabilizers such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a "-(methylene-2,4,6-triyl) tri-p-cresol, 1 , 3, 5 Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenyl) benzylbenzene, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like Hindered phenol heat stabilizers, sulfur heat stabilizers, amine heat stabilizers, etc. In addition, one or more of these can be used, and among them, phosphite heat stabilizer Agents and hindered phenol heat stabilizers are preferred.

Other Additives The ethylene-based resin composition of the present invention can appropriately contain various components other than the components detailed above within a range not impairing the object of the present invention.

For example, various polyolefins other than the ethylene polymer (A), such as an ethylene / α-olefin copolymer having a density lower than 900 kg / m ³ , a styrene or ethylene block copolymer, a propylene polymer, etc. Can be mentioned. These may be contained in an amount of 0.0001 to 50 parts by weight, preferably 0.001 to 40 parts by weight, based on 100 parts by weight of the ethylene polymer (A). Also, one or two kinds selected from various resins other than polyolefin, various rubbers, plasticizers, fillers, pigments, dyes, antistatic agents, antibacterial agents, antifungal agents, flame retardants, crosslinking aids, dispersants, etc. Although the above additive can be contained suitably, it is not limited to these.

  Particularly, in the crosslinking aid, the blending amount is 0 to 5 parts by weight with respect to 100 parts by weight of the ethylene-based polymer (A), so that it can have an appropriate crosslinked structure, heat resistance, mechanical properties, Since adhesiveness can be improved, it is preferable.

  As the crosslinking aid, conventionally known ones generally used for olefin resins can be used. Such a crosslinking aid is a compound having two or more double bonds in the molecule, and specifically includes t-butyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, 2-methoxyethyl acrylate, ethyl carbyl. Monoacrylates such as tall acrylate and methoxytripropylene glycol acrylate, t-butyl methacrylate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, methoxyethylene glycol methacrylate, monomethacrylates such as methoxypolyethylene glycol methacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, die Diacrylates such as lenglycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1 , 9-nonanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and other dimethacrylates, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, penta Tris such as erythritol triacrylate Trimethacrylates such as acrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetraacrylates such as pentaerythritol tetraacrylate, tetramethylolmethane tetraacrylate, divir aromatic compounds such as divinylbenzene, di-i-propenylbenzene, tri Examples include cyanurates such as allyl cyanurate and triallyl isocyanurate, triallyl compounds such as diallyl phthalate and diallyl compounds, oximes such as p-quinonedioxime and pp-dibenzoylquinonedioxime, and maleimides such as phenylmaleimide. . Among these crosslinking aids, diacrylate, dimethacrylate, and divinyl aromatic compounds are more preferable.

Ethylene-based resin composition The ethylene-based resin composition of the present invention is an infrared absorption spectrum of a modified product comprising an ethylene-based polymer (A), a radically polymerizable unsaturated compound (B1), and a radically polymerizable unsaturated compound (B2). The graft group concentration attributable to the radically polymerizable unsaturated compound (B2) measured in step (b) was 0.05 to 5.0% by weight, preferably the graft group concentration attributable to the radically polymerizable unsaturated compound (B2) was 0.02 to 4%. More preferably, the graft group concentration resulting from the radically polymerizable unsaturated compound (B2) is in the range of 0.02 to 4.0% by weight. When the graft group concentration is less than 0.05% by weight, the adhesive strength to glass, backsheet and thin film electrode is lowered. If the graft group concentration is more than 5.0% by weight, a large amount of organic peroxide is used to increase the graft group concentration, resulting in the generation of gel, which reduces the adhesion to the adherend and the solar cell. The appearance of the encapsulant sheet is deteriorated.

  In addition, the ethylene resin composition of the present invention is a free radical polymerizable compound in a modified product comprising an ethylene polymer (A), a radical polymerizable unsaturated compound (B1), and a radical polymerizable unsaturated compound (B2). The amount of (B2) is 500 ppm or less, preferably the amount of free radical polymerizable compound (B2) is 450 ppm or less, more preferably the amount of free radical polymerizable compound (B2) is 400 ppm or less. . When the amount of the free radical polymerizable compound (B2) exceeds 500 ppm, corrosion of the electrode occurs during long-term use of the solar cell module.

  Further, the ethylene-based resin composition of the present invention is a modified radical-polymerizable unsaturated compound comprising an ethylene-based polymer (A), a radical-polymerizable unsaturated compound (B1), and a radical-polymerizable unsaturated compound (B2). It is also characterized in that the Si content derived from (B1) is 50 to 8000 ppm, preferably 100 to 7000 ppm. When the Si content is less than 50 ppm, the adhesive strength to glass, backsheet, and thin film electrode is lowered. If the Si content exceeds 8000 ppm, a large amount of radically polymerizable unsaturated compound (B1) and organic peroxide is used to increase the Si content, resulting in gel generation and adhesion to the adherend. Deterioration and the appearance of the solar cell encapsulant sheet deteriorate.

  Furthermore, in the ethylene resin composition of the present invention, the gel fraction of the modified product comprising the ethylene polymer (A), the radical polymerizable unsaturated compound (B1) and the radical polymerizable unsaturated compound (B2) is 30%. It is also characterized by the following. When the gel fraction is more than 30%, the adhesiveness to the adherend is deteriorated and the appearance of the solar cell encapsulant sheet is deteriorated.

Solar cell encapsulant The ethylene-based resin composition of the present invention is adhesive to glass and a solar cell back surface protective sheet, weather resistance, heat resistance, volume resistivity, electrical insulation, moisture permeability, electrode corrosion, moldability It is excellent in process stability and is suitably used as a solar cell sealing material for conventionally known solar cell modules. In particular, if the density ethylene-based resin composition using the modified product comprising an ethylene-based polymer of ^{900kg / m 3 ~920kg / m 3} (A), excellent transparency, also flexible, crystalline solar cell module Also, it can be suitably used.

  As a method for producing the solar cell encapsulant of the present invention, a commonly used method can be used, but it is preferably produced by melt blending with a kneader, roll, Banbury mixer, extruder or the like.

Solar cell encapsulating sheet A solar cell encapsulating material in which the ethylene resin composition of the present invention is in the form of a sheet is also a preferred embodiment of the present invention. Moreover, the composite solar cell sealing material which has at least 1 layer of the sheet | seat which consists of an ethylene-type resin composition of this invention can also be used suitably.

  The thickness of the layer of the solar cell encapsulant of the present invention is usually 0.01 mm to 2 mm, preferably 0.05 to 1 mm, more preferably 0.1 to 1 mm, more preferably 0.15 mm to 1 mm, More preferably, it is 0.2-1 mm, More preferably, it is 0.2-0.9 mm, More preferably, it is 0.3-0.9 mm, Most preferably, it is 0.3-0.8 mm. When the thickness is within this range, damage to the glass, solar battery cell, thin film electrode, etc. in the laminating step can be suppressed, and a high amount of photovoltaic power can be obtained by ensuring sufficient light transmittance, And since it can laminate-mold the solar cell module at low temperature, it is preferable.

  The method for forming the solar cell encapsulant sheet of the present invention is not particularly limited, but various known forming methods (cast molding, extrusion sheet molding, inflation molding, injection molding, compression molding, calendar molding, etc.) are employed. Is possible. For example, extrusion melting modification of the aforementioned ethylene polymer (A), radical polymerizable unsaturated compound (B1) and radical polymerizable unsaturated compound (B2) in an extruder, an ultraviolet absorber (D), and a light stabilizer. (E), a heat-resistant stabilizer (F), and if necessary, extrusion sheet molding can be performed while melt-kneading with other additives to obtain a solar cell encapsulant in a sheet form.

  Further, an ethylene polymer (A-1), a radically polymerizable unsaturated compound (B1), a radically polymerizable unsaturated compound (B2) modified by extrusion melting and an ethylene polymer (A-2), Various additives (D, E, F, etc.) melt-kneaded, various additives (D, E, F, etc.) and ethylene polymer (A-2) previously melt-kneaded with ethylene heavy A melt-kneaded modified product obtained by extrusion melting modification of a polymer (A-1), a radically polymerizable unsaturated compound (B1) and a radically polymerizable unsaturated compound (B2), an ethylene polymer (A-1) and a radical A modified product obtained by subjecting the polymerizable unsaturated compound (B1) and the radical polymerizable unsaturated compound (B2) to extrusion melt modification and various additives (D, E, F, etc.) previously melt-kneaded with an ethylene polymer ( A-2) melt-kneaded, Various additives (D, E, F, etc.) were melt-kneaded at the time of extrusion melting modification of the tyrene polymer (A-1), the radical polymerizable unsaturated compound (B1) and the radical polymerizable unsaturated compound (B2). It is also possible to obtain a solar cell encapsulant in the form of a sheet by extrusion molding with various combinations of a melted and kneaded ethylene polymer (A-2).

  Here, if the ethylene polymer (A-1) and the ethylene polymer (A-2) satisfy various requirements of the ethylene polymer (A) in the present invention, they are the same or have different properties. Things can be used.

  In addition, the surface of the sheet can be embossed, and the surface of this layer can be decorated by embossing to prevent blocking between the sealing sheets or between the sealing sheet and other sheets. In addition, the embossing serves as a cushion for the solar cell element or the like at the time of lamination, and can prevent these damages.

  Further, the sheet can be used as a solar cell encapsulant in a single wafer form cut according to the size of the solar cell module or in a roll form that can be cut according to the size immediately before creating the solar cell module. .

  The sheet comprising the ethylene-based resin composition of the present invention desirably has an internal haze in the range of 1% to 60%, preferably 1% to 40% when measured with a sample having a thickness of 0.5 mm or less.

  The solar cell encapsulating sheet, which is a preferred embodiment of the present invention, may have at least one layer composed of the ethylene-based resin composition of the present invention. Accordingly, the number of layers made of the ethylene resin composition of the present invention may be one or may be two or more. From the viewpoint of simplifying the structure and reducing the cost, and from the viewpoint of effectively utilizing light by minimizing interface reflection between layers, a single layer is preferable.

  The solar cell encapsulating sheet, which is a preferred embodiment of the present invention, may be composed of only a layer comprising the ethylene resin composition of the present invention, or other than the layer containing the ethylene resin composition of the present invention. Layer (hereinafter also referred to as “other layers”).

  Examples of other layers, if classified according to purpose, are hard coat layers for protecting the front or back surface, adhesive layers, antireflection layers, gas barrier layers, antifouling layers, back sheets, and back surface sealing for solar cell modules. A material etc. can be provided. If classified by material, layer made of UV curable resin, layer made of thermosetting resin, layer made of polyolefin resin, layer made of carboxylic acid modified polyolefin resin, layer made of fluorine-containing resin, cyclic olefin (co) A layer made of a polymer, a layer made of a polyester resin, glass, a layer made of an inorganic compound, and the like can be provided. Preferably, a layer made of a polyolefin resin, a layer made of a carboxylic acid-modified polyolefin resin, a layer made of a fluorine-containing resin, a layer made of a cyclic olefin (co) polymer, a layer made of a polyester resin, or glass can be used.

  There is no particular limitation on the positional relationship between the layer made of the ethylene-based resin composition of the present invention and the other layers, and a preferable layer configuration is appropriately selected in relation to the object of the invention. That is, the other layer may be provided between two or more layers made of the ethylene resin composition of the present invention, or may be provided in the outermost layer of the solar cell encapsulating sheet. It may be provided at the location. Other layers may be provided only on one side of the layer made of the ethylene-based resin composition of the present invention, or other layers may be provided on both sides. There is no restriction | limiting in particular in the number of layers of another layer, Arbitrary number of other layers can be provided and it is not necessary to provide another layer.

  From the viewpoint of reducing the cost by simplifying the structure, and from the viewpoint of effectively utilizing light by minimizing interface reflection, the other layers are not provided, only the layer made of the ethylene resin composition of the present invention, What is necessary is just to produce the sealing sheet for solar cells, and if there exists other layers which are necessary or useful in relation to the objective, what is necessary is just to provide such other layers suitably.

  There are no particular restrictions on the method of laminating the layer comprising the ethylene-based resin composition of the present invention and the other layer when other layers are provided, but a cast molding machine, an extrusion sheet molding machine, an inflation molding machine, and an injection molding machine. A method of obtaining a laminate by co-extrusion using a known melt extruder such as the above, or a method of obtaining a laminate by melting or heating and laminating the other layer on one previously formed layer. Also suitable adhesives (for example, maleic anhydride modified polyolefin resins (for example, Admer made by Mitsui Chemicals, Modic made by Mitsubishi Chemical), low (non) crystalline soft polymers such as unsaturated polyolefins, ethylene / Acrylic ester / maleic anhydride terpolymers (for example, bondine manufactured by Sumika DF Chemical Co., Ltd.), acrylic adhesives, ethylene / vinyl acetate copolymers or adhesive resin compositions containing these For example, a dry laminating method or a heat laminating method. As the adhesive, those having a heat resistance of about 120 ° C. to 150 ° C. are preferably used, and a polyester-based or polyurethane-based adhesive is exemplified as a suitable one. Moreover, in order to improve the adhesiveness of both layers, for example, a silane coupling treatment, a titanium coupling treatment, a corona treatment, a plasma treatment, or the like may be used.

  The solar cell encapsulating sheet of the present invention desirably has an internal haze in the range of 1% to 60%, preferably 5% to 50% when measured with a sample having a thickness of 0.5 mm or less.

Solar cell module The solar cell encapsulant of the present invention and the solar cell encapsulating sheet which is a preferred embodiment of the present invention have the excellent characteristics as described above. Therefore, the solar cell module obtained using such a solar cell encapsulant and / or solar cell encapsulating sheet can utilize the effects of the present invention, and is one of the preferred embodiments of the present invention. It is.

  Examples of the solar cell module include a crystalline solar cell module in which solar cell elements formed of polycrystalline silicon or the like are usually sandwiched and stacked between solar cell sealing sheets, and both front and back surfaces are covered with protective sheets. That is, a typical solar cell module is a solar cell module protective sheet (surface protective sheet) / solar cell sealing sheet / solar cell element / solar cell sealing sheet / solar cell module protective sheet (back surface protective sheet). It is the composition. However, the solar cell module which is one of the preferred embodiments of the present invention is not limited to the above-described configuration, and a part of each of the above layers is appropriately omitted as long as the object of the present invention is not impaired. Layers other than the above can be provided as appropriate. Typically, an adhesive layer, a shock absorbing layer, a coating layer, an antireflection layer, a back surface rereflection layer, a light diffusion layer, and the like can be provided, but not limited thereto. There is no particular limitation on the positions where these layers are provided, and the layers can be provided at appropriate positions in consideration of the purpose of providing such layers and the characteristics of such layers.

  Furthermore, for example, a solar cell in which amorphous silicon formed by chemical vapor deposition (CVD) from silane gas is formed on a glass or film substrate with a thin silicon film of several μm, and an electrode such as silver is sputtered as necessary. A thin film (amorphous) solar cell module in which the element is covered in the order of a solar cell sealing sheet and a solar cell module protective sheet (back surface protective sheet) is also included.

In addition, as other solar cell modules, solar cell modules using silicon for solar cells, hybrid type (HIT type) solar cell modules in which crystalline silicon and amorphous silicon are laminated, and multiple silicon layers having different absorption wavelength ranges are laminated. Junction type (tandem type) solar cell module, spherical silicon type solar cell module combining innumerable spherical silicon particles (diameter of about 1 mm) and concave mirror with a diameter of 2 to 3 mm (also serving as an electrode) to increase the light collecting ability, conventional pin Examples include a field effect solar cell module having a structure in which the role of an amorphous silicon p-type window layer having a junction structure is replaced with an inversion layer induced by a field effect from an insulated transparent electrode. Also, a GaAs-based solar battery module using single-crystal GaAs for solar cells, and a light-absorbing layer material called a chalcopyrite system made of Cu, In, Ga, Al, Se, S, etc. instead of silicon CIS or CIGS type (chalcopyrite type) solar cell module using a I-III-VI group compound as a solar cell, CdTe-CdS type solar cell using a Cd compound thin film as a solar cell, Cu ₂ ZnSnS ₄ (CZTS) ) Solar cell module and the like. The solar cell encapsulant of the present invention can be used as a solar cell encapsulant for all these solar cell modules.

  In particular, the filler layer laminated under the photovoltaic element constituting the solar cell module needs to have the following functions. (I) having adhesiveness with a filler layer, an electrode, and a back surface protective layer laminated on top of the photovoltaic element; and (ii) maintaining the smoothness of the back surface of the solar cell element as the photovoltaic element. Since it has thermoplasticity to fulfill its function, and (iii) it protects solar cell elements as photovoltaic elements, it has excellent scratch resistance, shock absorption and the like.

  Here, the filler layer preferably has heat resistance. In particular, when manufacturing solar cell modules, due to the heating action in the lamination method, etc., vacuum suction and thermocompression bonding, the action of heat such as sunlight in the long-term use of solar cell modules, etc. It is desirable that the ethylene-based resin composition constituting the filler layer does not change or deteriorate or decompose. If the additives contained in the ethylene resin composition are eluted or decomposed products are generated, they act on the electromotive force surface (element surface) of the solar cell element, and the function, performance, etc. Therefore, heat resistance is indispensable as a characteristic of the filler layer of the solar cell module.

  Further, the filler layer has a low water vapor transmission rate, can prevent moisture from being transmitted from the back side of the solar cell module, and can prevent corrosion and deterioration of the photovoltaic element of the solar cell module.

  Further, the filler layer does not necessarily need to be transparent, unlike the filler layer laminated under the surface protective layer for the solar cell module (on the photovoltaic element).

  The solar cell encapsulant of the present invention has the above-described characteristics, and is used as a solar cell encapsulant on the back side of a crystalline solar cell module and a solar cell encapsulant for a thin film solar cell module that is vulnerable to moisture penetration. It can be used suitably.

Although there is no restriction | limiting in particular in the surface protection sheet for solar cell modules used in the solar cell module which is a preferable embodiment of this invention, since it is located in the outermost layer of a solar cell module, a weather resistance, In addition to water repellency, stain resistance, and mechanical strength, it is preferable to have performance for ensuring long-term reliability in outdoor exposure of solar cell modules. Moreover, in order to utilize sunlight effectively, it is preferable that it is a highly transparent sheet | seat with a small optical loss.

  As a material of the surface protection sheet for solar cell modules suitably used for the solar cell module, a resin film made of polyester resin, fluororesin, acrylic resin, cyclic olefin (co) polymer, ethylene-vinyl acetate copolymer, etc. In addition, a glass substrate etc. are mentioned.

  Particularly suitable as the resin film is a polyester resin excellent in transparency, strength, cost and the like, particularly a polyethylene terephthalate resin.

  A fluororesin having particularly good weather resistance is also preferably used. Specifically, tetrafluoroethylene-ethylene copolymer (ETFE), polyvinyl fluoride resin (PVF), polyvinylidene fluoride resin (PVDF), polytetrafluoroethylene resin (TFE), tetrafluoroethylene-6 There are fluorinated propylene copolymer (FEP) and poly (trifluorotrifluoroethylene resin) (CTFE). Polyvinylidene fluoride resin is excellent in terms of weather resistance, but tetrafluoroethylene-ethylene copolymer is excellent in terms of both weather resistance and mechanical strength. Moreover, it is desirable to perform a corona treatment and a plasma treatment on the surface protection sheet in order to improve the adhesiveness with a material constituting another layer such as a sealing material layer. It is also possible to use a sheet that has been subjected to stretching treatment for improving mechanical strength, for example, a biaxially stretched polypropylene sheet.

  When glass is used as the surface protective sheet for a solar cell module, the total light transmittance of light having a wavelength of 350 to 1400 nm is preferably 80% or more, and more preferably 90% or more. As such a glass substrate, it is common to use white plate glass with little absorption in the infrared part, but even blue plate glass has little influence on the output characteristics of the solar cell module if the thickness is 3 mm or less. Further, tempered glass can be obtained by heat treatment to increase the mechanical strength of the glass substrate, but float plate glass without heat treatment may be used. Further, an antireflection coating may be provided on the light receiving surface side of the glass substrate in order to suppress reflection.

Back surface protection sheet for solar cell module The back surface protection sheet for solar cell module used in the solar cell module which is a preferred embodiment of the present invention is not particularly limited, but is located on the outermost layer of the solar cell module, and thus the above-mentioned surface Like the protective sheet, various properties such as weather resistance and mechanical strength are required. Therefore, you may comprise the back surface protection sheet for solar cell modules with the material similar to a surface protection sheet. That is, the above-mentioned various materials that can be used in the surface protective sheet can also be used in the back surface protective sheet. In particular, a polyester resin and glass can be preferably used.

  Moreover, since the back surface protection sheet does not assume the passage of sunlight, the transparency required for the surface protection sheet is not necessarily required. Therefore, a reinforcing plate may be attached to increase the mechanical strength of the solar cell module or to prevent distortion and warpage due to temperature change. For example, a steel plate, a plastic plate, an FRP (glass fiber reinforced plastic) plate or the like can be preferably used.

  Moreover, it is one of the preferable aspects of this invention that the solar cell sealing material of this invention is integrated with the said back surface protection sheet for solar cell modules. By integrating with the back surface protection sheet for solar cell modules, shortening the cutting to the module size of the solar cell encapsulant and the back surface protection sheet for solar cell modules at the time of module assembly, Advantages such as shortening the process of laying up can be obtained.

  There are no particular restrictions on the method of laminating the solar cell encapsulant of the present invention and the back surface protection sheet for solar cell modules when they are integrated, but there are cast molding machines, extrusion sheet molding machines, inflation molding machines, injection molding machines, etc. A method of obtaining a laminate by co-extrusion using a known melt extruder, or a method of obtaining a laminate by melting or heating and laminating the other layer on one previously formed layer. Also suitable adhesives (for example, maleic anhydride modified polyolefin resins (for example, Admer made by Mitsui Chemicals, Modic made by Mitsubishi Chemical, etc.), low (non) crystalline soft polymers such as unsaturated polyolefins, ethylene / Acrylic ester / maleic anhydride terpolymers (for example, Bondin made by Sumika CDF Chemical Co., Ltd.), acrylic adhesives, ethylene / vinyl acetate copolymers or adhesive resin compositions containing these For example, a dry laminating method or a heat laminating method. As the adhesive, those having a heat resistance of about 120 ° C. to 150 ° C. are preferably used, and a polyester-based or polyurethane-based adhesive is exemplified as a suitable one. Moreover, in order to improve the adhesiveness of both layers, for example, a silane coupling treatment, a titanium coupling treatment, a corona treatment, a plasma treatment, or the like may be used.

Solar cell element The solar cell element in the solar cell module which is a preferred embodiment of the present invention is not particularly limited as long as it can generate power using the photovoltaic effect of a semiconductor. For example, silicon (single crystal, Crystalline, amorphous (amorphous) solar cells, compound semiconductor (III-V group, II-VI group, etc.) solar cells, wet solar cells, organic semiconductor solar cells, and the like can be used. Among these, a polycrystalline silicon solar cell is preferable from the viewpoint of balance between power generation performance and cost.

  Both silicon and compound semiconductors have excellent characteristics as solar cell elements, but are known to be easily damaged by external stress, impact, and the like. Since the solar cell sealing material of the present invention is excellent in flexibility, it has a great effect of absorbing stress, impact, etc. on the solar cell element and preventing damage to the solar cell element. Therefore, in the solar cell module which is a preferred embodiment of the present invention, it is desirable that the layer made of the solar cell sealing material of the present invention is directly joined to the solar cell element.

  Further, when the solar cell encapsulant has thermoplasticity, it is possible to take out the solar cell element relatively easily even after the solar cell module is once manufactured, and it is excellent in recyclability. Yes. Since the essential component of the solar cell encapsulant of the present invention has thermoplasticity, it is easy to impart thermoplasticity to the entire solar cell encapsulant, which is preferable from the viewpoint of recyclability.

Power Generation Facility The solar cell module which is a preferred embodiment of the present invention is excellent in productivity, power generation efficiency, life and the like. For this reason, the power generation equipment using such a solar cell module is excellent in cost, power generation efficiency, life, etc., and has a high practical value.

  The power generation equipment described above is suitable for long-term use regardless of whether it is outdoors or indoors, such as being installed on the roof of a house, used as a mobile power source for outdoor use such as camping, or used as an auxiliary power source for automobile batteries.

  Hereinafter, the present invention will be specifically described by way of examples. However, the scope of the present invention is not limited by the examples in any way.

(Measuring method)
In the following examples and comparative examples, various characteristics were measured by the following methods.
-Density 190 degreeC and the strand after MFR measurement in a 2.16kg load were gradually cooled to room temperature over 1 hour, Then, it measured by the density gradient tube method.

Melting peak temperature Using DSC7 manufactured by PerkinElmer, about 5 mg of sample is packed in a dedicated aluminum pan, heated from 0 ° C to 200 ° C at 320 ° C / min, held at 200 ° C for 5 minutes, and then from 200 ° C. The temperature was lowered to 0 ° C. at 10 ° C./min, held at 0 ° C. for another 5 minutes, and then the peak peak of the melting peak was determined as the melting peak temperature from the endothermic curve when the temperature was raised at 10 ° C./min. In addition, when several peaks were detected at the time of DSC measurement, the peak detected on the highest temperature side was made into melting peak temperature (Tm).

・ MFR2
The measurement was performed at 190 ° C. and a load of 2.16 kg in accordance with JIS K-6721.

-Molecular weight distribution (Mw / Mn); ethylene polymer (A) analysis Molecular weight distribution (Mw / Mn) was measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters. The separation columns are two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is o -Using dichlorobenzene (Wako Pure Chemical Industries) and 0.025% by weight of BHT (Takeda Pharmaceutical) as an antioxidant, moving at 1.0 ml / min, the sample concentration is 15 mg / 10 mL, and the sample injection volume is 500 μL A differential refractometer was used as a detector. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

Molecular weight distribution (Mw / Mn); ethylene / α-olefin copolymer (C) analysis Molecular weight distribution (Mw / Mn) was measured as follows using GPC-150C manufactured by Waters.
The separation columns were TSKgel GMH6-HT and TSKgel GMH6-HTL, the column size was 7.5 mm in inner diameter and 600 mm in length, the column temperature was 140 ° C., and o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.) was used as the mobile phase. Industry) and 0.025 wt% BHT (Takeda Pharmaceutical) as an antioxidant, moved at 1.0 ml / min, the sample concentration was 0.1 wt%, the sample injection volume was 500 μl, and the detector A differential refractometer was used. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ . The molecular weight calculation is a value that is universally calibrated and converted to an ethylene / α-olefin copolymer according to each α-olefin used.

-Metal residue After wet decomposition of the ethylene-based polymer (A), the volume of aluminum, zirconium, titanium, hafnium, and magnesium is determined with an ICP emission analyzer (ICPS-8100, manufactured by Shimadzu Corp.) with pure water. The total amount was made metal residue.

・ Si content Denatured modified polymer of ethylene polymer (A) is wet-decomposed, then is made up to volume with pure water, and silicon (Si) is quantified with an ICP emission analyzer (ICPS-8100, manufactured by Shimadzu Corporation). did.

-Graft group density | concentration of radically polymerizable unsaturated compound (B2) It carried out by analysis of the absorption peak of a radically polymerizable unsaturated compound (B2) by infrared absorption spectrum (IR) measurement. For the IR measurement, a polymer made into a film using FT / IR-470 manufactured by JASCO Corporation was used.

-Determination of free radical polymerizable unsaturated compound (B2) A sample, p-xylene and water were placed in a glass container, and the sample was dissolved while heating and stirring. Methanol was added to the solution to precipitate a polymer, and the polymer and filtrate were separated by filtration. The filtrate was concentrated and the free radical polymerizable unsaturated compound (B2) dissolved in the aqueous phase was subjected to quantitative analysis by HPLC using Shim-Pack WAX-1 (manufactured by Shimadzu Corporation).

Adhesive strength A sheet sample having a thickness of 0.5 mm is placed between a polyethylene terephthalate resin back sheet (Lintec Co., Ltd., Reprea) and a glass plate (hereinafter abbreviated as a thin film electrode) in which silver is sputtered at the center. It was put in a vacuum laminator, placed on a hot plate adjusted to 150 ° C., and heated under vacuum for 2 minutes and 13 minutes to produce a thin film electrode sputtered glass / sheet sample / back sheet laminate. A sheet sample of this laminate was cut to a width of 15 mm, and the peel strength from each adherend (back sheet, thin film electrode, glass) was measured at 180 degrees peel. For example, using an Instron tensile tester Instron 1123, measurement was performed at 23 ° C. with a span of 30 mm and a tensile speed of 30 mm / min at 180 ° peel, and an average value of three measurements was adopted. .

・ Constant Temperature and Humidity Test A simulation module in which the periphery of the laminate prepared in the above adhesive strength test is sealed with butyl rubber and the exterior is covered with an aluminum frame is manufactured by Suga Test Instruments Co., Ltd. according to JIS C8917. Under the XL75 special specification, the accelerated test of the sample for adhesive strength was performed for 2000 hours under the conditions of 85 ° C. and 85% humidity. The adhesion strength test with respect to the glass of the obtained acceleration test sample was implemented. The adhesive strength maintenance rate indicates a maintenance rate relative to the initial adhesive strength.

・ High-strength xenon irradiation test A simulation module in which the periphery of the above laminate is sealed with butyl rubber and the exterior is covered with an aluminum frame is compliant with JIS C8917, and XL75 special specification manufactured by Suga Test Instruments Co., Ltd. The accelerated test of the sample for adhesive strength was conducted for 2000 hours under the conditions of black panel temperature (BPT) 83 ° C. and humidity 50%. The adhesion strength test with respect to the glass of the obtained acceleration test sample was implemented. The adhesive strength maintenance rate indicates a maintenance rate relative to the initial adhesive strength.

Heat cycle test A simulated module in which the periphery of the laminate was sealed with butyl rubber and the exterior was covered with an aluminum frame was tested in accordance with JIS C8917, using XL75 special specifications manufactured by Suga Test Instruments Co., Ltd. The temperature inside the tank was repeatedly raised and lowered from -40 to 90 ° C within 2 hours, held for 1 hour after reaching -40 ° C and 90 ° C, and under the conditions of a 6 hour cycle of raising and lowering temperature and holding temperature, The acceleration test of the adhesive strength sample was performed 200 times (1200 hours). The adhesion strength test with respect to the glass of the obtained acceleration test sample was implemented. The adhesive strength maintenance rate indicates a maintenance rate relative to the initial adhesive strength.

-Dielectric breakdown resistance It measured at 23 degreeC using the test piece of thickness 0.4mm based on JIS-K6911.
The test piece was prepared by molding a 10 MPa pressure sheet using a hydraulic heat press machine manufactured by Shindo Metal Industry Co., Ltd. set at 200 ° C. In the case of a 0.4 mm thick sheet (spacer shape; 240 × 240 × 2 mm thick plate 80 × 80 × 0.5-3 mm, 4 pieces), the residual heat is about 2 minutes and the pressure is applied at 10 MPa for 1 minute. Then, using another hydraulic hot press machine manufactured by Shinfuji Metal Industry Co., Ltd. set to 20 ° C., the sample was compressed at 10 MPa and cooled for about 3 minutes to prepare a measurement sample. A 5 mm thick brass plate was used as the hot plate.

-Gel fraction A 1g sample is taken from the sheet obtained by the extruder, subjected to Soxhlet extraction with boiling xylene for 10 hours, filtered through a 30 mesh stainless steel mesh, and then dried under reduced pressure at 110 ° C for 8 hours. And was calculated from the remaining amount on the mesh.

・ Electrode corrosion 1
The state of the silver electrode of the sample after the constant temperature and humidity test of the simulation module in which the periphery of the laminate was sealed with butyl rubber and the exterior was covered with an aluminum frame was evaluated as follows.
○: No change due to corrosion △: Some change due to corrosion is observed ×: Electrode changes to brown due to corrosion

・ Electrode corrosivity 2
A sheet sample of 0.5 mm thickness is sandwiched between glass plates (hereinafter abbreviated as thin film electrodes) in which silver is sputtered in the center, charged in a vacuum laminator, and placed on a hot plate adjusted to 150 ° C. for vacuum. A thin film electrode sputtered glass / sheet sample laminate was prepared by heating under reduced pressure for 2 minutes and 13 minutes. After the constant temperature and humidity test of this laminate, the state of the sample silver electrode was visually evaluated, and the scores were as follows.
○: No change due to corrosion △: Some change due to corrosion is observed ×: Electrode changes to brown due to corrosion

-Water vapor transmission rate Based on JIS-Z0208 and JIS-K7129, the water vapor transmission rate by the cup method was measured using the test piece of thickness 0.5mm under the conditions of 23 degreeC and 90% humidity.

[Preparation of solid catalyst component]
A solid catalyst component containing dimethylsilylenebis (3-methylcyclopentadienyl) zirconium dichloride, which is a metallocene compound, was prepared by the method described in JP-A-9-328520. The zirconium content per gram was 2.3 mg.

[Preparation of prepolymerization catalyst]
Similarly, by the method described in JP-A-9-328520, a prepolymerized catalyst composed of 1-hexene and ethylene was obtained using 4 g of the solid catalyst obtained above. The zirconium content per 1 g of the solid catalyst was 2.2 mg, and a prepolymerized catalyst obtained by prepolymerizing 3 g of polyethylene was obtained.

[Polymerization Example 1] Ethylene polymer (A) 1
800 ml of dehydrated and purified hexane was charged into a 2 liter stainless steel autoclave sufficiently purged with nitrogen, and the inside of the system was replaced with a mixed gas of ethylene and hydrogen (hydrogen content: 0.7 mol%).

  Next, the system was heated to 60 ° C., and 1.5 mmol of triisobutylaluminum, 200 ml of 1-hexene, and 0.015 mg atom in terms of zirconium atom were added to the prepolymerized catalyst prepared as described above.

Thereafter, a mixed gas of ethylene and hydrogen having the same composition as above was introduced, and polymerization was started at a total pressure of 3 MPaG. Thereafter, only the mixed gas was supplied, the total pressure was kept at 3 MPaG, and polymerization was carried out at 70 ° C. for 1.5 hours.
After completion of the polymerization, the polymer was filtered and dried overnight at 80 ° C. to obtain 101 g of ethylene polymer (A) 1.

  The ethylene polymer (A) 1 obtained by repeating the above polymerization was subjected to a die temperature = 190 ° C. with a single screw extruder (screw diameter 20 mmφ · L / D = 28) manufactured by Thermo Plastic Co., Ltd. Thus, an ethylene polymer (A) 1 ′ which is a pellet of the ethylene polymer (A) 1 was obtained. The results are shown in Table 3.

[Polymerization Example 2]
The same procedure as in Polymerization Example 1 was conducted except that the amount of hexane was changed to 795 ml and the amount of 1-hexene was changed to 205 ml. Ethylene polymer (A) 2 was 95 g. After repeating the same polymerization, ethylene polymer (A) 2 ′ was obtained with a single screw extruder. The results are shown in Table 3.

[Polymerization Example 3]
The same procedure as in Polymerization Example 1 was conducted except that the hydrogen content of the mixed gas of ethylene and hydrogen was changed to 0.5 mol%, the amount of hexane was changed to 870 ml, and the amount of 1-hexene was changed to 230 ml. Ethylene polymer (A) 3 was 130 g. The results are shown in Table 3. Further, after repeating the same polymerization, an ethylene polymer (A) 3 ′ was obtained with a single screw extruder. The results are shown in Table 3.

[Polymerization Example 4]
The same procedure as in Polymerization Example 1 was conducted except that the hydrogen content of the mixed gas of ethylene and hydrogen was changed to 0.2 mol%, the amount of hexane was changed to 910 ml, and the amount of 1-hexene was changed to 90 ml. Ethylene polymer (A) 4 was 145 g. After repeating the same polymerization, ethylene polymer (A) 4 ′ was obtained with a single screw extruder. The results are shown in Table 3.

[Polymerization Example 5]
The same procedure as in Polymerization Example 1 was conducted except that the hydrogen content of the mixed gas of ethylene and hydrogen was changed to 0.8 mol%, the amount of hexane was changed to 780 ml, and the amount of 1-hexene was changed to 220 ml. Ethylene polymer (A) 5 was 78 g. After repeating the same polymerization, an ethylene polymer (A) 5 ′ was obtained with a single screw extruder. The results are shown in Table 3.

[Polymerization Example 6]
The same procedure as in Polymerization Example 1 was conducted except that the hydrogen content of the mixed gas of ethylene and hydrogen was changed to 0.2 mol%, the amount of hexane was changed to 915 ml, and the amount of 1-hexene was changed to 85 ml. Ethylene polymer (A) 6 was 146 g. After repeating the same polymerization, an ethylene polymer (A) 6 ′ was obtained with a single screw extruder. The results are shown in Table 3.

[Polymerization Example 7]
The same procedure as in Polymerization Example 1 was conducted except that the hydrogen content of the mixed gas of ethylene and hydrogen was changed to 0.2 mol%, the amount of hexane was changed to 830 ml, and the amount of 1-hexene was changed to 179 ml. Ethylene polymer (A) 7 was 94 g. After repeating the same polymerization, ethylene polymer (A) 7 ′ was obtained with a single screw extruder. The results are shown in Table 4.

[Polymerization Example 8]
The same procedure as in Polymerization Example 7 was conducted except that the hydrogen content of the mixed gas of ethylene and hydrogen was changed to 0.3 mol%. Ethylene polymer (A) 8 was 84 g. After repeating the same polymerization, an ethylene polymer (A) 3 ′ was obtained with a single screw extruder. The results are shown in Table 4.

[Polymerization Example 9]
The same procedure as in Polymerization Example 7 was conducted except that the hydrogen content of the mixed gas of ethylene and hydrogen was changed to 1.0 mol%. Ethylene polymer (A) 9 was 145 g. After repeating the same polymerization, an ethylene polymer (A) 9 ′ was obtained with a single screw extruder. The results are shown in Table 4.

[Polymerization Example 10]
The same procedure as in Polymerization Example 7 was conducted except that the hydrogen content of the mixed gas of ethylene and hydrogen was changed to 1.3 mol%. Ethylene polymer (A) 10 was 162 g. After repeating the same polymerization, an ethylene polymer (A) 10 ′ was obtained with a single screw extruder. The results are shown in Table 4.

[Polymerization Example 11]
Polymerization was carried out in the same manner as in Polymerization Example 7, except that the hydrogen content of the mixed gas of ethylene and hydrogen was 1.6 mol%, and the prepolymerization catalyst was changed to 0.013 mg atom in terms of zirconium atom. Ethylene polymer (A) 11 was 151 g. After repeating the same polymerization, an ethylene polymer (A) 11 ′ was obtained with a single screw extruder. The results are shown in Table 4.

[Polymerization Example 12]
Polymerization was carried out in the same manner as in Polymerization Example 7 except that the hydrogen content of the mixed gas of ethylene and hydrogen was 2.0 mol% and the prepolymerization catalyst was changed to 0.012 mg atom in terms of zirconium atom. Ethylene polymer (A) 12 was 151 g. After repeating the same polymerization, ethylene polymer (A) 12 'was obtained with a single screw extruder. The results are shown in Table 4.

[Polymerization Example 13]
It carried out similarly to the polymerization example 7 except having replaced with the supply of only ethylene, without mixing hydrogen. Ethylene polymer (A) 13 was 85 g. After repeating the same polymerization, ethylene polymer (A) 12 'was obtained with a single screw extruder. The results are shown in Table 4.

[Polymerization Example 14]
Polymerization was carried out in the same manner as in Polymerization Example 1 except that the amount of hexane was 820 ml, the amount of 1-hexene was 180 ml, and the prepolymerization catalyst was changed to 0.024 mg atom in terms of zirconium atom. Ethylene polymer (A) 14 was 125 g. After repeating the same polymerization, an ethylene polymer (A) 14 ′ was obtained with a single screw extruder. The results are shown in Table 5.

[Polymerization Example 15]
The same procedure as in Polymerization Example 1 was conducted except that the amount of hexane was 830 ml, the amount of 1-hexene was 170 ml, the prepolymerization catalyst was changed to 0.013 mg atom in terms of zirconium atom, and the polymerization time was changed to 0.75 hour. . Ethylene polymer (A) 15 was 85 g. After repeating the same polymerization, ethylene polymer (A) 15 ′ was obtained with a single screw extruder. The results are shown in Table 5.

[Polymerization Example 16]
A toluene solution (Zr = 0.0103 mmol / ml) of dimethylsilylene bis (3-methylcyclopentadienyl) zirconium chloride as a solid catalyst component was added to 5.55 ml of bis (3-methylcyclopentadienyl) zirconium chloride. The prepolymerized catalyst obtained by preliminarily polymerizing the toluene solution (Zr = 0.0103 mmol / ml) with 5.55 ml of the solid catalyst component was 0.017 mg atom in terms of zirconium atom, the amount of hexane was 820 ml, 1 -The same procedure as in Polymerization Example 1 was conducted except that the amount of hexene was changed to 180 ml and the polymerization time was changed to 3 hours. Ethylene polymer (A) 16 was 165 g. After repeating the same polymerization, ethylene polymer (A) 16 'was obtained with a single screw extruder. The results are shown in Table 5.

[Polymerization Example 17]
The hydrogen content of the mixed gas of ethylene and hydrogen is 0.8 mol%, the amount of hexane is 750 ml, the amount of 1-hexene is 250 ml, the prepolymerized catalyst is 0.008 mg atom in terms of zirconium atom, and the total pressure is 4 MPaG. The procedure was the same as in Polymerization Example 1 except that it was replaced. Ethylene polymer (A) 17 was 150 g. After repeating the same polymerization, an ethylene polymer (A) 17 ′ was obtained with a single screw extruder. The results are shown in Table 5.

[Polymerization Example 18]
The hydrogen content of the mixed gas of ethylene and hydrogen is 0.2 mol%, the amount of hexane is 950 ml, the amount of 1-hexene is 50 ml, the prepolymerized catalyst is 0.045 mg atom in terms of zirconium atom, and the total pressure is 1. It carried out similarly to the polymerization example 1 except having replaced with 2 MPaG. Ethylene polymer (A) 18 was 80 g. After repeating the same polymerization, an ethylene polymer (A) 18 ′ was obtained with a single screw extruder. The results are shown in Table 5.

[Polymerization Example 19]
The hydrogen content of the mixed gas of ethylene and hydrogen is 0.8 mol%, the amount of hexane is 750 ml, the amount of 1-hexene is 250 ml, the prepolymerized catalyst is 0.008 mg atom in terms of zirconium atom, and the total pressure is 4 MPaG. The procedure was the same as in Polymerization Example 1 except that it was replaced. Thereafter, 5 ml of 1N hydrochloric acid and 500 ml of distilled water were added to the polymerization solution, and decalcification was performed. After separating the water, neutralization was performed until the pH of the recovered water was neutralized with distilled water. . The polymer was then filtered and dried at 80 ° C. overnight. Ethylene polymer (A) 19 was 150 g. After repeating the same polymerization, an ethylene polymer (A) 19 ′ was obtained with a single screw extruder. The results are shown in Table 5.

[Polymerization Example 20]
The hydrogen content of the mixed gas of ethylene and hydrogen is 0.2 mol%, the amount of hexane is 945 ml, the amount of 1-hexene is 55 ml, the prepolymerized catalyst is 0.055 mg atom in terms of zirconium atom, and the total pressure is 1 MPaG. The procedure was the same as in Polymerization Example 1 except that it was replaced. Ethylene polymer (A) 20 was 70 g. After repeating the same polymerization, an ethylene polymer (A) 20 ′ was obtained with a single screw extruder. The results are shown in Table 5.

[Polymerization Example 21]
The same procedure as in Polymerization Example 7 was conducted except that the hydrogen content of the mixed gas of ethylene and hydrogen was changed to 0.7 mol%. Ethylene polymer (A) 21 was 105 g. After repeating the same polymerization, ethylene polymer (A) 21 ′ was obtained with a single screw extruder. The results are shown in Table 5.

[Synthesis example 1 of ethylene / α-olefin copolymer]
Copolymerization of ethylene and 1-butene was continuously carried out at a polymerization temperature of 105 ° C. using a fully stainless steel polymerization vessel (stirring rotation speed = 500 rpm) having a substantial internal volume of 1 L equipped with stirring blades. From the side of the polymerization vessel to the liquid phase every hour, 1.60 L of hexane, 56 g of ethylene, 170 g of 1-butene, and 1.4 NL of hydrogen, [dimethyl (t-butylamide) (tetramethyl-η5-cyclo Pentadienyl) silane] titanium dichloride is continuously supplied at a rate of 0.0004 mmol, triphenylcarbenium (tetrakispentafluorophenyl) borate is 0.004 mmol, and triisobutylaluminum is 0.2 mmol, and the polymerization pressure is 3.8 MPaG. The copolymerization reaction was carried out. In addition, the hexane solution of the ethylene / 1-butene copolymer obtained continuously was stored in a hold drum, and methanol was added at 0.2 ml per hour as a catalyst deactivator therefor to terminate the polymerization.
The obtained hexane solution of ethylene / 1-butene copolymer was extracted every 1 hour, and the polymer was precipitated from the polymerization solution in 2 L of methanol, and dried under vacuum at 130 ° C. for 10 hours to obtain ethylene / 1-butene copolymer. Coalescence was obtained. The yield was 47.3 g / h.
Table 13 shows the physical properties.

[Synthesis example 2 of ethylene / α-olefin copolymer]
1-butene of Synthesis Example 1 is 300 g of propylene, 1.4 L of hexane, [dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane] titanium dichloride is 0.001 mmol, triphenylcarbenium (tetrakis) An ethylene / propylene copolymer was obtained in the same manner as in Synthesis Example 1 except that the pentafluorophenyl) borate was changed to 0.01 mmol. The yield was 41.3 g / h.
Table 13 shows the physical properties.

[Synthesis Example 3 of Ethylene / α-Olefin Copolymer]
1-Butene of Synthesis Example 1 1-octene 80 g, hexane 1.8 L, [dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane] titanium dichloride 0.0002 mmol, triphenylcarbenium An ethylene / 1-octene copolymer was obtained in the same manner as in Synthesis Example 1 except that (tetrakispentafluorophenyl) borate was changed to 0.002 mmol. The yield was 46.7g / hour.
Table 13 shows the physical properties.

[Synthesis Example 4 of Ethylene / α-Olefin Copolymer]
Except having changed the propylene of the synthesis example 2 to 320 g, it carried out similarly to the synthesis example 2, and obtained the ethylene / propylene copolymer. The yield was 39.2 g / h.
Table 13 shows the physical properties.

[Production Example 1]
10 parts by weight of the ethylene-based polymer (A) 3 and 90 parts by weight of the ethylene-based polymer (A) 3 ′, 2 weights of γ-methacryloxypropyltrimethoxysilane as the radical polymerizable unsaturated compound (B1) 1 Part, 0.05 parts by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane as an organic peroxide was dry blended. Thereafter, a modified body 1 of the ethylene polymer (A) is obtained under the condition of a die temperature = 210 ° C. with a single screw extruder (screw diameter: 20 mmφ · L / D = 28) manufactured by Thermo Plastic Co., Ltd. It was. The results are shown in Table 6.

[Production Example 2]
50 parts by weight of the ethylene polymer (A) 3 and 50 parts by weight of the ethylene polymer (A) 3 ′, 5 weights of γ-methacryloxypropyltrimethoxysilane as the radical polymerizable unsaturated compound (B1) 1 Parts, the same as in Example 1 except that 2,5-dimethyl-2,5-di (t-butylperoxy) hexane was replaced by 0.2 parts by weight as the organic peroxide. A modified product 2 of A) was obtained. The results are shown in Table 6.

[Production Example 3]
10 parts by weight of ethylene polymer (A) 3, 90 parts by weight of ethylene polymer (A) 3 ′, 0.3 parts by weight of maleic anhydride as a radical polymerizable unsaturated compound (B2), As an oxide, 0.03 part by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane was dry blended. Thereafter, a modified body 3 of the ethylene polymer (A) is obtained under the condition of a die temperature = 230 ° C. with a single screw extruder (screw diameter: 20 mmφ · L / D = 28) manufactured by Thermo Plastic Co., Ltd. It was. The results are shown in Table 6.

[Production Example 4]
50 parts by weight of ethylene polymer (A) 3 and 50 parts by weight of ethylene polymer (A) 3 ′, 1.3 parts by weight of maleic anhydride as a radical polymerizable unsaturated compound (B2), Modification of ethylene polymer (A) in the same manner as in Production Example 3 except that 2,5-dimethyl-2,5-di (t-butylperoxy) hexane was changed to 0.1 parts by weight as an oxide. Body 4 was obtained. The results are shown in Table 6.

[Example 1]
100 parts by weight of the ethylene polymer (A) 1 ′, 0.5 parts by weight of γ-methacryloxypropyltrimethoxysilane as the radical polymerizable unsaturated compound (B1) 1, and the radical polymerizable unsaturated compound (B2) Maleic anhydride as 0.5 parts by weight, organic peroxide as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane as 0.05 parts by weight, and ultraviolet absorber (D) as 2 parts 0.4 parts by weight of 4-hydroxy-4-normal-octyloxybenzophenone, 0.1 parts by weight of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate as a radical scavenger (E), Add 0.1 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite as a heat stabilizer (F) and dry blend to obtain an ethylene polymer blend. .

  Next, a coat hanger type T die (lip shape; 270 ×) was applied to a single screw extruder (screw diameter 20 mmφ · L / D = 28) manufactured by Thermo Plastic Co., Ltd. from the obtained blend of ethylene polymers. 0.8 mm), a die temperature = 210 ° C., a roll temperature of 30 ° C. and a winding speed of 1.0 m / min, and a modified product modified with the ethylenically unsaturated silane compound (B) 1 is obtained. A sheet having a thickness of 500 μm composed of the ethylene-based resin composition contained was obtained. The obtained sheet was evaluated. The results are shown in Table 7.

[Example 2]
98 parts by weight of ethylene-based polymer (A) 1 'and 2 parts by weight of ethylene-based polymer (A) 3 were previously dry-blended, and various additives were added to the blend as in Example 1 and further dried. A sheet was obtained in the same manner as in Example 1 except for blending. The obtained sheet was evaluated. The results are shown in Table 7.

[Example 3]
Various additives were added to 100 parts by weight of the ethylene-based polymer (A) 3 in the same manner as in Example 1, and a sheet was obtained in the same manner as in Example 1 except that dry blending was performed. The obtained sheet was evaluated. The results are shown in Table 7.

[Example 4]
80 parts by weight of the ethylene polymer (A) 3 and 20 parts by weight of the modified polymer 1 of the ethylene polymer (A) are previously dry blended, and the blended product other than the radical polymerizable unsaturated compound (B1) 1 Various additives were added in the same manner as in Example 1, and a sheet was obtained in the same manner as in Example 1 except that dry blending was performed. The obtained sheet was evaluated. The results are shown in Table 7.

[Example 5]
A sheet was obtained in the same manner as in Example 4 except that the modified polymer 1 of the ethylene polymer (A) was replaced with the modified polymer 2 of the ethylene polymer (A). The obtained sheet was evaluated. The results are shown in Table 7.

[Example 6]
80 parts by weight of the ethylene-based polymer (A) 3 and 20 parts by weight of the modified body 3 of the ethylene-based polymer (A) are dry-blended in advance, and various kinds other than the radical polymerizable unsaturated compound (B2) are added to the blend. A sheet was obtained in the same manner as in Example 1 except that the additive was added in the same manner as in Example 1 and further dry blended. The obtained sheet was evaluated. The results are shown in Table 7.

[Example 7]
A sheet was obtained in the same manner as in Example 6 except that the modified polymer 3 of the ethylene polymer (A) was replaced with the modified polymer 4 of the ethylene polymer (A). The obtained sheet was evaluated. The results are shown in Table 7.

[Example 8]
50 parts by weight of the modified polymer 1 of the ethylene polymer (A) and 50 parts by weight of the modified polymer 3 of the ethylene polymer (A) are dry-blended in advance, and the radical polymerizable unsaturated compound (B1) is added to the blend. Various additives other than 1 and the radical polymerizable unsaturated compound (B2) were added in the same manner as in Example 1 and further dry blended to obtain a sheet in the same manner as in Example 1. The obtained sheet was evaluated. The results are shown in Table 7.

[Example 9]
A sheet was obtained in the same manner as in Example 2 except that 90 parts by weight of the ethylene polymer (A) 2 ′ and 10 parts by weight of the ethylene polymer (A) 3 were replaced. The obtained sheet was evaluated. The results are shown in Table 8.

[Example 10]
A sheet was obtained in the same manner as in Example 9 except that the ethylene polymer (A) 2 ′ was replaced with the ethylene polymer (A) 3 ′. The obtained sheet was evaluated. The results are shown in Table 8.

[Example 11]
A sheet was obtained in the same manner as in Example 9 except that the ethylene polymer (A) 2 ′ was replaced with the ethylene polymer (A) 4 ′. The obtained sheet was evaluated. The results are shown in Table 8.

[Comparative Example 1]
A sheet was obtained in the same manner as in Example 9, except that 100 parts by weight of the ethylene polymer (A) 5 ′ and 0 parts by weight of the ethylene polymer (A) 3 were replaced. The obtained sheet was evaluated. The results are shown in Table 8. As a result, the adhesion strength maintenance rate after the constant temperature and humidity test, the high strength xenon irradiation test, and the heat cycle test was lowered.

[Comparative Example 2]
A sheet was obtained in the same manner as in Example 9 except that 100 parts by weight of the ethylene polymer (A) 6 ′ and 0 parts by weight of the ethylene polymer (A) 3 were replaced. The obtained sheet was evaluated. The results are shown in Table 8. As a result, the ethylene resin composition was hardly melted under the present laminating conditions, and the initial adhesiveness was not exhibited.

[Example 12]
A sheet was obtained in the same manner as in Example 9, except that the ethylene polymer (A) 2 'was replaced with the ethylene polymer (A) 7'. The obtained sheet was evaluated. The results are shown in Table 9.

[Example 13]
A sheet was obtained in the same manner as in Example 9 except that the ethylene polymer (A) 2 ′ was replaced with the ethylene polymer (A) 8 ′. The obtained sheet was evaluated. The results are shown in Table 9.

[Example 14]
A sheet was obtained in the same manner as in Example 9 except that the ethylene polymer (A) 2 ′ was replaced with the ethylene polymer (A) 9 ′. The obtained sheet was evaluated. The results are shown in Table 9.

[Example 15]
A sheet was obtained in the same manner as in Example 9 except that the ethylene polymer (A) 2 ′ was replaced with the ethylene polymer (A) 10 ′. The obtained sheet was evaluated. The results are shown in Table 9.

[Example 16]
A sheet was obtained in the same manner as in Example 9 except that the ethylene polymer (A) 2 ′ was replaced with the ethylene polymer (A) 11 ′. The obtained sheet was evaluated. The results are shown in Table 9.

[Comparative Example 3]
Sheet molding was performed in the same manner as in Example 9, except that the ethylene polymer (A) 2 ′ was replaced with the ethylene polymer (A) 12 ′. However, the sheet was not stiff, the sticking to the first cooling roll was intense, and a uniform sheet having a thickness of 500 μm could not be obtained, and the evaluation of adhesiveness was not achieved.

[Comparative Example 4]
Sheet molding was performed in the same manner as in Example 9 except that 100 parts by weight of the ethylene polymer (A) 13 ′ and 0 parts by weight of the ethylene polymer (A) 3 were replaced. However, since the extruder torque was over and extrusion sheet molding was impossible, a sheet could not be obtained.

[Example 17]
A sheet was obtained in the same manner as in Example 9 except that the ethylene polymer (A) 2 'was replaced with the ethylene polymer (A) 14'. The obtained sheet was evaluated. The results are shown in Table 10.

[Example 18]
A sheet was obtained in the same manner as in Example 9 except that the ethylene polymer (A) 2 ′ was replaced with the ethylene polymer (A) 15 ′. The obtained sheet was evaluated. The results are shown in Table 10.

[Comparative Example 5]
Sheet molding was performed in the same manner as in Example 9, except that the ethylene polymer (A) 2 ′ was replaced with the ethylene polymer (A) 16 ′. However, the adhesion to the first cooling roll was intense, and a uniform sheet having a thickness of 500 μm could not be obtained, and the adhesiveness evaluation was not achieved.

[Example 19]
A sheet was obtained in the same manner as in Example 9 except that the ethylene polymer (A) 2 'was replaced with the ethylene polymer (A) 17'. The obtained sheet was evaluated. The results are shown in Table 11.

[Example 20]
A sheet was obtained in the same manner as in Example 9, except that the ethylene polymer (A) 2 ′ was replaced with the ethylene polymer (A) 18 ′. The obtained sheet was evaluated. The results are shown in Table 11.

[Comparative Example 6]
A sheet was obtained in the same manner as in Example 9, except that 100 parts by weight of the ethylene polymer (A) 19 ′ and 0 parts by weight of the ethylene polymer (A) 3 were replaced. The obtained sheet was evaluated. The results are shown in Table 11. As a result, since a very small amount of acid remained during decalcification, the silver electrode was corroded.

[Comparative Example 7]
A sheet was obtained in the same manner as in Example 9 except that 100 parts by weight of the ethylene polymer (A) 20 ′ and 0 parts by weight of the ethylene polymer (A) 3 were replaced. The obtained sheet was evaluated. The results are shown in Table 11. As a result, there were many metal residues and the dielectric breakdown resistance decreased.

[Example 21]
90 parts by weight of the ethylene polymer (A) 1 ′ and 10 parts by weight of the ethylene polymer (A) 3 are dry-blended in advance, and the blend is a radical polymerizable unsaturated compound (B1) 1 γ- A sheet was obtained in the same manner as in Example 4 except that methacryloxypropyltrimethoxysilane was replaced with vinyltrimethoxysilane as the radical polymerizable unsaturated compound (B1) 2. The obtained sheet was evaluated. The results are shown in Table 12.

[Example 22]
A sheet was obtained in the same manner as in Example 21 except that the addition amount of vinyltrimethoxysilane, which is the radical polymerizable unsaturated compound (B1) 2, and the organic peroxide was changed. The obtained sheet was evaluated. The results are shown in Table 12.

[Example 23]
A sheet was obtained in the same manner as in Example 21 except that the radical polymerizable unsaturated compound (B1) 2 was changed to the radical polymerizable unsaturated compound (B1) 1 and the addition amount was changed to the addition amount of the organic peroxide. It was. The obtained sheet was evaluated. The results are shown in Table 12.

[Example 24]
A sheet was obtained in the same manner as in Example 23 except that the addition amounts of the radical polymerizable unsaturated compound (B1) 1, the radical polymerizable unsaturated compound (B2) and the organic peroxide were changed. The obtained sheet was evaluated. The results are shown in Table 12.

[Example 25]
A sheet was obtained in the same manner as in Example 24 except that the amount of the organic peroxide added was changed. The obtained sheet was evaluated. The results are shown in Table 12.

[Example 26]
A sheet was obtained in the same manner as in Example 25 except that the addition amount of the radical polymerizable unsaturated compound (B2) and the organic peroxide was changed. The obtained sheet was evaluated. The results are shown in Table 12.

[Example 27]
90 parts by weight of the ethylene-based polymer (A) 21 ′, 2 parts by weight of the radically polymerizable unsaturated compound (B1) 2, 0.2 parts by weight of the radically polymerizable unsaturated compound (B2), and 0% of the peroxide A sheet was obtained in the same manner as in Example 21 except that the amount was changed to 0.03 part by weight. The obtained sheet was evaluated. The results are shown in Table 12.

[Example 28]
A sheet was obtained in the same manner as in Example 21, except that 90 parts by weight of the ethylene polymer (A) 21 ′ and 4 parts by weight of the radical polymerizable unsaturated compound (B1) 2 were replaced. The obtained sheet was evaluated. The results are shown in Table 12.

[Comparative Example 8]
A sheet was obtained in the same manner as in Example 22 except that the addition amounts of the radical polymerizable unsaturated compound (B1) 2 and the organic peroxide were changed. The obtained sheet was evaluated. The results are shown in Table 12. As a result, the gel fraction increased and the adhesive strength decreased.

[Comparative Example 9]
A sheet was obtained in the same manner as in Example 22 except that the addition amounts of the radical polymerizable unsaturated compound (B1) 2 and the organic peroxide were changed. The obtained sheet was evaluated. The results are shown in Table 12. As a result, the Si content in the sheet was small, and the adhesion to glass and the back sheet was lowered.

[Comparative Example 10]
A sheet was obtained in the same manner as in Example 24 except that the addition amounts of the radical polymerizable unsaturated compound (B1) 2 and the organic peroxide were changed. The obtained sheet was evaluated. The results are shown in Table 12. As a result, the gel fraction increased and the adhesive strength decreased.

[Comparative Example 11]
A sheet was obtained in the same manner as in Example 24 except that the addition amounts of the radical polymerizable unsaturated compound (B1) 2 and the organic peroxide were changed. The obtained sheet was evaluated. The results are shown in Table 12. As a result, the maleic acid graft group density | concentration in a sheet | seat was small, and the adhesiveness to glass, a back sheet | seat, and a thin film electrode fell.

[Comparative Example 12]
A sheet was obtained in the same manner as in Example 24 except that the addition amounts of the radical polymerizable unsaturated compound (B1) 2 and the organic peroxide were changed. The obtained sheet was evaluated. The results are shown in Table 12. As a result, the concentration of free maleic acid was high and the silver electrode was corroded.

[Example 29]
70 parts by weight of ethylene polymer (A) 21 ', 10 parts by weight of ethylene polymer (A) 3, 20 parts by weight of ethylene / α-olefin copolymer 1, radically polymerizable unsaturated compound (B1) A sheet was obtained in the same manner as in Example 1 except that 2 was changed to 2 parts by weight and the radical polymerizable unsaturated compound (B2) was changed to 0.2 parts by weight. The obtained sheet was evaluated. The results are shown in Table 14.

[Example 30]
Same as Example 28, except that ethylene polymer (A) 21 ′ was replaced by 0 parts by weight, ethylene polymer (A) 3 by 10 parts by weight, and ethylene / α-olefin copolymer 3 by 90 parts by weight. Thus, a sheet was obtained. The obtained sheet was evaluated. The results are shown in Table 14.

[Example 31]
A sheet was obtained in the same manner as in Example 28 except that 85 parts by weight of the ethylene polymer (A) 21 ′ and 5 parts by weight of the ethylene / α-olefin copolymer 2 were replaced. The obtained sheet was evaluated. The results are shown in Table 14.

[Comparative Example 13]
Sheet molding was performed in the same manner as in Example 28 except that 85 parts by weight of the ethylene polymer (A) 21 ′ and 5 parts by weight of the ethylene / α-olefin copolymer 4 were replaced. However, the adhesion to the first cooling roll was intense, and a uniform sheet having a thickness of 500 μm could not be obtained, and the adhesiveness evaluation was not achieved.

[Comparative Example 14]
Same as Example 28, except that the ethylene polymer (A) 21 ′ was replaced by 0 parts by weight, the ethylene polymer (A) 3 by 8 parts by weight, and the ethylene / α-olefin copolymer 1 by 92 parts by weight. Then, sheet forming was performed. However, the adhesion to the first cooling roll was intense, and a uniform sheet having a thickness of 500 μm could not be obtained, and the adhesiveness evaluation was not achieved.

[Example 32]
As a back surface sealing material for a solar cell module, a back sheet (i) made of polyethylene terephthalate resin (Repnea, manufactured by Lintec Corporation) is set inside the first roll surface, and the ethylene-based resin composition of Example 27 is used. And extrusion lamination was performed. As a result, the solar cell sealing in which the solar cell sealing material and the back surface sealing material for the solar cell module having the same performance as in Example 27 in terms of adhesion to the back sheet, silver electrode, and glass are integrated. The material was obtained.

[Example 33]
As a back surface sealing material for a solar cell module, a back sheet (i) made of polyethylene terephthalate resin (Repnea, manufactured by Lintec Corporation) is set inside the first roll surface, and the ethylene-based resin composition of Example 29 is used. And extrusion lamination was performed. As a result, the solar cell sealing in which the solar cell sealing material and the back surface sealing material for the solar cell module having the same performance as in Example 29 in terms of adhesion to the back sheet, silver electrode, and glass are integrated. The material was obtained.

[Example 34]
Solar cell encapsulant surface of solar cell encapsulant integrated with solar cell encapsulant prepared in Example 32 and back surface encapsulant for solar cell module / commercially available EVA solar cell encapsulant (Mitsui Chemicals) Fabricated by Fabro Co., Ltd. (Solar EVA) / glass, charged in a vacuum laminator, placed on a hot plate adjusted to 150 ° C., heated under vacuum for 2 minutes, 13 minutes, and sealed with glass / EVA / solar cell A laminated laminate of a sealing material / back surface sealing material for a solar cell module is prepared, and then left for 60 minutes in an air circulation oven at 150 ° C. to crosslink EVA and to make glass / EVA / solar cell sealing material / sun The laminated body of the back surface sealing material for battery modules was obtained. The solar cell encapsulant sheet sample of this laminate was cut to a width of 15 mm, and the peel strength with EVA was measured at 180 degrees peel. As a result, the adhesive strength between EVA and the solar cell encapsulant was sufficiently developed, and the base material of the solar cell encapsulant was destroyed.

[Example 35]
The solar cell encapsulant prepared in Example 33 was obtained in the same manner as in Example 33 to obtain a laminate of glass / EVA / solar cell encapsulant / back surface encapsulant for solar cell module. The solar cell encapsulant sheet sample of this laminate was cut to a width of 15 mm, and the peel strength with EVA was measured at 180 degrees peel. As a result, the adhesive strength between EVA and the solar cell encapsulant was sufficiently developed, and the base material of the solar cell encapsulant was destroyed.

[Example 36]
The solar cell encapsulant of Example 2 was sandwiched between a glass plate (hereinafter abbreviated as a thin film electrode) in which silver was sputtered at the center, and a sheet sample having a thickness of 0.5 mm was sandwiched and charged in a vacuum laminator at 150 ° C. And then heated for 2 minutes and 13 minutes under vacuum to prepare a thin film electrode sputtered glass / sheet sample laminate. This sample was put into a constant temperature and humidity tester, and the state of the silver electrode after 2000 hours was confirmed. As a result, the silver electrode was not corroded as it was at the beginning of charging. In addition, Table 15 shows the results of water vapor permeability.

[Example 37]
A laminated body of thin-film electrode sputtered glass / sheet sample was produced from the solar cell encapsulant of Example 28 in the same manner as in Example 36. This sample was put into a constant temperature and humidity tester, and the state of the silver electrode after 2000 hours was confirmed. As a result, the silver electrode was not corroded as it was at the beginning of charging. In addition, Table 15 shows the results of water vapor permeability.

[Example 38]
A thin film electrode sputtered glass / sheet sample laminate was produced from the solar cell encapsulant of Example 27 in the same manner as in Example 36. This sample was put into a constant temperature and humidity tester, and the state of the silver electrode after 2000 hours was confirmed. As a result, the silver electrode was not corroded as it was at the beginning of charging. In addition, Table 15 shows the results of water vapor permeability.

[Comparative Example 15]
A commercially available EVA solar cell encapsulating material (Solar EVA, manufactured by Mitsui Chemicals Fabro Co., Ltd.) is 0.5 mm thick between glass plates (hereinafter abbreviated as thin film electrodes) in which silver is sputtered at the center. The sheet sample was sandwiched, charged in a vacuum laminator, placed on a hot plate adjusted to 150 ° C., and heated under vacuum for 2 minutes for 13 minutes to prepare a thin film electrode sputtered glass / sheet sample laminate. Subsequently, it was allowed to stand for 60 minutes in an air circulation oven at 150 ° C., and EVA was crosslinked to prepare a thin film electrode sputtered glass / sheet sample. This sample was put into a constant temperature and humidity tester, and the state of the silver electrode after 2000 hours was confirmed. As a result, the silver electrode was slightly corroded from the initial stage. In addition, Table 15 shows the results of water vapor permeability.

  The present invention relates to an ethylene resin composition excellent in adhesion to glass, a back sheet, and a thin film electrode, electrical insulation, transparency, moldability and process stability, and further relates to a solar cell encapsulant using the same.

  The present invention further relates to a solar cell sealing sheet using such a solar cell sealing material, and a solar cell module using the sealing material and / or the sealing sheet.

  Moreover, the solar cell sealing material of this invention is excellent also in moisture permeability, and is useful as a solar cell sealing material of the solar cell module for thin films, and the solar cell sealing material of the back surface side of a crystalline solar cell module.

Claims (18)

An ethylene polymer (A) that simultaneously satisfies the following requirements a) to e):
A radically polymerizable unsaturated compound (B1) comprising an ethylenically unsaturated silane compound;
Selected from hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or their derivatives, vinyl ester compounds, vinyl chloride and carbodiimide compounds A radically polymerizable unsaturated compound (B2) comprising at least one compound
An ethylene-based resin composition containing a modified product obtained by modification.
a) Density is 900-940 kg / m ³
b) 90-125 ° C melting peak based on DSC
c) Melt flow rate (MFR2) measured at 190 ° C. and 2.16 kg load in accordance with JIS K-6721 is 0.1 to 100 g / 10 minutes d) Mw / Mn is 1.2 to 3.5
e) 0.1-50 ppm of metal residue (I) A modified product (1) obtained by modifying an ethylene polymer (A) with a radically polymerizable unsaturated compound (B1), or an ethylene polymer (A) and an ethylene / α-olefin copolymer Modified product (3) obtained by modifying the mixture of (C) with the radical polymerizable unsaturated compound (B1)
A modified body selected from
(Ii) A modified product (2) obtained by modifying an ethylene polymer (A) with a radically polymerizable unsaturated compound (B2), or an ethylene polymer (A) and an ethylene / α-olefin copolymer. Modified product (4) obtained by modifying the mixture of (C) with the radical polymerizable unsaturated compound (B2)
A modified body selected from
The ethylene resin composition according to claim 1, comprising: (I) Modified polymer (5) obtained by modifying ethylene polymer (A) with radical polymerizable unsaturated compound (B1) and radical polymerizable unsaturated compound (B2), or ethylene polymer (A ) And an ethylene / α-olefin copolymer (C) modified with a radically polymerizable unsaturated compound (B1) and a radically polymerizable unsaturated compound (B2) (6)
A modified body selected from
(Ii) A modified product (1) obtained by modifying an ethylene polymer (A) with a radically polymerizable unsaturated compound (B1), or an ethylene polymer (A) and an ethylene / α-olefin copolymer Modified product (3) obtained by modifying the mixture of (C) with the radical polymerizable unsaturated compound (B1)
A modified body selected from
The ethylene resin composition according to claim 1, comprising: (I) Modified polymer (5) obtained by modifying ethylene polymer (A) with radical polymerizable unsaturated compound (B1) and radical polymerizable unsaturated compound (B2), or ethylene polymer (A ) And an ethylene / α-olefin copolymer (C) modified with a radically polymerizable unsaturated compound (B1) and a radically polymerizable unsaturated compound (B2) (6)
A modified body selected from
(Ii) A modified product (2) obtained by modifying an ethylene polymer (A) with a radically polymerizable unsaturated compound (B2), or an ethylene polymer (A) and an ethylene / α-olefin copolymer. Modified product (4) obtained by modifying the mixture of (C) with the radical polymerizable unsaturated compound (B2)
A modified body selected from
The ethylene resin composition according to claim 1, comprising: The ethylene-based resin composition according to any one of claims 2 to 4, wherein the ethylene / α-olefin copolymer (C) satisfies the following requirement f).
f) density of 850 kg / m ³ or more, 895kg / m less than ³ The reaction for obtaining the modified product is an ethylene polymer (A) or a mixture of an ethylene polymer (A) and an ethylene / α-olefin copolymer (C),
A radically polymerizable unsaturated compound (B1) and / or a radically polymerizable unsaturated compound (B2);
Organic peroxides,
The ethylene-based resin composition according to any one of claims 2 to 5, wherein the ethylene-based resin composition is formed by extrusion-melting modification. The ethylene-based resin composition according to claim 6, wherein the ethylene-based polymer (A) used for the reaction for obtaining the modified product is a powder of the ethylene-based polymer (A). The ethylene-based resin composition according to claim 6, wherein the ethylene-based polymer (A) used in the reaction for obtaining the modified product is a mixture of powder and pellets of the ethylene-based polymer (A). The reaction for obtaining the modified product is a radically polymerizable unsaturated compound (B1) and / or a radically polymerizable unsaturated compound (B2) and an organic peroxide impregnated in advance with a powder of an ethylene-based polymer (A). The ethylene resin composition according to claim 6, wherein the ethylene resin composition is formed in the presence of a mixture of pellets of an ethylene polymer (A). The graft group concentration attributable to the radically polymerizable unsaturated compound (B2), measured by the infrared absorption spectrum of the ethylene resin composition, is in the range of 0.05 to 5.0% by weight, and the free radically polymerizable compound ( The amount of B2) is 500 ppm or less, and a gel fraction is 30% or less, The ethylene-type resin composition of any one of Claims 1-9 characterized by the above-mentioned. The ethylene-based resin composition according to any one of claims 1 to 10, wherein the radically polymerizable unsaturated compound (B2) is an unsaturated carboxylic acid or a derivative thereof. The ethylene-based resin composition according to any one of claims 1 to 11, further comprising at least one additive selected from an ultraviolet absorber (D), a radical scavenger (E), and a heat stabilizer (F). object. The solar cell sealing material which consists of an ethylene-type resin composition of any one of Claims 1-12. The solar cell encapsulant according to any one of claims 1 to 13, wherein the ethylene-based resin composition is in a sheet form. The solar cell sealing material according to claim 13 or 14, which is integrated with a back surface sealing material for a solar cell module. The solar cell module obtained using the solar cell sealing material of Claims 13-15. A thin film solar cell module obtained by using the solar cell encapsulant according to claim 13-15. A crystalline solar cell module obtained by using the solar cell encapsulant according to claim 13 as a solar cell encapsulant on the back surface side.