JPS5860579A - Filled adhesive sheet for solar battery and bonding method using the same - Google Patents

Abstract

PURPOSE:To obtain an excellent solar battery module, by interposing a solar battery element between filled adhesive sheet comprising an ehtylene copolymer resin containing a coupling agent and an organic peroxide, followed by heating. CONSTITUTION:A dry-blended mixture of 100pts.wt. ethylene vinyl acetate copolymer, 1.5pts.wt. tert-butyl peroxybenzoate, 1pt.wt. c-methacryloxypropyltrimethoxysilane, and the like is extruded in sheet form at the resin temperature of 95 deg.C using a T-die extruder to prepare an embossed sheet. This sheet is placed on a white plate glass and silicon semiconductor wafers for solar battery are arranged on the sheet. Another embossed sheet and a polyvinyl floride sheet are superposed thereon successively, molten and laminated at a heating temperature of 110 deg.C. The organic peroxide is decomposed by heating at 150 deg.C for 30min to effect crosslinking of the ethylene/vinyl acetate copolymer, thereby obtaining the intended module.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a filling adhesive sheet for solar cells and an adhesion method using the same. More specifically, the present invention relates to a filled adhesive sheet for solar cells exhibiting modified adhesive properties and an adhesion method using the same.

In recent years, it has been pointed out that existing energy sources, mainly petroleum, are depleted, and the development of alternative energy sources has become necessary.In this context, solar power generation has been recognized as a clean energy source and an inexhaustible source of solar radiation. As a means of utilizing energy, it is hoped that it will be put to practical use and become popular as soon as possible. Solar power generation uses solar cells to directly convert the sun's radiant energy into electrical energy.This function is achieved by utilizing the quantum effects of semiconductors, generally silicon semiconductors, selenium conductors, etc. can get.

By the way, the functions of silicon semiconductors and the like deteriorate when exposed directly to the outside air, so for the purpose of protecting them from the outside air, an upper transparent protective material made of glass, acrylic resin, carbonate resin, etc., glass, stainless steel, etc. GaAe is provided by a lower substrate maintenance material made of steel, aluminum, plastic, etc. At this time, the high-performance silicon semiconductors used for solar power generation are usually wafers (small thin film pieces), so these wafers are arranged in series or parallel using interconnectors, electrically connected, There is a need for fixation, and filler adhesives are generally used because of their adhesive properties.

The physical properties required of this filling adhesive include the following.

(1) In order to prevent wafers such as silicon semiconductors from being destroyed by internal strain caused by thermal expansion and contraction, they must have elastomer-like properties. (2) External protection materials and filling adhesives that are exposed to sunlight must have elastomeric properties. Since power generation is possible only after passing through the silicon semiconductor in sequence, the filler adhesive used during this time must have a high photofat transmittance of sunlight.(3) Outside m4M material ε0 adhesiveness (4) Wafers such as silicon semiconductors have a small electromotive force;
For this reason, a useful voltage can be obtained by connecting wafers in series or parallel, so the connection material must not corrode and have a high dielectric strength. No change in properties Conventionally, heat-crosslinking liquid silicone resins have been used to have these properties, but these are expensive, require long coating and bonding processes, and are not suitable for automation. There was a drawback. For this reason, sheets of polyvinyl butyral resin, which has a proven track record in laminated glass, have recently begun to be used, but is this also for solar cells? It cannot be said that it is necessarily satisfactory as a filling adhesive. That is, the polyvinyl butyral sheet has K starch and sodium bicarbonate attached to its surface to prevent pronking.
Prior to use, it must be washed off, dried and conditioned. Furthermore, since the fluidity of the resin is poor, it is necessary to use an autoclave for bonding, which takes a long time and is not suitable for automation. Furthermore, qualitative KFi
, due to its high water absorption rate, it has poor moisture resistance f%, and if left under high g and temperature for a long time, it will cause devitrification phenomenon, which will not only reduce the light transmittance, but also cause adhesion! The thermal conductivity also decreases significantly, and a peeling phenomenon occurs at the interface between the upper transparent protective material, the lower substrate protective material, and the solar cell element. Furthermore, low-temperature properties (flexibility) are not necessarily good.

In place of polyvinyl butyral sheets, which have these disadvantages, ethylene-vinyl acetate comonomer sheets have recently begun to be considered from the viewpoint of reducing the cost of solar cell modules. However, the commonly used ethylene
Vinyl acetate copolymers cannot satisfy the characteristics required as filler adhesives for solar cells. That is, as the vinyl acetate content increases in this copolymer, transparency and flexibility improve, but sheet formability and prongability deteriorate, making it difficult to satisfy both properties at the same time. In addition, the heat resistance and light resistance are insufficient. Furthermore, the durable adhesion between the upper transparent protective material and the lower substrate and koji material, which determines the reliability of the solar cell module, is not sufficient.

The inventors used an ethylene copolymer resin such as ethylene-vinyl acetate copolymer, and also achieved various properties required for charging materials for solar cells, especially initial adhesion and durable adhesion with storage materials. As a result of various studies in search of a 7-filled adhesive sheet with excellent adhesive properties and suitable for automating and shortening the bonding process, and an adhesive method using the same, we developed a ethylene-based adhesive sheet containing a compressing agent and an organic peroxide. The present invention has been completed based on the discovery that a sheet formed from a copolymer is fully suitable for such purposes.

Therefore, the present invention relates to a filling adhesive sheet for solar cells,
This filler adhesive consists of an ethylene copolymer resin containing a coupling agent and an organic peroxide. The present invention also relates to a method of adhering a solar cell protective material and a filler.
The adhesive between the agricultural preservation material and the filler is achieved by sandwiching the large tilt pond element between at least two filler adhesive sheets made of an ethylene copolymer resin containing a coupling agent and an organic peroxide, and then Either the upper transparent protective material and the lower substrate protective material are layered on both 98, or a filled adhesive sheet made of an ethylene copolymer resin containing a camping agent and an organic peroxide is used as an intermediate layer to protect either one. In the module lamination process in which the upper transparent protective material and the lower substrate protective material, each of which has a solar cell element formed on its inward facing surface, are stacked above and below the intermediate layer filling adhesive sheet,
Heating above the decomposition temperature of the organic peroxide is carried out.

As an ethylene copolymer resin, Hikari fi! Transmittance is about 8
0% or more, preferably about 90% or more, and an elastic modulus of about 1 to 30 MPa, preferably about 3 to 12 MPa, is used as a suitable copolymer resin. Specifically, for example, copolymers of ethylene and vinyl esters such as vinyl acetate and vinyl fluohionate, copolymers of ethylene and unsaturated fatty acid esters such as ethyl acrylate, butyl acrylate, and methyl methacrylate, and ethylene. and copolymers with α-olefins such as propylene and butene-1,4-methylpentene-1, as well as ethylene-vinyl ester-unsaturated fatty acid ternary copolymers, and ethylene-unsaturated fatty acid esters! A combination of ternary and monounsaturated fatty acids or a metal salt thereof (ionomer resin) is used.

Among these ethylene-based copolymer resins, the most preferable one from the viewpoint of stability is ethylene-vinyl acetate copolymer, in which case the vinyl acetate content in the copolymer is about 20%.
~40% by weight, preferably about 25-40% by weight are suitable. If the vinyl acetate content is less than this, the light a transmittance will be low and the power generation efficiency of the module will be low, and the elastic modulus will also be high, increasing the risk of damage to the power generation element due to thermal expansion and contraction. . However, in the case where a filling adhesive sheet is pasted under the solar cell element formed on the lower surface of the upper transparent protective material, the light transmittance of that part is irrelevant, so the vinyl acetate content is approximately 20% by weight. % or less of ethylene-vinyl acetate copolymer can also be used. On the other hand, if the vinyl acetate content increases more than this, the extrusion moldability of the sheet will deteriorate, and the resulting sheet will become more sticky and prone to bronking.

These ethylene copolymer resins contain a camping agent and an organic peroxide.

As the camping agent, there is used one that has a good bonding function when the ethylene copolymer resin containing the compound is thermally bonded to the external protective material in the coexistence of an organic peroxide. As such a coupling agent, the general formula R
81X3 (where R is a vinyl group, an aminoalkyl group,
methacryloxyalkyl group, acryloxyalkyl group,
A monosilane compound represented by the general formula R', which is a reactive organic group such as a mercagto alkyl group or an epoxy group, and X is a hydrolyzable group such as a halogen atom, an alkoxy group, or an acetoxy group. 81 Organosilane peroxide represented by (○OR')n (where R' is a vinyl group or an alkyl group υ, R' is a hydrocarbon group, and n is an integer from 1 to 4) or general formula R”0Ti(OYR”)
Z ) 3 (Connie, fFi is an alkyl group, Y is a carboxyl group, phosphate group, pyrophosphate group, phosphite group, or sulfonyl group, Z is a hydrogen atom, an amino group, a hydroxyl group, a mercapto group) Typical examples include organic titanate compounds represented by , acrylic or methacrylic groups.

In addition to the above-mentioned adhesion function, consideration must be given to these camping agents in terms of kneadability and compatibility with the ethylene copolymer resin, odor, light resistance, non-corrosion to interconnectors, etc., and cost. There is. From this point of view, preferred coupling agents include vinyltriethoxysilane and vinyltris(β-methoxyethoxy).
Silane, r-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, r-glycidoxyglobiltrimethoxysilane, γ-glycidoxyglobiltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane It is an organic silane compound having an unsaturated group or an epoxy group such as.

When using an organic silane peroxide as a coupling agent, it is suitable that its decomposition temperature (temperature at which the half-life is 1 hour) is about 90 to 190°C, preferably about 120 to 160°C. As a dark organosilane peroxide,
CH381 (oo-t, -Bu included, CH2-CH31
(OOR') (where R' is a tertiary butyl group, a cumyl group, or a p-menthyl group).

These camping agents are: 1. Ethylene copolymer resin 1
From the viewpoint of economy and adhesion, it is generally used in a proportion of about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight, per 0.00 parts by weight. The combination of this and the organic peroxide provides a strong adhesive force between the ethylene copolymer resin and the external protective material, which is useful in practice. That is, compared to the case where only the camping agent or the organic peroxide is used, the adhesiveness is clearly improved when these are used in combination.

The cause of this is not fully understood, but for example, when using a silane coupling agent with an unsaturated group,
During heating and bonding, the organic peroxide decomposes and generates radicals in the ethylenic copolymer resin. The majority of these polymer radicals are thought to be involved in the crosslinking reaction of the ethylenic copolymer resin, but the remaining A part of the silane coupling agent reacts with the unsaturated group of the silane coupling agent, that is, the coupling agent is grafted onto the ethylene copolymer resin, and this grafted coupling agent is transferred between the ethylene copolymer resin and the protective material. It is also thought that these molecules exist and are involved in the formation of very strong adhesion.

Organosilane peroxides used as camplinking agents are also thought to have the function of crosslinking ethylene copolymer resins, similar to the organic peroxides used in combination, but their crosslinking efficiency is lower than that of organic peroxides. It is not preferable to use organic silane peroxide as a substitute for organic peroxide because it is inferior to organic peroxide and disadvantageous in terms of cost, and it is preferable to use both in combination.

Organic peroxides (thus, organosilane peroxides are naturally excluded) used in combination with compulsions must be A material that does not decompose but quickly decomposes at a temperature below the decomposition temperature of the ethylene copolymer resin during the molecularization process is used. In general,
Those having a decomposition temperature (a temperature with a half-life of 1 hour) of about 90-190°C, preferably about 120-160°C are used.

Examples of such organic peroxides include tert-butyl peroxyisopropyl carbonate, t-butyl peroxy acetate, t-butyl no-oxybenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-bis( tertiary-butylperoxy)hexane, di-tertiary-butylperoxide, 2,5-dimethyl-2,5-bis(tertiary-butylperoxy)
butylperoxy)hexyne-3, Ll-bislR3butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, methyl ethyl ketone peroxide, 2,5-
Dimethylhexyl-2,5-bisperoxybenzoate, tert-butyl hydroperoxide, p-menthane hydroperoxide, benzoyl peroxide,
Examples include p-chlorobensyyl peroxide, tert-butyl peroxyisobutyrate, hydroxybutyl peroxide, and chlorhexanone peroxide.

These organic peroxides are used to crosslink the ethylene copolymer resin during the solar cell module bonding process and improve heat resistance, and also to cause interaction between the camping agent and the filler adhesive. , only the amount necessary to contribute to improved adhesion is added.

Generally, about 01 to 5 N parts, preferably about 05 to 3 N parts, of the organic peroxide is added to 100 parts of the ethylene copolymer resin. If the addition ratio is less than this, transparency, heat resistance, and adhesion between the filling adhesive and each external retaining material will not be sufficient.

When the filling adhesive is required to have very high light resistance, it is preferable to add a secondary light stabilizer, for example, 2-hydroxy-4-methoxypentuphenone, 2-hydroxy-4-methoxypentuphenone,
．． 2'-dihydroxy-4-methoxybenzophenone,
Benzophenone series such as 2-hydroxy-4-methoxy-2'-carboxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone, 2-(2'-hydroxy-a'5'-di-tert-butylphenyl) pen Tutriazole, 2-(2'-hydroxy-5-methylphenyl)pentutriazole 2 (27-hydroxy-
Benzotriazole-based stabilizers such as 5-tertiary octylphenyl) benzotriazole, salicylic acid ester-based stabilizers such as phenyl salicylate and p-octylphenyl salicylate, ninkel complex salt-based stabilizers, hindered amine-based stabilizers, and the like are used as light stabilizers.

By using these light stabilizers Fi in combination with antioxidants such as hindered phenol threads and phosphite threads, a synergistic effect may be expected.

The sheet used as the filling adhesive can be formed by a known method using an r-die extruder or the like. That is, 1 ethylene copolymer resin 1 cambling agent, an organic peroxide, and a light stabilizer added as necessary are tri-blended in advance and fed from the hopper of the extruder, so that the organic peroxide is substantially Molding is carried out by extrusion into a sheet at a molding temperature that does not cause decomposition, preferably with an embossed patterned take-up roll. Formation of an arbitrary embossed pattern is effective for preventing sheet pronking and for degassing during the solar cell modularization process. The thickness of the sheet is not particularly specified, but is generally approximately α1 to 11.
It is about 1J1.

In addition, if the camping agent or organic peroxide is in the form of a solution or used as a solution, use an extruder with a well-known vent function to prepare pellets from which the solvent has been removed in advance, and then perform the above steps. Alternatively, a T-die may be installed directly at the tip of an extruder having a vent function, and the solvent may be removed by the vent device to form a sheet at once.

Modularization of solar cells can be carried out as follows. When solar cell elements are made of silicon semiconductor or selenium semiconductor wafers, these solar cell elements are sandwiched between at least two filled adhesive sheets, and a surfactant solution or an organic solvent is further applied on both sides as necessary. This is done by laminating the protective material that has been cleaned by cleaning or surface treated with K such as corona discharge or chemical agents, that is, the upper transparent protective material and the lower substrate protective material, by heating and bonding them under vacuum. be exposed. At this time, the lower substrate protective material, the filling adhesive sheet, the solar cell element, the filling adhesive sheet, and the upper transparent protective material are overlaid in a j-order order (industrial practice is to perform 9 laminations). It is also preferable to pre-laminate the solar cell element with at least two filled adhesive sheets made of an ethylene-based amalgamated resin containing a combing agent and an organic peroxide, and then cover the upper transparent preservation material and the lower substrate. It may be laminated with a protective material.Heating is
It is desirable that the organic peroxide added to the filler adhesive be completely decomposed. Through this heat treatment, the filling adhesive material and the external protection material are firmly adhered, and the solar cell element is laminated with two sheets of the filling adhesive material, and it is also bonded to the upper transparent koji protective material and the lower part. A solar cell module is formed thereon, which is firmly bonded to the substrate protection material.

In addition, when the solar cell element is formed on a protective material such as glass, glasstic, ceramic, stainless steel, etc., a filling adhesive sheet is used as an intermediate layer, and the inner surface of one of the protective materials (filling An upper transparent protective material and a lower substrate protective material on which solar cell elements are formed on the adhesive sheet a (touch surface) are laid one above and below the intermediate layer filling adhesive sheet,
Specifically, a Kffi-filling adhesive sheet and an upper transparent protective material are placed over the solar cell element formed on the upper surface of the lower substrate protective material, or a filling adhesive sheet is placed under the solar cell element formed on the lower surface of the upper transparent protective material. and the lower substrate protective material are stacked one on top of the other and heated and bonded under vacuum in the same way as in the previous case. One protective material, the filled adhesive sheet, and the other protective material form a solar cell element. A solar cell module is formed therein, in which the solar cell modules are firmly bonded together.

In this way, the solar cell formed by adhering by the method using the optical filler adhesive sheet according to the present invention has a high peel strength between the protective material and the filler adhesive, and has good peel resistance under humid conditions. It fully satisfies all of the properties required for solar cell modules, such as excellent initial adhesion and durable adhesion, little change under UV irradiation, and good light transmittance. It also has the effect of enabling automated and shortened lamination.

Next, the present invention will be described with reference to one embodiment.

Example 1 Ethylene-vinegar #R Renyl copolymer (Mitsui Polychemical product Evaflex 250, vinyl acetate content 2Bk violet%,
Melt index 15) 100 parts (A11L, same below), 15 parts of tert-butyl peroxybenzoate, γ-
1 part methacryloxyglobil trimethoxysilane, 2-
A tri-blend mixture of 03 parts of hydroxy-4-n-octylbenzophenone and 01 part of tetrakis-[methylene-3-(35'-di-tert-butyl-4'-hydroxyphenyl)globionate]methane was extruded through a T-die. The resin was extruded into a sheet using a machine at a resin temperature of 95° C., and taken up with an embossed pattern-containing take-up roll to form an embossed sheet having a thickness α5+u with embossed patterns on both sides of the sheet.

Modularization of solar cells using this embossed sheet was carried out as follows.

After washing the surface with a neutral detergent aqueous solution, the embossed sheet was placed on white glass (thickness 3 m, light transmittance 91% at 450 mμ) that had been washed with distilled water and air-dried, and the interconnector was placed on top of it. multiple silicon semiconductor wafers for solar cells (element light-receiving area 18α/piece) using
are arranged in series, and the embossed sheet and polyfluorinated vinyl sheet → (Tetra-400B manufactured by DuPont, USA) are arranged in series.
S 30WH) were stacked one on top of the other and melted and bonded using a vacuum 2minator at a heating temperature of 1 0°C, and further heated at 150°C for 30 minutes to decompose the organic peroxide and form ethylene-vinyl acetate. A module was produced in which the copolymer was cross-linked and firmly adhered to each IH agricultural product. When the power generation performance of this solar cell module is measured, the incident energy is 1. OOmW/c+
A value of a shunt current of 370 +++ J/l 8cIn2 and a voltage of 6 V/18α2 was obtained at u.

Example 2 The white plate glass-embossed sheet-bore blown vinyl sheet laminate used in Example 1 was used in Example 1.
The peel strength of this laminate was measured using a tensile tester at a tensile speed WL2 Q am/min and a temperature [23°C,
Measurement was performed by T-peeling under conditions of relative humidity of 60%, and the average value of 5 samples was calculated. As shown in the results in the table below, good peel strength was observed between the embossed sheet and the white glass, or between the poly7-containing material and Nilnote.

Example 3 The white rice glass-embossed sheet-white plate glass laminate used in Example I was produced in the same manner as in Example 1, and the laminate was measured at wavelength 5 using a Uv meter.
The light transmittance at 00711μ was measured, and the appearance was observed by continuously irradiating ultraviolet rays for 100 hours using an ultraviolet irradiator. As shown in the results of post-dressing, the light transmittance was good and the appearance after UV irradiation was also good.

Example 4 The module produced in Example 1 was subjected to a temperature cycle test and a humidity cycle test. In the temperature cycle test, high temperature (+90℃) and low temperature (-
40℃), one cycle is 4 hours each, and this is 20 cycles.
When the appearance of the module after the cycle was observed, no abnormality was observed. In the humidity cycle test, 90% relative humidity and 40°C pig enclosure atmosphere [16 hours,
When the appearance of the module was observed after 20 cycles of 6 hours of VC under an atmosphere of 9.0% phase relative change and 23° C., no abnormality was found.

From the results of Examples 1 to 4 above, the sheet containing the ethylene copolymer resin, camping agent, and organic peroxide used in the present invention is extremely useful as a filling adhesive sheet for solar cells. I understand that.

Example 5 Ethylene-vinyl acetate copolymer (Mitsui Polychemical product Eva 7 Lenx 1501 Vinyl acetate wrinkles 33%, melt index 3o) 100ss2.5-dimethyl-
15 parts of 2,5-bis(tert-butylperoxy)hexane, 1 part of γ-methacryloxyglobyltrimethoxysilane, 0 parts of 2-hydroxy-4-n-octylbenzoneenone
The same procedure as in Example 1 was carried out using a dot-blended mixture of 3 parts of bis(2°2.6.6-tetramethyl-4-piperidine) sebacate 01N and 2 parts of tris(mixed mono-dinonylphenyl) phosphite α. Emboss 7-
A solar cell module was fabricated using this embossed sheet.

Example 6 White board gas 2 suede/
Bossi 〒Tobori 7-layer vinyl sheet laminated metal example 1
The peeling strength of this laminate was 1r.
It was measured in the same manner. As shown in the results in the table below,
Good peel strength was observed between the embossed sheet and the white glass or poly7inated vinyl sheet.

Example 7 The white glass-embossed sheet-white glass laminates used in Example 5 were produced in the same manner as in Example 1, and the laminate was measured for light transmittance and irradiated with ultraviolet rays in the same manner as in Example 3. I conducted a test. As shown in the results in the table below, the light transmittance was good, and the light transmittance was good even when exposed to ultraviolet rays.

Example Day In Example I, the same amount of γ-glycidoxyglobyltrimethoxysilane was used instead of r-methacryloxypropyltrimethoxysilane, and an embossed sheet was formed and a solar cell module was produced using this embossed sheet. I did this.

Example 9 The white glass-embossed sheet-polyvinyl fluoride sheet laminate used on the day of the example was used in Example 1.
The peel strength of this laminate was measured in the same manner as in Example 2, and the results are shown below.

Example 10 In Example 1, the same amount of r-mercaptoglobil trimethoxysilane was used instead of r-methacryloxypropyltrimethoxysilane, and an embossed sheet was formed and a solar cell module was produced using this embossed sheet. 9.

Example 11 The white glass-embossed sheet-polyfluorinated vinyl sheet laminates used in Example 10 were prepared in the same manner as in Example 1, and the peel strength of this laminate was measured in the same manner as in Example 2. The results are shown in the light below.

Example 12 In Example 1, CH-CH-8i-(oo
Using 3 parts of a 30% by weight toluene solution (Shin-Etsu Silicon Products X-12-530) of t Bu A bereft was prepared by extruding at 90°C to remove toluene, and other ingredients were added to this pereft to form an embossed sheet. Furthermore, a solar cell module was manufactured using this embossed notebook.

Implementation 1r1413 Implemented the white rice glass-embossed sheet-polyfluorinated vinyl sheet layered material used in Example 12, respectively?
! The peel strength of this laminate was measured by pressing in the same manner as in Example 2, and the results are shown in the light below.

5!11! In Example 1, the same amount of vinyltriethoxysilane was used in place of r-methacryloxypropyltrimethoxysilane, and an embossed sheet was formed and a solar cell module was fabricated using this embossed sheet.

Example 5 The white glass embossed sheet-polyfluorinated vinyl sheet B laminate used in Example 14 was prepared in the same manner as in Example 1, and the peel strength of this laminate was determined as in Example 2.
It was measured in the same manner as above, and the results are shown in the section below.

Comparative Example 1 In Example Y, an embossed sheet was molded without using r-methacryloxypropyltrimethoxysilane. Using this embossed sheet, a white glass-embossed sheet-polyvinyl 7-phosphate sheet laminate was prepared using Example 2 and fi', and the peel strength of this laminate was measured in the same manner as in Example 2. added. As shown in the optical results described below, practically sufficient adhesive strength could not be obtained between the embossed sheet and the white glass or U-holinated vinyl sheet.

Comparative Example 2 In Example 5, 2,5-dimethyl-2,5-bis(
tert-butylperoxy) without hexano-h fa form Schiff'c. This embossed sheet? I
- In the same manner as in Example 2, a white plate glass-Enphosnote-polyfluorinated vinyl sheet laminate was prepared, and the peel strength of this laminate was measured in the same manner as in Example 2. Postscript The conclusion of light! As shown in JK, a practically sufficient adhesive strength was obtained between the embossed sheet and the polyvinyl 7-vinyl sheet.

From the comparison with Example 2.6.9, U1, and Comparative Example 1.2 above, it is clear that in these laminates, the reaction between the cannoling agent and the organic peroxide affects the adhesion between each layer. I can clearly see that it has contributed greatly.

Comparison? ! l 3 In Example 1, the vinyl acetate gold lid was made of an embossed sheet using 45% by weight ethylene-vinyl acetate copolymer (three-piece polychemical product Evaflex 45x1 melt index 80) instead of the 28-layer one. Although molding was carried out, it was not possible to obtain a satisfactory embossed sheet due to significant adhesion to the take-up roll.

Comparative Example 4 In Example 1, instead of the vinyl acetate content of 28 coul%, an ethylene-vinyl acetate copolymer (Mitsui Polychemical product Evaflex 550, melt index 15) with a content of 141 L is used! An embossed sheet was formed using R (resin temperature: 110°C), and a white glass-embossed sheet-white glass laminate was produced using this embossed sheet in the same manner as in Example 3. The light transmittance was measured and the results are shown in the light section below.

From the comparison of Examples 1.3.5 and 3.4 with Comparative Example 3.4, it can be seen that it is preferable to use an ethylene-vinyl acetate copolymer having a vinyl acetate content of about 20 to 40%.

Comparative Example 5 In Example 1, an embossed sheet was formed using only the ethylene-vinyl acetate copolymer, and this embossed sheet was used in the same manner as in Example 2 to form a white board embossed sheet - polyvinyl fluoride/- Create a layered material,
The peel strength of this laminate was measured in the same manner as in Example 2. As shown in the optical results described below, practically insufficient adhesive strength was obtained between the embossed sheet and the white glass or polyfluorinated vinyl sheet.

Comparative Example 6 The starch adhering to the surface of a Futilal town resin sheet (DuPont product Butasite) was washed with water, dried, and processed, and used as an intermediate layer, and heated under pressure using an autocube at a heating temperature of 160℃. A laminate was prepared by melt-bonding the white glass and the polyfluorinated vinyl sheet at ℃ for 30 minutes, and the peel strength of this laminate was measured in Example 2.
Measurements were made in the same manner as above, and the results are shown in the table below.

Example 2 & 4 2.3
-1 86 〃 3 - #62.9 2.0
-- 90 〃 7 - #92.4 1.9
-I/ll 2.7 2
・〇 -#13 18
13 -/'115
1. '+2.2
- Comparative Example 1 01 No. 0
−〃 2 α
α1 --
68 No. - 5 αl α1
-//64,0 2・0
Example 16 The embossed sheet (h) obtained in Example 1 and the polyfluorinated vinyl sheet were sequentially stacked on top of the solar cell element formed on the white glass substrate to form a module in the same manner as in Example 1 and ()I51. Pasting was done.

A temperature cycle test and a humidity cycle test were conducted on the sampled solar cell module in the same manner as in Example 4. When the external appearance of the module was observed after 20 cycles of the temperature cycle test and 20 cycles of the humidity cycle test, no abnormalities were found in either case.

Representative Patent Attorney Toshio Yoshida Proceeding Sleeve Masashi (spontaneous) 1 Description of the case 1982 Patent Registration No. 158102 2 Name of the invention Filled adhesive sheet for solar cells and adhesion method using the same 3 Person making the amendment 4 Agent address: 1-2-10 Shiba Koen, Minato-ku, Tokyo Logiman Shiba Koen 6CF No. 7 a Specification subject to amendment - Detailed description of invention column d Contents of amendment (1) No. 9 Hata Lines 2-3 Correct "filling adhesive sheet material" to "filling adhesive sheet".

(2) 1 of the 6th row directly below the 14th, the 5th row of the lower box, and the 2nd row of the lower box
Corrected "Ethylene-based" to "Each 1 ethylene-based".

Claims (1)

[Claims] A filled adhesive sheet for solar cells comprising an ethylene copolymer resin containing an L-camping agent and an organic peroxide. 2. The filled adhesive sheet according to claim 1, wherein an organic silane compound is used as the complative agent, and an organic titanate compound is used as the organic silane/peroxide matrix. The filled adhesive sheet according to claim 1, wherein an organic peroxide having a decomposition temperature of about 90 to 190°C is used. 4. As an ethylene copolymer resin, the vinyl acetate content is approximately 4.
The filled adhesive sheet according to claim 1, wherein 0% by weight or less of the ethylene-vinyl acetate copolymer is used. & Vinyl acetate content as ethylene copolymer resin is approximately 20
A filled adhesive sheet according to claim 1 in which ~40% by weight of an ethylene-vinyl acetate copolymer is used. During the module bonding process in which the module is sandwiched between at least two filler adhesive sheets made of resin and an upper transparent adhesive material and a lower substrate adhesive material are stacked on both sides, the organic peroxide is A method of adhering a solar cell preservation material and a filler, which involves heating to a temperature above the decomposition temperature, with - being the % mark. Claim 6: The γ lower substrate protective material, the filling adhesive sheet, the thick #i battery element, the filling adhesive sheet, and the upper transparent membrane protective material are 11th overlaid or arranged, and the module is bonded. Adhesion method described. 7. The bonding method according to claim 6, wherein an organic silane compound, an organic silane peroxide, or an organic titanate compound is used as the complative agent. 7. The bonding method according to claim 6, wherein an organic peroxide having a decomposition temperature of about 90 DEG to 190 DEG C. is used. 7. The bonding method according to claim 6, wherein the ethylene copolymer resin molded into the 1α-filled adhesive sheet is an ethylene-vinyl acetate copolymer having a vinyl acetate content of about 20 to 40% by weight. 11. The bonding method according to claim 6, wherein the solar cell element is laminated in advance with at least two filled adhesive sheets and bonded to the upper transparent protective material and the lower substrate film retaining material. 12. An upper transparent protective material having a filled adhesive sheetra intermediate layer made of an ethylene-based copolymer resin containing a camping agent and an organic peroxide, and a solar cell element formed on the inner surface of one of the protective materials. and a solar cell protective material that is heated to a temperature higher than the decomposition temperature of the organic peroxide during the module bonding process in which the lower substrate protective material is stacked under the intermediate layer filling adhesive sheet. and the method of adhesion with the filler. 13. The bonding method according to claim 12, wherein an organic silane compound, an organic silane peroxide, or an organic titanate compound is used as the coupling agent. 14. The method of claim 12, wherein an organic peroxide having a decomposition temperature of about 90-190'C is used. 15 Ethylene-vinyl acetate copolymer resin having a vinyl acetate content of approximately 20 to 40% by weight is used as the ethylene-based copolymer resin to be formed into the filling adhesive sheet to be laminated onto the solar cell element formed on the upper surface of the lower substrate protection material. 13. The bonding method according to claim 12, wherein a polymer is used. 1a Ethylene-vinyl acetate with a vinyl acetate content of about 40% by weight or less as an ethylene-based copolymer resin molded into a filling adhesive sheet to be laminated under the solar cell element formed on the lower surface of the upper transparent sleeping material. 13. The adhesion method according to claim 12, wherein a copolymer is used.