CN107760253B - Sealing agent for solar cell, solar cell module, and method for sealing solar cell module - Google Patents

Sealing agent for solar cell, solar cell module, and method for sealing solar cell module Download PDF

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CN107760253B
CN107760253B CN201610675568.2A CN201610675568A CN107760253B CN 107760253 B CN107760253 B CN 107760253B CN 201610675568 A CN201610675568 A CN 201610675568A CN 107760253 B CN107760253 B CN 107760253B
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organopolysiloxane
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马静
李振忠
邓祚主
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Beijing Kmt Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention provides a sealing agent for a solar cell, a solar cell module and a sealing method thereof. The sealant for a solar cell according to the present invention includes a linear organopolysiloxane having a cyclohexylidene skeleton, a branched organopolysiloxane, and a linear organohydrogenpolysiloxane that is addition-cured by a hydrosilylation reaction between a cyclohexenyl group bonded to a silicon atom and a hydrogen atom bonded to a silicon atom; and further comprises an adhesion promoter which has a hydrosilylation reaction activity and is capable of introducing a trialkoxysilyl group bonded via a cyclohexylene group by a hydrosilylation reaction. Due to the matched use of the components, the cured layer of the sealant for the solar cell has low yellowing resistance, low water vapor permeability and low oxygen permeability, and can maintain long-term stable adhesion to a solar cell module in high-temperature high-humidity and ultraviolet environments.

Description

Sealing agent for solar cell, solar cell module, and method for sealing solar cell module
Technical Field
The present invention relates to a sealant for a solar cell, a solar cell module including a cured layer thereof, and a method of sealing a solar cell module using the same.
Background
Solar cells that use solar radiation as a source of energy are currently gaining increasing attention. In order to generate a higher voltage and protect it from the external environment, a solar cell module is generally manufactured by sealing a plurality of electrically connected solar cells between a light-receiving surface protective layer and a back-light surface protective layer with a sealant. The commonly used solar cell sealant is mainly an EVA sealant or a silicone sealant. Among them, the silicone sealant is widely used in the field of solar cell sealing because it does not cause the problem of corrosion of solar cell electrodes due to the generation of acetic acid in the hot and humid environment by EVA sealants.
JP2013-112719A, CN102276989A, CN102892837A each disclose a sealant for a solar cell. Although these sealants can exhibit good adhesion to the back sheet of a solar cell module, these sealants cannot maintain stable adhesion to the solar cell module for a long period of time when used in an external environment in which ultraviolet radiation is present, such as sunlight. In particular, since the organopolysiloxane used in the sealant disclosed in CN102276989A contains a large amount of phenyl groups, the sealant is likely to yellow when exposed to sunlight for a long period of time, which affects the appearance of the sealant. Also, the above documents do not mention the water vapor permeability and oxygen permeability of the sealant thereof, and thus it is not known whether the sealant can prevent the solar cell failure due to the permeation of moisture and oxygen.
CN103525094A discloses a silicone composition for a photovoltaic module for encapsulating a photovoltaic cell (i.e. a solar cell) having after curing at least 80g/m at 40 ℃ and 1mm thickness2The water vapor permeability of the day. The sealant disclosed in this document still has a problem that it cannot maintain sufficient and long-term stable adhesion to a solar cell module under sunlight, and it still provides a water vapor permeability that cannot meet the severe requirements for outdoor use.
JP2011-42744A and JP2013-209386A disclose the introduction of a methylene group (-CH) into the main chain of an organopolysiloxane used for a sealant2-) to reduce the water vapor permeability of the sealant; CN103571209A and CN105038253A disclose that ethylene (-CH) is introduced into the backbone of an organopolysiloxane used in a sealant2-CH2-) to reduce the oxygen permeability of the sealant. However, since the methylene or ethylene groups in the main chain of these organopolysiloxanes are very susceptible to oxidation in air, the heat stability of these sealants in air is poor, and the adhesion is affected.
CN104140679A discloses a silicone composition having a main chain containing an alkylene structure, which contains (a) a linear organopolysiloxane having a main chain containing an norbornyl structure, and (B) a linear organohydrogenpolysiloxane having a main chain containing an norbornyl structure. Although the cured product of the silicone composition has good ultraviolet resistance and moisture resistance, the adhesive strength thereof is still to be improved. Moreover, this document does not mention the oxygen permeability of the encapsulant, and therefore it is not known whether the encapsulant can prevent the failure of the solar cell due to oxygen permeation.
In view of the above technical problems in the prior art, there is an urgent need for a sealant for a solar cell, which has a cured layer that is resistant to yellowing, has low water vapor permeability and oxygen permeability, and can maintain stable adhesion to a solar cell module for a long period of time in a high-temperature, high-humidity and ultraviolet environment.
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a solar cell sealing agent which has a cured layer that is resistant to yellowing, has low water vapor permeability and low oxygen permeability, and can maintain stable adhesion to a solar cell module for a long period of time in a high-temperature, high-humidity and ultraviolet environment. Another object of the present invention is to provide a solar cell module including a cured layer formed by curing the sealant for a solar cell. It is still another object of the present invention to provide a method for sealing a solar cell module using the encapsulant for a solar cell.
Means for solving the problems
In order to achieve the above object of the present invention, the present invention provides a solar cell sealant comprising:
(A) a linear organopolysiloxane represented by formula (I):
Figure BDA0001080189810000031
in the formula (I), a is a positive integer of 1-100, and b is a positive integer of 1-100;
(B) a branched organopolysiloxane represented by the formula (II):
Figure BDA0001080189810000032
formula (II) wherein c + d is 1 and c/d is 0.1 to 4.0;
(C) a linear organohydrogenpolysiloxane represented by the formula (III):
Figure BDA0001080189810000033
in the formula (III), e is a positive integer of 1-100, and f is a positive integer of 1-100;
(D) an adhesion promoter represented by formula (IV) and/or formula (V):
RaSi(ORb)3(IV)
in the formula (IV), RaRepresents cyclohexenyl or norbornenyl, RbRepresents an alkyl group having 1 to 4 carbon atoms;
Figure BDA0001080189810000034
in the formula (V), RbAs defined in formula (IV), RcRepresents cyclohexylene or norbornylene; and
(E) a hydrosilylation reaction catalyst.
According to the sealant for a solar cell of the present invention, it is preferable that the weight ratio of the linear organopolysiloxane (a) and the branched organopolysiloxane (B) is 95:5 to 50: 50.
According to the solar cell sealant of the present invention, it is preferable that the adhesion promoter is used in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the total amount of the linear organopolysiloxane (a), the branched organopolysiloxane (B), and the linear organohydrogenpolysiloxane (C).
According to the sealant for a solar cell of the present invention, it is preferable that the molar ratio of the hydrogen atom bonded to the silicon atom in the linear organopolysiloxane (C) to the cyclohexenyl group bonded to the silicon atom in the linear organopolysiloxane (a) and the branched organopolysiloxane (B) is 0.1 to 5.0.
According to the solar cell sealant of the present invention, it is preferable that the hydrosilylation catalyst (E) is used in an amount of 0.1 to 1000ppm in terms of the weight of the platinum group metal element, based on the total amount of the linear organopolysiloxane (a), the branched organopolysiloxane (B), and the linear organohydrogenpolysiloxane (C).
The present invention also provides a solar cell module comprising a cured layer formed by curing the sealant for a solar cell.
According to the solar cell module of the present invention, preferably, the thickness of the cured layer is 10 to 2000 μm.
The present invention also provides a method of sealing a solar cell module, comprising: the solar cell sealing agent is applied to a solar cell module and cured.
ADVANTAGEOUS EFFECTS OF INVENTION
The sealant for a solar cell according to the present invention includes a linear organopolysiloxane having a cyclohexylidene skeleton, a branched organopolysiloxane, and a linear organohydrogenpolysiloxane that is addition-cured by a hydrosilylation reaction between a cyclohexenyl group bonded to a silicon atom and a hydrogen atom bonded to a silicon atom; and further comprises an adhesion promoter which has a hydrosilylation reaction activity and is capable of introducing a trialkoxysilyl group bonded via a cyclohexylene group by a hydrosilylation reaction. Due to the matched use of the components, the cured layer of the sealant for the solar cell has low yellowing resistance, low water vapor permeability and low oxygen permeability, and can maintain long-term stable adhesion to a solar cell module in high-temperature high-humidity and ultraviolet environments.
Drawings
Fig. 1 is a schematic view of a solar cell module according to the present invention.
In fig. 1: 1 is a light-receiving surface protective layer, 2 is a solar cell unit, 3 is a backlight surface protective layer, 4 is a sealant cured layer, and 5 is a wire.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the scope of the present invention is not limited thereto.
The "solar cell module" referred to as a "photovoltaic module" in the present invention is composed of a plurality of solar cell units electrically connected by a lead.
"Cy" in the present invention represents a cyclohexenyl group, and "Vi" in the present invention represents a vinyl group.
<Sealing agent for solar cell>
The solar cell sealing agent according to the present invention includes: the linear organopolysiloxane (A), the branched organopolysiloxane (B), the linear organohydrogenpolysiloxane (C), the adhesion promoter (D), and the hydrosilylation reaction catalyst (E). The components of the solar cell sealing agent of the present invention and the preparation thereof will be described in detail below.
Straight-chain organopolysiloxane (A)
The linear organopolysiloxane (a) that has a cyclohexylidene skeleton and is addition-cured by a hydrosilylation reaction between a cyclohexenyl group bonded to a silicon atom and a hydrogen atom bonded to a silicon atom.
In the present invention, the linear organopolysiloxane (a) has a structure represented by formula (I):
Figure BDA0001080189810000061
in the formula (I), a is a positive integer of 1-100, preferably a positive integer of 1-50; b is a positive integer of 1 to 100, preferably 1 to 50.
In the present invention, the linear organopolysiloxane (a) can be obtained by a hydrolytic condensation reaction between the following monomers:
(a-1) a monofunctional monomer represented by the formula (i-1):
Figure BDA0001080189810000062
in the formula (i-1), RaRepresents a hydroxyl group or a hydrolyzable group;
(a-2) a bifunctional monomer represented by the formula (i-2):
Figure BDA0001080189810000063
in the formula (i-2), RaThe same as defined in formula (i-1); and
(a-3) a bifunctional monomer represented by the formula (i-3):
Figure BDA0001080189810000064
in the formula (i-3), RaThe same as defined in formula (i-1).
In the formulae (i-1) to (i-3), the hydrolyzable group may be selected from a halogen atom or an alkoxy group of 1 to 4 carbon atoms, preferably a chlorine atom, a methoxy group, an ethoxy group or a propoxy group.
Examples of the monofunctional monomer (a-1) include, but are not limited to: cyclohexenyl dimethyl silanol, cyclohexenyl dimethyl chlorosilane, cyclohexenyl dimethyl methoxysilane, cyclohexenyl dimethyl ethoxysilane or cyclohexenyl dimethyl propoxysilane.
Examples of the bifunctional monomer (a-2) include, but are not limited to: 1, 4-bis (dimethylhydroxysilyl) cyclohexane, 1, 4-bis (dimethylchlorosilyl) cyclohexane, 1, 4-bis (dimethylmethoxysilyl) cyclohexane, 1, 4-bis (dimethylethoxysilyl) cyclohexane or 1, 4-bis (dimethylpropoxysilyl) cyclohexane.
Examples of the bifunctional monomer (a-3) include, but are not limited to: dimethylsilanol, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane or dimethyldipropoxysilane.
The process for preparing the linear organopolysiloxane (A) from the monofunctional monomer (a-1), the bifunctional monomer (a-2), and the bifunctional monomer (a-3) by hydrolytic condensation reaction is not particularly limited, and processes known in the art can be employed. For example, the related process disclosed by CN104140679A may be employed.
Branched organopolysiloxane (B)
The solar cell sealing agent of the present invention comprises the branched organopolysiloxane (B) having a cyclohexylene skeleton and undergoing addition curing by a hydrosilylation reaction between a cyclohexenyl group bonded to a silicon atom and a hydrogen atom bonded to a silicon atom.
In the present invention, the branched organopolysiloxane (B) has a structure represented by formula (II):
Figure BDA0001080189810000071
in formula (II), c + d is 1, and c/d is 0.1 to 4.0, preferably 0.1 to 3.0.
In the present invention, the branched organopolysiloxane (B) can be obtained by a hydrolytic condensation reaction between the following monomers:
(a-1) a monofunctional monomer represented by the formula (i-1); and
(b) a tetrafunctional monomer of formula (ii):
Figure BDA0001080189810000081
in the formula (ii), RaThe same as defined in formula (i-1).
Examples of the tetrafunctional monomer (b) include, but are not limited to: 1, 4-bis (dimethyldihydroxysilyl) cyclohexane, 1, 4-bis (dimethyldichlorosilyl) cyclohexane, 1, 4-bis (dimethyldimethoxysilyl) cyclohexane, 1, 4-bis (dimethyldiethoxysilyl) cyclohexane or 1, 4-bis (dimethyldipropoxysilyl) cyclohexane.
The process for preparing the branched organopolysiloxane (B) from the monofunctional monomer (a-1) and the tetrafunctional monomer (B) by hydrolytic condensation reaction is not particularly limited, and a process known in the art may be employed.
In the present invention, the weight ratio of the linear organopolysiloxane (a) and the branched organopolysiloxane (B) is 95:5 to 50:50, preferably 95:5 to 65: 35.
Straight-chain organohydrogenpolysiloxane (C)
The sealant for a solar cell according to the present invention includes the linear organohydrogenpolysiloxane (C) having a cyclohexylidene skeleton, and being addition-cured by a hydrosilylation reaction between a hydrogen atom bonded to a silicon atom and a cyclohexenyl group bonded to a silicon atom.
In the present invention, the linear organohydrogenpolysiloxane (C) has a structure represented by the formula (III):
Figure BDA0001080189810000082
in the formula (III), e is a positive integer of 1 to 100, preferably a positive integer of 1 to 50; f is a positive integer from 1 to 100, preferably from 1 to 50.
In the present invention, the linear organohydrogenpolysiloxane (C) can be obtained by a hydrolytic condensation reaction between the following monomers:
(c-1) a monofunctional monomer represented by the formula (iii-1) or the formula (iii-2):
Figure BDA0001080189810000091
in the formula (iii-1), RaThe same as defined in formula (i-1);
(a-2) a bifunctional monomer represented by the formula (i-2); and
(c-2) a bifunctional monomer represented by the formula (iii-3):
Figure BDA0001080189810000092
in the formula (iii-3), RaThe same as defined in formula (i-1).
Examples of the monofunctional monomer (c-1) include, but are not limited to: trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane or hexamethyldisiloxane.
Examples of the bifunctional monomer (c-2) include, but are not limited to: methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane or methyldipropoxysilane.
The process for preparing the linear organohydrogenpolysiloxane (C) from the monofunctional monomer (C-1), the bifunctional monomer (a-2) and the bifunctional monomer (C-2) by hydrolytic condensation reaction is not particularly limited, and a process known in the art may be employed. For example, the related process disclosed by CN104140679A may be employed.
In the present invention, the linear organohydrogenpolysiloxane (C) is used in an amount such that the molar ratio of the hydrogen atom bonded to the silicon atom in the linear organohydrogenpolysiloxane (C) to the cyclohexenyl group bonded to the silicon atom in the linear organopolysiloxane (a) and the branched organopolysiloxane (B) (SiH/SiCy) is usually 0.1 to 5.0, preferably 0.5 to 3.0.
Adhesion promoter (D)
The solar cell sealing agent of the present invention contains an adhesion promoter (D) which has a hydrosilylation reaction activity and can introduce a trialkoxysilyl group bonded via a cyclohexylene group by a hydrosilylation reaction.
In the present invention, the adhesion promoter (D) has a structure represented by formula (IV) and/or formula (V):
RaSi(ORb)3(IV)
in the formula (IV), RaRepresents cyclohexenyl or norbornenyl, RbRepresents an alkyl group having 1 to 4 carbon atoms;
Figure BDA0001080189810000101
in the formula (V), RbAs defined in formula (IV), RcRepresents cyclohexylene or norbornylene.
Examples of the adhesion promoter (D) having the structure represented by formula (IV) include, but are not limited to: cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, cyclohexenyltripropoxysilane, norbornenyltrimethoxysilane, norbornenyltriethoxysilane or norbornenyltripropoxysilane. Preferably, the adhesion promoter (D) having the structure represented by formula (IV) is cyclohexenyltrimethoxysilane or norbornenyltrimethoxysilane.
Examples of the adhesion promoter (D) having the structure represented by formula (V) include, but are not limited to:
Figure BDA0001080189810000102
Figure BDA0001080189810000111
preferably, the adhesion promoter (D) having the structure represented by formula (V) is represented by formula (V-1) or formula (V-3).
In the present invention, the adhesion promoter (D) having a structure represented by formula (V) can be obtained by a hydrosilation reaction between tetramethylcyclotetrasiloxane and the adhesion promoter (D) having a structure represented by formula (IV). The process for producing the adhesion promoter (D) having the structure represented by formula (V) from tetramethylcyclotetrasiloxane and the adhesion promoter (D) having the structure represented by formula (IV) by hydrosilylation is not particularly limited, and a process known in the art may be used, and will not be described herein again.
In the present invention, the amount of the adhesion promoter (D) is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total amount of the linear organopolysiloxane (a), the branched organopolysiloxane (B) and the linear organohydrogenpolysiloxane (C).
Hydrosilylation catalyst (E)
The solar cell sealant according to the present invention includes a hydrosilylation catalyst (E).
In the present invention, the hydrosilylation catalyst (E) generally uses a compound containing a platinum group metal element such as platinum, rhodium, palladium, or the like. Examples of the platinum group metal element-containing compound include, but are not limited to: platinum-containing compounds such as chloroplatinic acid, reaction products of chloroplatinic acid with alcohols, platinum-olefin complexes, platinum-vinylsilane complexes, platinum-ketone complexes, platinum-phosphine complexes; rhodium-containing compounds, such as rhodium-phosphine complexes, rhodium-sulfur compound complexes; palladium-containing compounds, such as palladium-phosphine complexes. Preferably, the hydrosilylation catalyst (E) is a platinum-vinylsiloxane complex, such as platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex.
In the present invention, the hydrosilylation catalyst (E) is used in an amount of 0.1 to 1000ppm, preferably 0.5 to 500ppm, in terms of the weight of the platinum group metal element, based on the total amount of the linear organopolysiloxane (a), the branched organopolysiloxane (B), and the linear organohydrogenpolysiloxane (C).
Other Components
Optionally, the encapsulant for solar cells of the present invention may further comprise other components, as long as the other components and the amount thereof do not significantly impair the adhesion, light transmittance, and mechanical properties of the encapsulant for solar cells of the present invention. Examples of such other components include, but are not limited to, hydrosilylation inhibitors such as 1-ethynylcyclohexanol, 3, 5-dimethyl-1-hexyn-3-ol, 3-methylbutynol, or dimethyl maleate; fillers, such as titanium dioxide, zinc oxide, aluminum oxide, iron oxide, aerosil silica, zirconium silicate, powdered quartz, diatomaceous earth or chalk; a heat stabilizer; a plasticizer; colorants, and the like.
Preparation of encapsulant for solar cell
The process for preparing the sealant for a solar cell according to the present invention is not particularly limited as long as the linear organopolysiloxane (a), the branched organopolysiloxane (B), the linear organohydrogenpolysiloxane (C), the adhesion promoter (D), the hydrosilylation catalyst (E), and optionally other components can be uniformly mixed. In general, the formulation can be carried out by homogeneously mixing the components in a mixing apparatus. Examples of such mixing devices include, but are not limited to, a spatula, a drum roll, a mechanical stirrer, a three-roll mill, a sigma blade mixer, a dough mixer, a planetary mixer, a screw, a dissolver, a butterfly mixer, an extrusion mixer, or a vacuum mixer.
In the present invention, the encapsulant for solar cells may be formulated and packaged in a one-component form, or may be formulated and packaged in a two-component form. When the two-component form is employed, there is no particular limitation on the composition in each component as long as the linear organohydrogenpolysiloxane (C) is kept separate from the hydrosilylation reaction catalyst (E).
< solar cell Module >
The solar cell module according to the present invention is not particularly limited in structure and type as long as it contains a cured layer formed from the sealant for a solar cell according to the present invention.
Fig. 1 shows a typical structure of a solar cell module of the present invention, which includes:
a light-receiving surface protective layer 1 on the side on which sunlight is incident,
a backlight surface protection layer 3 which is positioned on the side opposite to the incident direction of the sunlight,
solar battery cells 2 electrically connected to each other by leads 5 and located between the light-receiving-surface protective layer 1 and the backlight-surface protective layer 3, and
the sealant cured layer 4 is formed by curing the sealant for a solar cell according to the present invention on the surface of the solar cell 2.
In the present invention, the light-receiving surface protective layer 1 may be made of glass or synthetic resin. Wherein the glass is preferably float glass, colorless glass or toughened glass; the synthetic resin is preferably an acrylic resin, a Polycarbonate (PC) resin, a polyethylene terephthalate (PET) resin, or an epoxy resin. The thickness of the light-receiving surface protective layer 1 is usually 0.1 to 10mm, preferably 0.3 to 5 mm.
In the present invention, the backlight surface protection layer 3 may be made of glass, metal, synthetic resin, or a laminate thereof. Wherein the glass may be of a type used for constituting the light-receiving-surface protective layer 1; the metal is preferably copper, iron or aluminum; the synthetic resin is preferably a polyethylene terephthalate resin or a fluorine-containing polyolefin resin. The thickness of the back surface protection layer 3 is usually 0.1 to 10mm, preferably 0.3 to 5 mm.
In the present invention, the solar cell unit 2 generally uses a crystal type solar cell or a thin film type solar cell. Wherein the crystalline solar cell may be a single crystalline silicon or polycrystalline silicon solar cell; the thin film type solar cell may be a thin film silicon type solar cell, a thin film amorphous silicon type solar cell, or a Copper Indium Selenide (CIS) type solar cell.
In the present invention, the thickness of the sealant cured layer 4 is generally 10 to 2000. mu.m, preferably 100-1000. mu.m.
< method for sealing solar cell Module >
The method for sealing the solar cell module comprises the following steps: the solar cell sealing agent is applied to a solar cell module and cured.
In the method of the present invention, the manner of applying the sealant for a solar cell is not particularly limited, and spray coating, flow coating, dip coating, blade coating, curtain coating, or transfer coating may be employed.
In the method of the present invention, the curing temperature and curing time are not particularly limited. In general, the curing temperature may be from 50 to 150 ℃, preferably from 60 to 120 ℃; the curing time may be 5 minutes to 3 hours, preferably 5 minutes to 1 hour.
The present invention will be further described below by comparing examples with comparative examples and application examples with comparative application examples, but the scope of the present invention is not limited thereto.
Synthesis example 1 Linear organopolysiloxane (A-1) according to the present invention
130.08g (0.50mol) of 1, 4-bis (dimethylmethoxysilyl) cyclohexane and 60.03g (0.50mol) of dimethyldimethoxysilane are charged into a 4L four-necked flask equipped with a stirrer, a thermometer, a condenser and a dropping funnel, the temperature is raised to 50 ℃, a mixed solution containing 1100g of deionized water and 15g of hydrochloric acid (5N in concentration) is slowly dropped into the flask under stirring, then 8.51g (0.05mol) of cyclohexenyldimethylmethoxysilane is slowly dropped into the flask, the temperature in the flask is maintained at 50 ℃ after dropping, the reaction is continued for 4 hours under stirring, the reaction product is allowed to stand for demixing, an aqueous phase is separated, and the collected organic phase is washed with water to neutrality, sodium sulfate is added to the washed with water, dried, and filtered after drying, the sodium sulfate is removed, the organic phase after drying is vacuum distilled to obtain 137.77g of organic phaseThe linear organopolysiloxane (A-1). By carbon nuclear resonance spectroscopy analysis (13C-NMR) and silicon nuclear resonance spectroscopy analysis (29Si-NMR) to confirm that the linear organopolysiloxane (A-1) has the chemical structure represented by formula (I-1).
Figure BDA0001080189810000141
Synthesis example 2 branched organopolysiloxane (B-1) according to the present invention
116.86g (0.40mol) of 1, 4-bis (methyldimethoxysilyl) cyclohexane and 18.71g (0.11mol) of cyclohexenyldimethylmethoxysilane are charged into a 4L four-necked flask equipped with a stirrer, a thermometer, a condenser and a dropping funnel, the temperature is raised to 50 ℃, a mixed solution containing 500g of deionized water and 6g of hydrochloric acid (5N in concentration) is slowly dropped into the flask under stirring, after the dropping is completed, the temperature in the flask is maintained at 50 ℃, the reaction is continued for 4 hours under stirring, the reaction product is allowed to stand for demixing, an aqueous phase is separated, a collected organic phase is washed with water to neutrality, sodium sulfate is added into the washed organic phase for drying, sodium sulfate is filtered out after drying, the dried organic phase is vacuum distilled to obtain 85.64g of branched organopolysiloxane (B-1), and then, the branched organopolysiloxane (B-1) is subjected to carbon nuclear resonance spectroscopy analysis13C-NMR) and silicon nuclear resonance spectroscopy analysis (29Si-NMR) to confirm that the branched organopolysiloxane (B-1) has the chemical structure represented by formula (II-1).
Figure BDA0001080189810000151
Synthesis example 3 Linear Organohydrogenpolysiloxane (C-1) according to the invention
A4L four-necked flask equipped with a stirrer, a thermometer, a condenser and a dropping funnel was placed in an ice bath, 104.06g (0.40mol) of 1, 4-bis (dimethylmethoxysilyl) cyclohexane and 31.82g (0.30mol) of methyldimethoxysilane were charged into the flask, and a mixed solution containing 800g of deionized water and 12g of hydrochloric acid was slowly dropped into the flask under stirring, followed by charging into the flask5.20g (0.05mol) of trimethylmethoxysilane are slowly added dropwise. After the completion of the dropwise addition, the flask inner temperature was maintained at 5 ℃ or lower, and the reaction was continued for 4 hours under stirring. The reaction product is kept stand for layering, the water phase is separated out, and the collected organic phase is washed to be neutral. The organic phase after washing was dried by adding sodium sulfate and after drying the sodium sulfate was filtered off. The dried organic phase was subjected to vacuum distillation to obtain 92.62g of the linear organohydrogenpolysiloxane (C-1). By carbon nuclear resonance spectroscopy analysis (13C-NMR) and silicon nuclear resonance spectroscopy analysis (29Si-NMR) to confirm that the linear organohydrogenpolysiloxane (C-1) has the chemical structure represented by the formula (III-1).
Figure BDA0001080189810000161
Synthesis example 4 adhesion promoter (D-1) according to the present invention
In a 150ml four-necked flask equipped with a stirrer, a thermometer, a condenser, a dropping funnel and a nitrogen gas introducing tube, after replacing the air in the flask with nitrogen gas, 24.05g (0.10mol) of tetramethylcyclotetrasiloxane and 10ml of a toluene solution of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex having a platinum content of about 2 wt% were introduced into the flask. After the temperature in the flask was raised to 80 ℃ with stirring, a mixture containing 20.21g (0.10mol) of cyclohexenyltrimethoxysilane and 0.02g of p-hydroxyanisole was slowly added dropwise. After the completion of the dropwise addition, the flask inner temperature was kept at 90 ℃ and the reaction was continued for 2 hours under stirring. Distillation under reduced pressure gave 42.23g of the adhesion promoter (D-1). By carbon nuclear resonance spectroscopy analysis (13C-NMR) and silicon nuclear resonance spectroscopy analysis (29Si-NMR) to confirm that the adhesion promoter (D-1) has the chemical structure represented by the formula (V-1).
Figure BDA0001080189810000162
Examples 1 to 6 and comparative examples 1 to 3
Preparation of a sealant for a solar cell:
the components listed in table 1 were mixed in the ratio shown in table 1 below to prepare sealants for solar cells of examples 1 to 6 of the present invention and comparative examples 1 to 3, respectively.
The components listed in table 1 are described in detail below.
The following components were used as linear organopolysiloxane (a):
a-1: the linear organopolysiloxane (a-1) of the present invention prepared by synthesis example 1;
a' -1: as a comparison, a linear type organopolysiloxane represented by the following formula:
Figure BDA0001080189810000171
a' -2: as a comparison, a linear type organopolysiloxane represented by the following formula:
Figure BDA0001080189810000172
as the branched organopolysiloxane (B), the following components were used:
b-1: a branched organopolysiloxane (B-1) of the present invention prepared by Synthesis example 2;
b' -1: for comparison, a branched organopolysiloxane represented by the following formula:
Figure BDA0001080189810000173
the following components were used as the linear organohydrogenpolysiloxane (C):
c-1: the linear organohydrogenpolysiloxane (C-1) of the present invention prepared in Synthesis example 3;
c' -1: as a comparison, a linear organohydrogenpolysiloxane represented by the following formula:
Figure BDA0001080189810000174
c' -2: as a comparison, a linear organohydrogenpolysiloxane represented by the following formula:
Figure BDA0001080189810000175
as adhesion promoter (D), the following components were used:
d-1: the adhesion promoter (D-1) of the present invention prepared from Synthesis example 4;
d-2: the norbornenyl trimethoxy silane is prepared by the following steps;
d' -1: as a comparison, an adhesion promoter of the formula:
Figure BDA0001080189810000181
as the hydrosilylation reaction catalyst (E), the following components were used:
e: a toluene solution of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex having a platinum content of about 2 weight percent;
as the hydrosilylation reaction inhibitor, the following components were used:
f: 1-ethynylcyclohexanol.
Evaluation of encapsulant for solar cell:
adhesive stability
The solar cell sealant was sandwiched between two glass plates each having a width of 25mm at a bonding area of 12.5mm × 25mm under a pressure of 0.3Kg/cm2And the temperature was 120 ℃ for 1 hour, thereby obtaining a sample. The adhesive stability was evaluated by exposing the sample to a temperature of 85 ℃, a relative humidity of 100%, and an exposure to a fluorescent ultraviolet lamp (340nm) for 0 hour and 1000 hours, respectively, then stretching both ends of the sample in horizontally opposite directions with a tensile tester, measuring the tensile strength (unit: MPa) at break, and calculating the retention of the tensile strength.
The retention of tensile strength was × 100% (tensile strength of sample exposed for 1000 hours/tensile strength of sample exposed for 0 hour).
Water vapor permeability
The solar cell sealant was cured by heating at 120 ℃ for 1 hour to prepare a sample having a thickness of 1 mm. The water vapor permeability of the sample was measured by a water vapor permeability measuring apparatus (unit: g/m)2Day).
Permeability of oxygen
The solar cell sealant was cured by heating at 120 ℃ for 1 hour to prepare a sample having a thickness of 1 mm. The oxygen permeability (unit: cc/m) of the sample was measured by a gas permeability measuring apparatus2Day).
Yellowing resistance
The solar cell sealant is heated and cured at 120 ℃ for 1 hour to prepare a sample with the size of 40mm × 20mm × 2mm, the sample is exposed for 1000 hours in an environment with the temperature of 85 ℃, the relative humidity of 100 percent and the exposure of a fluorescent ultraviolet lamp (340nm), and the appearance color of the sample is observed, wherein the sample is recorded as ○ if the appearance of the sample is colorless, and is recorded as × if the appearance of the sample is yellow.
TABLE 1
Figure BDA0001080189810000191
Application examples 1-6 and comparative application examples 1-3
The solar cell modules of application examples 1 to 6 of the present invention and comparative application examples 1 to 3 have the structure shown in fig. 1, wherein the light receiving surface protection layer 1 and the backlight surface protection layer 3 both adopt colorless tempered glass plates with the thickness of 3mm, and the solar cell units 2 adopt single crystal silicon solar cell sets, are electrically connected through wires 5, and are arranged in a 2 × 2 array form.
Manufacturing and sealing the solar cell module:
two of the above-described colorless tempered glass plates were coated on one surface thereof with the sealants for solar cells according to examples 1 to 6 and comparative examples 1 to 3 of the present invention to form sealant coatings having a thickness of about 400 μm, respectively, and an array of 2 × 2 was sequentially laminated on the sealant coating of one of the colorless tempered glass platesA single crystal silicon solar battery set, another colorless tempered glass plate coated with the sealant coating (the sealant coating faces to the solar cell unit side), and a pressure of 0.3Kg/cm in an oven2And maintained at 120 ℃ for 1 hour, and the sealant coating layer was cured to form a cured sealant layer 4 shown in fig. 1, thereby producing solar cell modules according to application examples 1 to 6 of the present invention and comparative application examples 1 to 3.
Appearance evaluation of solar cell module:
the solar cell modules of application examples 1 to 6 of the present invention and comparative application examples 1 to 3 were exposed to an environment of 85 ℃ and 100% relative humidity with exposure to a fluorescent ultraviolet lamp (340nm) for 1000 hours, and the appearance was evaluated by observation, i) as "○" if the sealant cured layer was kept in a gapless seal with the solar cell unit, the light-receiving-surface protective layer, and the backlight protective layer, and the sealant cured layer was colorless, and ii) as "×" if a gap or crack was present between the sealant cured layer and the solar cell unit, the light-receiving-surface protective layer, or the backlight protective layer, or the sealant cured layer was yellow.
TABLE 2
Figure BDA0001080189810000201
As can be seen from comparison of examples 1 to 6 of the present invention with comparative examples 1 to 3, cured layers of the sealants for solar cells of examples 1 to 6 of the present invention exhibited excellent yellowing resistance and water vapor permeability of 10g/m2Oxygen permeability below 350cc/m2Days or less, and after exposure for 1000 hours in an environment where the temperature is 85 ℃, the relative humidity is 100% and the fluorescent ultraviolet lamp (340nm) is exposed, the retention rate of the tensile strength can still reach more than 92%, showing excellent adhesion stability. Meanwhile, as can be seen from comparison of application examples 1 to 6 of the present invention with comparative application examples 1 to 3, the solar cell modules of application examples 1 to 6 of the present invention respectively comprise cured layers of sealants formed by curing the sealants for solar cells of examples 1 to 6 at temperatures ofNo yellowing after exposure to an environment of 85 ℃, 100% relative humidity and 1000 hours of exposure to a fluorescent ultraviolet lamp (340nm), and still maintaining gapless sealing between the sealant cured layer and the solar cell unit, the light-receiving-surface protective layer or the backlight-surface protective layer.
As described above, since the linear organopolysiloxane having a cyclohexylene skeleton, the branched organopolysiloxane, and the linear organohydrogenpolysiloxane are included, addition curing is performed by a hydrosilation reaction between a cyclohexenyl group bonded to a silicon atom and a hydrogen atom bonded to a silicon atom; the sealant for the solar cell has cured layer with low yellowing resistance, low water vapor permeability and low oxygen permeability, and can maintain long-term stable adhesion to a solar cell module in high-temperature high-humidity and ultraviolet environments.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.

Claims (8)

1. A solar cell sealing agent, comprising:
(A) a linear organopolysiloxane represented by formula (I):
Figure FDA0002409629510000011
in the formula (I), a is a positive integer of 1-100, and b is a positive integer of 1-100;
(B) a branched organopolysiloxane represented by the formula (II):
Figure FDA0002409629510000012
formula (II) wherein c + d is 1 and c/d is 0.1 to 4.0;
(C) a linear organohydrogenpolysiloxane represented by the formula (III):
Figure FDA0002409629510000013
in the formula (III), e is a positive integer of 1-100, and f is a positive integer of 1-100;
(D) an adhesion promoter represented by formula (IV) and/or formula (V):
RaSi(ORb)3(IV)
in the formula (IV), RaRepresents cyclohexenyl or norbornenyl, RbRepresents an alkyl group having 1 to 4 carbon atoms;
Figure FDA0002409629510000014
in the formula (V), RbAs defined in formula (IV), RcRepresents cyclohexylene or norbornylene; and
(E) a hydrosilylation reaction catalyst.
2. The sealant for a solar cell according to claim 1, wherein a weight ratio of the linear organopolysiloxane (a) and the branched organopolysiloxane (B) is 95:5 to 50: 50.
3. The sealant for a solar cell according to any one of claims 1 to 2, wherein the adhesion promoter is used in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the total amount of the linear organopolysiloxane (a), the branched organopolysiloxane (B), and the linear organohydrogenpolysiloxane (C).
4. The sealant for a solar cell according to any one of claims 1 to 2, wherein a molar ratio of the hydrogen atom bonded to the silicon atom in the linear organohydrogenpolysiloxane (C) to the cyclohexenyl group bonded to the silicon atom in the linear organopolysiloxane (a) and the branched organopolysiloxane (B) is 0.1 to 5.0.
5. The sealant for a solar cell according to any one of claims 1 to 2, wherein the hydrosilylation catalyst (E) is used in an amount of 0.1 to 1000ppm in terms of the weight of the platinum group metal element, based on the total amount of the linear organopolysiloxane (a), the branched organopolysiloxane (B), and the linear organohydrogenpolysiloxane (C).
6. A solar cell module comprising a cured layer formed by curing the sealant for a solar cell according to any one of claims 1 to 5.
7. The solar cell module of claim 6 wherein the cured layer has a thickness of 10-2000 μm.
8. A method of sealing a solar cell module, comprising: the sealant for a solar cell according to any one of claims 1 to 5 is applied on a solar cell module and cured.
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CN103045158A (en) * 2013-01-23 2013-04-17 北京海斯迪克新材料有限公司 Halogen-free high-flame retardance addition type heat conduction silicon rubber adhesive
TW201331322A (en) * 2011-10-07 2013-08-01 Shinetsu Chemical Co Temporary adhesive composition and method for manufacturing thin wafer using the same

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JP4648146B2 (en) * 2005-09-26 2011-03-09 信越化学工業株式会社 Addition-curing silicone composition with excellent crack resistance

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TW201331322A (en) * 2011-10-07 2013-08-01 Shinetsu Chemical Co Temporary adhesive composition and method for manufacturing thin wafer using the same
CN103045158A (en) * 2013-01-23 2013-04-17 北京海斯迪克新材料有限公司 Halogen-free high-flame retardance addition type heat conduction silicon rubber adhesive

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