CN102321450A - Solar energy photovoltaic assembly organosilicon sealant material and preparation method thereof - Google Patents
Solar energy photovoltaic assembly organosilicon sealant material and preparation method thereof Download PDFInfo
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- CN102321450A CN102321450A CN201110242335A CN201110242335A CN102321450A CN 102321450 A CN102321450 A CN 102321450A CN 201110242335 A CN201110242335 A CN 201110242335A CN 201110242335 A CN201110242335 A CN 201110242335A CN 102321450 A CN102321450 A CN 102321450A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The invention belongs to the field of solar energy photovoltaic assembly manufacturing, and particularly provides a solar energy photovoltaic assembly organosilicon sealant material which comprises the following raw material components by weight: (A) 100 parts of polyorganosiloxane, (B) 50-120 parts of fillers, (C) 20-160 parts of fire retardants, (D) 5-30 parts of plasticizers, (E) 5-20 parts of oxime cross-linking agents, (F) 0.05-2 parts of catalysts, (G) 0.1-5 parts of tackifiers. The invention also provides a preparation method of the material, which comprises the following steps: firstly mixing the polyorganosiloxane, the filler and the fire retardant to obtain a base adhesive compound, adding the plasticizer and the oxime cross-linking agent and mixing, finally adding the tackifier and the catalyst and mixing to obtain the solar energy photovoltaic assembly organosilicon sealant material. The product of the invention has a falme retardant grade of up to V-0 grade, has good adhesion to photovoltaic cell glass, aluminium materials, backplanes, and terminal boxes, and has no corrosion for EVA adhesive films and cell circuits; the preparation method has a simple process.
Description
Technical field
The invention belongs to solar photovoltaic assembly and make the field, be specifically related to a kind of have excellent weather-resistant, high and low temperature resistance, yellowing resistance; Various aluminiums, backboard, terminal box had good cementability; To EVA glued membrane and the non-corrosive self cure of battery circuit (RTV) solar photovoltaic assembly organosilicon sealant material and preparation method thereof.
Background technology
Development solar energy power generating industry recent years rapidly, so-called solar photovoltaic generation system is a photovoltaic effect of utilizing solar cell, solar radiation can be directly changed into a kind of new-generation system of electric energy.Solar panel is also referred to as " photovoltaic module-PV assembly ", and it is by arranging one group of good crystal silicon cell in advance, is laminated between ultra-thin, transparent, high strength glass and the sealing bottom and constitutes.Photovoltaic module is fixed on sealer forms solar panel on the framework, organosilicon sealant is important subsidiary material indispensable in the solar photovoltaic assembly, and in the solar photovoltaic assembly production process, framework and photovoltaic battery panel are used to bond.
Solar photovoltaic assembly from its applied environment, mainly is out of doors with glue, must satisfy the difference of the outside geographic climate of environment for use, has also just proposed following requirement for its performance characteristics:
Good weather-proof ability: can tolerate the high and low temperature environment test, hot dry like western province, like the southern province, high temperature is moist, moistureproof, anti-environmental corrosion ability;
Good UV resistant tans by the sun ability; Yellowing resistance;
Good cementability (at UV irradiation, heavy rain, strong wind, high and low temperature environment);
Good anti-burning capacity;
Anti-physical shock, thermal shocking, shake-proof ability;
From construction application, except manually beating the glue, sealer must use with high speed XY table and the combination of automatically dropping glue equipment, improves the finished product efficient of photovoltaic module.
Other is according to the requirement of photovoltaic industry relevant criterion (UL1703 and UL1741); Photovoltaic module there is the requirement of flame retardant resistance with the material that is bonded and sealed; The present invention is guaranteeing under photovoltaic component seal gum required mechanical property, weather resistance, electric property and the adhesive property, through screening suitable fire retardant, to reach flame retardant rating V-0; Various materials are effectively coordinated, reached the performance index requirement.
At present the disclosed publication number patent documentation that is CA 101805585 N provides a kind of one-component flame retardant solar photovoltaic subassembly sealant and preparation method thereof, and there are in essence different in its component raw material and preparation method and the present invention.
Summary of the invention
The object of the invention provides solar photovoltaic assembly organosilicon sealing material of a kind of each item excellent performance and preparation method thereof.
For realizing goal of the invention of the present invention, the contriver provides following technical scheme:
The contriver at first provides a kind of solar photovoltaic assembly organosilicon sealant material, and its feed composition is following by weight:
(A) organopolysiloxane is 100 parts,
(B) filler is 50~120 parts,
(C) fire retardant is 20~160 parts,
(D) softening agent is 5~30 parts,
(D) crosslinking and curing agent is 5~20 parts,
(E) catalyzer is 0.05~2 part,
(F) tackifier are 0.1~5 part.
As preferred version, according to a kind of solar photovoltaic assembly organosilicon sealant material of the present invention, in, described organopolysiloxane is a hydroxyl-terminated injecting two methyl siloxane, viscosity is 10000~100000 mPa * s in the time of 25 ℃.
As preferred version; According to a kind of solar photovoltaic assembly organosilicon sealant material of the present invention; In, described filler is any one or the compsn in light calcium carbonate, water-ground limestone, silicon powder, nano-calcium carbonate, the white carbon black of gas phase and the precipitated silica, wherein; Described light calcium carbonate is the super-fine active calcium carbide of being handled by Triple Pressed Stearic Acid or silane coupling agent, and particle size range is 0.01~50 μ m.
As preferred version; According to a kind of solar photovoltaic assembly organosilicon sealant material of the present invention; In; Described fire retardant is any one or the compsn in white lake, Marinco H, decabromodiphynly oxide, zinc borate and the Antimony Trioxide: 99.5Min, and wherein, described white lake or Marinco H are the material of being handled by Triple Pressed Stearic Acid or silane coupling agent.
As preferred version, according to a kind of solar photovoltaic assembly organosilicon sealant material of the present invention, in, described softening agent is that viscosity is any one or the compsn in white oil, methyl-silicone oil and the phenyl silicone oil of 50~500 mPa * s.
As preferred version, according to a kind of solar photovoltaic assembly organosilicon sealant material of the present invention, in, but described ketoxime linking agent is ketoximinosilanes or the ketoxime based polysiloxane that contains moisture hydrolyzes more than two.For example: the vinyl tributanoximo silane of vinyl tributanoximo silane, methyl tributanoximo silane, partly hydrolysed, four Diacetylmonoxime base silanes etc.
As preferred version; According to a kind of solar photovoltaic assembly organosilicon sealant material of the present invention; In; Described catalyzer is organic carboxyl acid tin system, is selected from any one or compsn in dioctyl two LAURIC ACID 99 MIN tin, dibutyl tin acetate, dibutyl phenylformic acid tin and the dibutyl tin dilaurate.
As preferred version, according to a kind of solar photovoltaic assembly organosilicon sealant material of the present invention, in, described tackifier are the silane coupling agent that contains cyanic acid and secondary amino group, its molecular structural formula is (R
1O)
3~xSiR
2 xR
3NHR
4NH
y(C
2H
4CN)
z, R wherein
1, R
2Be the straight or branched alkyl of 1~6 identical or different carbon atom, R
3, R
4Be the arylmethylene alkyl and the alkyl arylene of alkylidene group, aryl or 6~10 carbon atoms of 1~6 carbon atom, x, y are 0 or 1, and z is 1 or 2.For example: the r-aminopropyltriethoxywerene werene; The r-TSL 8330; N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan; N-β-(aminoethyl)-γ-An Bingjisanyiyangjiguiwan, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, polyamino alkyltrialkoxysilaneand (in Virahol) etc.
The contriver also provides above-mentioned a kind of solar photovoltaic assembly organosilicon sealant preparation methods, and step is following:
(1) with organopolysiloxane 100 weight parts, filler 50~120 weight parts and fire retardant 20~160 weight parts in planetary mixer; Controlled temperature is that 100~150 ℃, vacuum tightness are 0.05~0.1MPa; In vacuum seal mixed 2~3 hours down, obtain sizing;
(2) in sizing, adding softening agent 5~30 weight parts and ketoxime linking agent 5~20 weight parts, is to mix 10~30 minutes under 0.05~0.1MPa in vacuum tightness;
(3) add tackifier 0.1~5 weight part and catalyzer 0.05~2 weight part then; Under vacuum seal, mix 10~30 minutes; Vacuum tightness is 0.05~0.1MPa, obtains the good solar photovoltaic assembly organosilicon sealant material of single-component stability in storage behind mixed the end.
As preferred version, according to a kind of solar photovoltaic assembly organosilicon sealant preparation methods of the present invention, wherein, described filler is at first following dry 3~4 hours at 100~120 ℃.
Compared with prior art, technical scheme provided by the invention has following technique effect:
The present invention adopts the mode of batch charging; Promptly earlier that hydroxyl-terminated injecting two methyl siloxane, filler and fire retardant is evenly mixed under vacuum seal; Add softening agent and ketoxime linking agent then, add catalyzer and tackifier at last, improved the stability in storage of product;
Product flame retardant rating provided by the invention reaches the V-0 level, and photovoltaic cell glass, aluminium, backboard and terminal box are all had good adhesive, to EVA glued membrane and battery circuit non-corrosiveness;
Preparing method's technology simple device provided by the invention is less demanding, and the byproduct of reaction non-corrosiveness can ensure comprehensive embodiment of the technique effect of solar photovoltaic assembly organosilicon sealant excellent fire retardant effect and quick solidifying.
Embodiment
Below in conjunction with embodiment, content of the present invention is described more specifically.Should be appreciated that enforcement of the present invention is not limited to following embodiment, all will fall into protection domain of the present invention any pro forma accommodation and/or the change that the present invention made.
In the present invention, if not refer in particular to, all part, per-cents are weight unit, and all equipment and raw material etc. all can be buied from market or the industry is commonly used.Do not specialize if having, the method that embodiment adopts is this area current techique.
The raw material explanation:
Softening agent: the viscosity of white oil, methyl-silicone oil or phenyl silicone oil is 50~500 mPa * s.
Filler: light calcium carbonate, water-ground limestone, silicon powder, nano-calcium carbonate, the white carbon black of gas phase or precipitated silica, at first following dry 3~4 hours at 100~120 ℃.
Embodiment 1
By weight; With viscosity be 10000 mPa * 100 parts of s hydroxyl-terminated injecting two methyl siloxanes, exsiccant through the acid-treated particle size range of tristearin at 5 parts of 45 parts of super-fine active calcium carbides, the gas-phase silicas of 0.04~20 μ m with through 160 parts in stearic acid-treated white lake; (temperature is that 100~150 ℃, vacuum tightness are 0.05~0.1MPa) in planetary mixer mixed 2 hours, obtains sizing under the vacuum seal condition; Behind the cool to room temperature, add 25 parts of methyl-silicone oils, 15 parts of vinyl tributanoximo silanes and 5 parts of methyl tributanoximo silanes, (vacuum tightness is 0.05~0.1MPa) mixed 30 minutes under the vacuum seal condition; Add 2 parts of dibutyl tin dilaurates and 0.1 part of r-aminopropyltriethoxywerene werene at last; (vacuum tightness is 0.05~0.1MPa) mixed 20 minutes under vacuum seal; Behind the part lower-molecular substance that generates in last vacuum removal bubble and the reaction; Obtain the good solar photovoltaic assembly organosilicon sealant material of single-component stability in storage, sealing is preserved.Product performance test result for details see attached table 1.
Embodiment 2
By weight; With viscosity is 10000 mPa * 100 parts of s hydroxyl-terminated injecting two methyl siloxanes, exsiccant through the acid-treated particle size range of tristearin 20 parts of 80 parts of the super-fine active calcium carbides of 0.04~20 μ m and silicon powders; 50 parts of the Marinco Hs of handling through silane coupling agent; (temperature is that 100~150 ℃, vacuum tightness are 0.05~0.1MPa) in planetary mixer mixed 3 hours, obtains sizing under the vacuum seal condition; Behind the cool to room temperature, add 5 parts of phenyl silicone oil, 3 parts of vinyl tributanoximo silanes and 7 parts of methyl tributanoximo silanes, (vacuum tightness is 0.05~0.1MPa) mixed 10 minutes under the vacuum seal condition; Add 0.5 part of dioctyl, two LAURIC ACID 99 MIN tin and 1 part of r-TSL 8330 at last; (vacuum tightness is 0.05~0.1MPa) mixed 30 minutes under vacuum seal; Behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction; Obtain the good solar photovoltaic assembly organosilicon sealant material of single-component stability in storage, sealing is preserved.Product performance test result for details see attached table 1.
Embodiment 3
By weight; With viscosity is 53000 mPa * 100 parts of s hydroxyl-terminated injecting two methyl siloxanes, 115 parts of exsiccant silicon powders, 5 parts of gas-phase silicas and through 18 parts of stearic acid-treated decabromodiphynly oxides, 2 parts of Antimony Trioxide: 99.5Mins; (temperature is that 100~150 ℃, vacuum tightness are 0.05~0.1MPa) in planetary mixer mixed 2 hours, obtains sizing under the vacuum seal condition; Behind the cool to room temperature, add 25 parts of white oils, 3 parts of vinyl tributanoximo silanes and 2 parts of methyl tributanoximo silanes, (temperature is that 100~150 ℃, vacuum tightness are 0.05~0.1MPa) mixed 30 minutes under the vacuum seal condition; Add 0.1 part of dibutyl tin acetate and 5 parts of N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwans at last; (vacuum tightness is 0.05~0.1MPa) mixed 20 minutes under vacuum seal; Behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction; Obtain the good solar photovoltaic assembly organosilicon sealant material of single-component stability in storage, sealing is preserved.Product performance test result for details see attached table 1.
Embodiment 4
By weight; With viscosity be 53000 mPa * 100 parts of s hydroxyl-terminated injecting two methyl siloxanes, exsiccant through the acid-treated particle size range of tristearin at 10 parts of 70 parts of super-fine active calcium carbides, the precipitated silicas of 0.04~20 μ m with through 80 parts in stearic acid-treated white lake, 20 parts of Marinco Hs; (temperature is that 100~150 ℃, vacuum tightness are 0.05~0.1MPa) in planetary mixer mixed 2 hours, obtains sizing under the vacuum seal condition; Behind the cool to room temperature, add 5 parts of white oils, 7 parts of the vinyl tributanoximo silanes of 3 parts of vinyl tributanoximo silanes and partly hydrolysed, (temperature is that 100~150 ℃, vacuum tightness are 0.05~0.1MPa) mixed 30 minutes under the vacuum seal condition; Add 1 part of dibutyl phenylformic acid tin and 1 part of N-β-(aminoethyl)-γ-An Bingjisanyiyangjiguiwan at last; (vacuum tightness is 0.05~0.1MPa) mixed 20 minutes under vacuum seal; Behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction; Obtain the good solar photovoltaic assembly organosilicon sealant material of single-component stability in storage, sealing is preserved.Product performance test result for details see attached table 1.
Embodiment 5
By weight; With viscosity be 53000 mPa * 100 parts of s hydroxyl-terminated injecting two methyl siloxanes, exsiccant through the acid-treated particle size range of tristearin at 50 parts of the super-fine active calcium carbides of 0.04~20 μ m with through 80 parts in stearic acid-treated white lake, 70 parts of zinc borates; (temperature is that 100~150 ℃, vacuum tightness are 0.05~0.1MPa) in planetary mixer mixed 3 hours, obtains sizing under the vacuum seal condition; Behind the cool to room temperature, add 20 parts of methyl-silicone oils and 5 parts of white oils, 5 parts of vinyl tributanoximo silanes and 5 parts of methyl tributanoximo silanes, (temperature is that 100~150 ℃, vacuum tightness are 0.05~0.1MPa) mixed 30 minutes under the vacuum seal condition; Add 1 part of dibutyl tin dilaurate, 1 part of dibutyl phenylformic acid tin and 1.5 parts of N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilanes at last; (vacuum tightness is 0.05~0.1MPa) mixed 20 minutes under vacuum seal; Behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction; Obtain the good solar photovoltaic assembly organosilicon sealant material of single-component stability in storage, sealing is preserved.Product performance test result for details see attached table 1.
Embodiment 6
By weight; With viscosity is 53000 mPa * 100 parts of s hydroxyl-terminated injecting two methyl siloxanes, exsiccant through 70 parts of the acid-treated nm-class active calcium carbonates of tristearin, 10 parts of WHITE CARBON BLACKs with through 10 parts of 80 parts in stearic acid-treated white lake and decabromodiphynly oxides; (temperature is that 100~150 ℃, vacuum tightness are 0.05~0.1MPa) in planetary mixer mixed 2 hours, obtains sizing under the vacuum seal condition; Behind the cool to room temperature, add 20 parts of methyl-silicone oils, 5 parts of vinyl tributanoximo silanes and 5 parts of methyl tributanoximo silanes, (temperature is that 100~150 ℃, vacuum tightness are 0.05~0.1MPa) mixed 30 minutes under the vacuum seal condition; Add 0.1 part of dibutyl tin dilaurate, 0.3 part of two zinc-base two LAURIC ACID 99 MIN tin and 1.5 parts of polyamino alkyltrialkoxysilaneand (in Virahol) at last; (vacuum tightness is 0.05~0.1MPa) mixed 20 minutes under vacuum seal; Behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction; Obtain the good solar photovoltaic assembly organosilicon sealant material of single-component stability in storage, sealing is preserved.Product performance test result for details see attached table 1.
Embodiment 7
By weight; With viscosity is that 100 parts of the hydroxy-end capped YSR 3286s of 53000 mPa * s, exsiccant are through 70 parts of the acid-treated light calcium carbonates of tristearin with through 80 parts in stearic acid-treated white lake, 15 parts of zinc borates; (temperature is that 100~150 ℃, vacuum tightness are 0.05~0.1MPa) in planetary mixer mixed 3 hours, obtains sizing under the vacuum seal condition; Behind the cool to room temperature, add 15 parts of methyl-silicone oils and 5 parts of phenyl silicone oil, 2 parts of four Diacetylmonoxime base silanes and 5 parts of methyl tributanoximo silanes, (temperature is that 100~150 ℃, vacuum tightness are 0.05~0.1MPa) mixed 30 minutes under the vacuum seal condition; Add 0.1 part of dibutyl tin dilaurate and 1 part of N-β-(aminoethyl)-γ-An Bingjisanyiyangjiguiwan, 0.5 part of polyamino alkyltrialkoxysilaneand (in Virahol) and 0.5 part of r-aminopropyltriethoxywerene werene at last; (vacuum tightness is 0.05~0.1MPa) mixed 20 minutes under vacuum seal; Behind the part lower-molecular substance that generates in vacuum removal bubble and the reaction; Obtain the good solar photovoltaic assembly organosilicon sealant material of single-component stability in storage, sealing is preserved.Product performance test result for details see attached table 1.
Although the contriver has done comparatively detailed elaboration to technical scheme of the present invention and has enumerated; Be to be understood that; For the those skilled in the art in this area, be obvious to the replacement scheme that the foregoing description modifies and/or flexible perhaps employing is equal to, all can not break away from the essence of spirit of the present invention; The term that occurs among the present invention is used for can not being construed as limiting the invention the elaboration of technical scheme of the present invention and understanding.
Claims (10)
1. solar photovoltaic assembly organosilicon sealant material is characterized in that its feed composition is following by weight:
(A) organopolysiloxane is 100 parts,
(B) filler is 50~120 parts,
(C) fire retardant is 20~160 parts,
(D) softening agent is 5~30 parts,
(D) the ketoxime linking agent is 5~20 parts,
(E) catalyzer is 0.05~2 part,
(F) tackifier are 0.1~5 part.
2. a kind of solar photovoltaic assembly organosilicon sealant material as claimed in claim 1 is characterized in that described organopolysiloxane is a hydroxyl-terminated injecting two methyl siloxane, and viscosity is 10000~100000 mPa * s in the time of 25 ℃.
3. a kind of solar photovoltaic assembly organosilicon sealant material as claimed in claim 1; It is characterized in that; Described filler is any one or the compsn in light calcium carbonate, water-ground limestone, silicon powder, nano-calcium carbonate, the white carbon black of gas phase and the precipitated silica; Wherein, described light calcium carbonate is the super-fine active calcium carbide of being handled by Triple Pressed Stearic Acid or silane coupling agent, and particle size range is 0.01~50 μ m.
4. a kind of solar photovoltaic assembly organosilicon sealant material as claimed in claim 1; It is characterized in that; Described fire retardant is any one or the compsn in white lake, Marinco H, decabromodiphynly oxide, zinc borate and the Antimony Trioxide: 99.5Min; Wherein, described white lake or Marinco H are the material of being handled by Triple Pressed Stearic Acid or silane coupling agent.
5. a kind of solar photovoltaic assembly organosilicon sealant material as claimed in claim 1 is characterized in that, described softening agent is that viscosity is any one or the compsn in white oil, methyl-silicone oil and the phenyl silicone oil of 50~500 mPa * s.
6. a kind of solar photovoltaic assembly organosilicon sealant material as claimed in claim 1 is characterized in that, but described ketoxime linking agent is ketoximinosilanes or the ketoxime based polysiloxane that contains moisture hydrolyzes more than two.
7. a kind of solar photovoltaic assembly organosilicon sealant material as claimed in claim 1; It is characterized in that; Described catalyzer is organic carboxyl acid tin system, is selected from any one or compsn in dioctyl two LAURIC ACID 99 MIN tin, dibutyl tin acetate, dibutyl phenylformic acid tin and the dibutyl tin dilaurate.
8. a kind of solar photovoltaic assembly organosilicon sealant material as claimed in claim 1 is characterized in that described tackifier are the silane coupling agent that contains cyanic acid and secondary amino group, and its molecular structural formula is (R
1O)
3~xSiR
2 xR
3NHR
4NH
y(C
2H
4CN)
z, R wherein
1, R
2Be the straight or branched alkyl of 1~6 identical or different carbon atom, R
3, R
4Be the arylmethylene alkyl and the alkyl arylene of alkylidene group, aryl or 6~10 carbon atoms of 1~6 carbon atom, x, y are 0 or 1, and z is 1 or 2.
9. one kind like the arbitrary described a kind of solar photovoltaic assembly organosilicon sealant preparation methods of claim 1 to 8, it is characterized in that step is following:
(1) with organopolysiloxane, filler and fire retardant in planetary mixer, controlled temperature is that 100~150 ℃, vacuum tightness are 0.05~0.1MPa, in vacuum seal mixed 2~3 hours down, obtains sizing;
(2) in sizing, adding softening agent and ketoxime linking agent, is to mix 10~30 minutes under 0.05~0.1MPa in vacuum tightness;
(3) add tackifier and catalyzer then, under vacuum seal, mix 10~30 minutes, vacuum tightness is 0.05~0.1MPa, obtains the good solar photovoltaic assembly organosilicon sealant material of single-component stability in storage behind mixed the end.
10. a kind of solar photovoltaic assembly organosilicon sealant preparation methods according to claim 9 is characterized in that, described filler is at first following dry 3~4 hours at 100~120 ℃.
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