CN103805002A - Coating composition, solar cell module back plate, and solar cell module - Google Patents
Coating composition, solar cell module back plate, and solar cell module Download PDFInfo
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Abstract
The invention relates to a coating composition, a solar cell module back plate, and a solar cell module. The coating composition is good in pigment dispersion and masking liquid stability, and is capable of forming a coating with good ultraviolet ray shielding. The coating composition is characterized in that the coating composition has fluorine-containing polymer having functional group, carbon black, dispersing agent and organic solvent. The base number of the dispersing agent is above 12mgKOH/g and the acid number is below 12mgKOH/g.
Description
Technical field
The present invention relates to coating composition, solar cell module back veneer and solar module.
Background technology
Solar module conventionally by the sealing material of solar battery cell, sealed solar energy battery unit, be separately positioned on the sealing sensitive surface side (face side) of material and the upper layer of rear side and backboard formation.
Solar module uses in the wild.Therefore,, for solar cell module back veneer, similarly need to there is high-weatherability, wet fastness, thermotolerance and insulativity with the upper layer of sensitive surface side.In addition, also need to have the performance that can tolerate by the photogenic UV degradation of reflection.
As solar cell module back veneer, known have a backboard (patent documentation 1) that forms fluororesin layer on base material.Such fluororesin layer is also by being coated on the coating composition that contains fluoropolymer, pigment, organic solvent etc. on base material and making it solidify to form (patent documentation 2).
In addition, being used to form in the coating composition of such backboard, from the viewpoint of making the beautiful appearance of solar module, wish to add pigment, conventionally coordinate as the titanium dioxide of white pigment, calcium carbonate or as (patent documentations 3) such as the composition metal such as carbon black, the Cu-Cr-Mn alloy classes of black pigment.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-227203 communique
Patent documentation 2: TOHKEMY 2010-238760 communique
Patent documentation 3: No. 2007/010706 brochure of International Publication
Summary of the invention
Invent problem to be solved
But, use as pigment in the situation of carbon black, in the time that aforementioned coating composition is preserved for a long time, there is the problem of carbon black generation sedimentation.
In view of above-mentioned present situation, the object of the present invention is to provide a kind of coating composition, its pigment-dispersing and masking liquid excellent in stability, and can form the film of ultraviolet-shielding type excellence.
Solve the means of problem
The inventor is studied above-mentioned requirements, found that, in containing containing the fluoropolymer of solidified nature functional group and the coating composition of carbon black, there is the base number of specified range and the compound of acid number as dispersion agent by use, can improve surprisingly pigment-dispersing and the masking liquid stability of coating composition, thereby complete the present invention.Find in addition, by using specific dispersion agent, the ultraviolet-shielding type of the film obtaining is improved simultaneously.
That is, the present invention relates to a kind of coating composition, it is characterized in that, it contains containing the fluoropolymer of solidified nature functional group, carbon black, dispersion agent and organic solvent, and the base number of above-mentioned dispersion agent is more than 12mgKOH/g and acid number is below 12mgKOH/g.
The base number of preferred above-mentioned dispersion agent is that 12mgKOH/g～40mgKOH/g and acid number are below 12mgKOH/g.
The base number of preferred above-mentioned dispersion agent is that 12mgKOH/g～40mgKOH/g and acid number are essentially 0mgKOH/g.
Preferred above-mentioned dispersion agent is made up of urethanes.
Preferred above-mentioned urethanes is for to have ethylene oxide chain and/or propylene oxide chain at main chain, and has the urethanes of quaternized dose of (four Gradeization drug) quaternised amino (four Gradeization さ れ ア ミ ノ yls).
The polymerized unit that preferably the above-mentioned fluoropolymer containing solidified nature functional group contains the polymerized unit based on fluorochemical monomer and the monomer based on containing solidified nature functional group should be at least one monomer selecting in the group of free hydroxyl monomer, carboxyl group-containing monomer, anhydride monomers, emulsion stability and silicone-based vinyl monomer composition containing the monomer of solidified nature functional group.
Preferred above-mentioned fluorochemical monomer is at least one that select in the group of free tetrafluoroethylene, trifluorochloroethylene and vinylidene fluoride composition.
Preferred above-mentioned fluorochemical monomer is tetrafluoroethylene.
The invention still further relates to a kind of solar cell module back veneer, it is characterized in that, it has base material and the fluororesin layer at least one face of above-mentioned base material, and above-mentioned fluororesin layer is the cured coating film that uses aforementioned coating composition to form.
The invention still further relates to a kind of solar module, it is characterized in that, it possesses above-mentioned solar cell module back veneer.
Below describe the present invention in detail.
Invention effect
The pigment-dispersing of coating composition of the present invention and masking liquid excellent in stability and can form the film of ultraviolet-shielding type excellence.
Accompanying drawing explanation
Fig. 1 is the generalized schematic of an example of solar module of the present invention.
Fig. 2 is the generalized schematic of an example of solar module of the present invention.
Embodiment
The present invention relates to coating composition, it is characterized in that, it contains containing the fluoropolymer of solidified nature functional group, carbon black, dispersion agent and organic solvent, and the base number of above-mentioned dispersion agent is more than 12mgKOH/g and acid number is below 12mgKOH/g.
Therefore, the pigment-dispersing of coating composition of the present invention and masking liquid excellent in stability.In addition use, the ultraviolet-shielding type excellence of the cured coating film that coating composition of the present invention obtains.
The base number of the contained dispersion agent of coating composition of the present invention is more than 12mgKOH/g.
If base number is less than 12mgKOH/g, the dispersion stabilization of carbon black reduces.
More than base number is preferably 14mgKOH/g.
In addition, base number is preferably below 40mgKOH/g, more preferably below 35mgKOH/g.
Base number can be measured by the acid base titration that has used acidic substance.
The acid number of the contained dispersion agent of coating composition of the present invention is below 12mgKOH/g.
If acid number exceedes 12mgKOH/g, can produce the liquid separation (liquid divides か れ) of coating composition.
Acid number is preferably below 10mgKOH/g, more preferably essence is 0mgKOH/g.Acid number essence is that 0mgKOH/g specifically refers to and is less than 0.1mgKOH/g.
Acid number can be measured by the acid base titration that has used alkaline matter.
The contained dispersion agent of coating composition of the present invention preferably has alkali (salt base).
As above-mentioned alkali, can enumerate for example amino etc.
As above-mentioned amino, can enumerate-NH
2,-NHR ,-NRR '.And comprise quaternised amino.
As long as above-mentioned dispersion agent has above-mentioned base number and acid number is just not particularly limited, preferably formed by the urethanes with above-mentioned base number and acid number.Above-mentioned urethanes is for having the polymkeric substance of amino-formate bond (CONH-).
Above-mentioned urethanes is preferably at main chain has ethylene oxide chain and/or propylene oxide chain, and has the urethanes of quaternized dose of quaternised amino.
As above-mentioned quaternizing agent, can enumerate and the amino organic acid that forms salt of uncle, mineral acid, Organohalogen compounds etc.As above-mentioned organic acid, can use formic acid, acetic acid, propionic acid, butyric acid, lactic acid, oxysuccinic acid, propanedioic acid, hexanodioic acid, Phenylsulfonic acid etc.; As above-mentioned mineral acid, can use hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid etc.In addition,, as above-mentioned Organohalogen compounds, can use the halogenated alkyl such as benzyl chloride, methyl chloride etc.And then also can use the sulfuric ester such as methyl-sulfate, ethyl sulfate.Wherein, preferably use sulfuric ester, as quaternizing agent, tertiary amino is made to quaternary ammonium salt, more preferably use methyl-sulfate that tertiary amino is made to quaternary ammonium salt.
Above-mentioned quaternised amino (quaternized amino) by-[NRR ' R ' ']
+x
-(wherein, R, R ' and R ' ' are alkyl, can be the same or different; X
-for counter ion such as halogens.) represent.
In above-mentioned dispersion agent, ethylene oxide chain and propylene oxide chain are preferably by quality ratio: ethylene oxide chain: propylene oxide chain is 0.1:99.9～15:85.
As above-mentioned urethanes, can enumerate urethanes obtaining as follows etc.: the polyvalent alcohol that makes to have ethylene oxide chain and propylene oxide chain and polyisocyanates and the amine compound that can react with isocyanate group react, use above-mentioned quaternizing agent that amino is quaternized, thereby obtain this urethanes.Specifically, for example can enumerate the urethanes obtaining as follows: make to have ethylene oxide chain and react with polyisocyanates with the polyvalent alcohol of propylene oxide chain, next react with the amine compound that can react with isocyanate group, further use above-mentioned quaternizing agent by quaternized the amino of obtained compound (tertiary amino), obtain this urethanes (quaternary ammonium salt) etc.
As the above-mentioned polyvalent alcohol with ethylene oxide (EO) chain and propylene oxide (PO) chain, for example, as long as for the polyvalent alcohol with EO chain and PO chain is just not particularly limited, can enumerate (the CH with OH-
2cH
2o)
l-(CH (CH
3)-CH
2o)
m-(CH
2cH
2o)
nthe segmented copolymer (l, m, n are more than 1 integer) that-H represents etc.
As above-mentioned polyisocyanates, preferably vulcabond.As above-mentioned vulcabond, for example can enumerate: the aliphatic diisocyanates such as ethylidene diisocyanate, trimethylene diisocyanate, butylidene vulcabond, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate; The ester ring type vulcabond such as isophorone diisocyanate, 4-4 '-dicyclohexyl methane diisocyanate, norcamphane vulcabond; Tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, Xylene Diisocyanate, 1, the aromatic diisocyanates such as 5-naphthalene diisocyanate etc.
As the amine compound that can react with above-mentioned isocyanate group, can enumerate such as butyl diethanolamine, ethyldiethanolamine, methyldiethanolamine, DMAE, 2-DEAE diethylaminoethanol, 3-dimethylamino propyl alcohol, dimethylamino ethamine, diethylamino-ethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine etc.
Above-mentioned dispersion agent is preferably branched chain polymer, comb shaped polymer more preferably.
The weight-average molecular weight of above-mentioned dispersion agent is preferably 10000～100000.If less than 10000 is may dispersion stabilization bad or ooze out.If exceed 100000, may be dispersed bad.
Above-mentioned weight-average molecular weight more preferably more than 20000, more preferably more than 40000, more preferably below 70000, more preferably below 60000.
Above-mentioned weight-average molecular weight can be measured by gel permeation chromatography (GPC) (polystyrene conversion).
As above-mentioned dispersion agent, can use commercially available product.As the commercially available product that can apply, can enumerate such as SOLSPERSE76500 (Japanese Lubrizol society manufacture) etc. in coating composition of the present invention.
In coating composition of the present invention, with respect to carbon black 100 mass parts, the content of above-mentioned dispersion agent is preferably 2.5 mass parts～40 mass parts.
If be less than 2.5 mass parts, may can not get the stably dispersing effect of carbon black.If exceed 40 mass parts, Physical properties of coating film may reduce.
The content of above-mentioned dispersion agent more preferably 5 mass parts above, more preferably more than 9 mass parts, more preferably 35 mass parts following, more preferably below 30 mass parts.
Coating composition of the present invention contains the fluoropolymer containing solidified nature functional group.By containing the fluoropolymer containing solidified nature functional group, can form the film of weathering resistance, wet fastness, thermotolerance and insulativity excellence.
As the above-mentioned fluoropolymer containing solidified nature functional group, can enumerate and in fluoropolymer, import the polymkeric substance that has solidified nature functional group.It should be noted that, fluoropolymer comprises having the resinousness polymkeric substance of sharp melting point, the elastomerics polymkeric substance that demonstrates caoutchouc elasticity, its middle thermoplastic elastomer polymkeric substance.
As the functional group that fluoropolymer is given to solidified nature, can enumerate for example hydroxyl and (wherein not comprise the hydroxyl that carboxyl is contained.Same below.), the represented group of carboxyl ,-COOCO-, amino, glycidyl, silyl, silane (シ ラ ネ ー ト) base, isocyanate group etc., property easy to manufacture or curing system that can conjugated polymer carry out suitable selection.Wherein, good from the viewpoint of solidification reactivity, preferably hydroxyl, carboxyl, represented group, amino, the silyl of-COOCO-, the aspect easily obtaining from polymkeric substance or reactive good aspect are considered, particularly preferably hydroxyl.These solidified nature functional groups conventionally carry out copolymerization by fluorochemical monomer with the monomer that contains solidified nature functional group and import in fluoropolymer.
As containing the monomer of solidified nature functional group, can enumerate for example hydroxyl monomer, carboxyl group-containing monomer, anhydride monomers, emulsion stability and silicone-based vinyl monomer, can use one kind or two or more in them.
The above-mentioned fluoropolymer containing solidified nature functional group preferably contains the polymerized unit of the polymerized unit based on fluorochemical monomer and the monomer based on containing solidified nature functional group, should be at least one that select in the group of free hydroxyl monomer, carboxyl group-containing monomer, anhydride monomers, emulsion stability and silicone-based vinyl monomer composition containing the monomer of solidified nature functional group.
As the above-mentioned monomer containing solidified nature functional group, can exemplify for example following monomer, but not only be defined in these.It should be noted that, can use one kind or two or more in them.
(1-1) hydroxyl monomer:
As hydroxyl monomer, can enumerate the vinyl ethers of the hydroxyls such as such as 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methyl propyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methyl butyl vinyl ether, 5-hydroxyl amyl group vinyl ether, 6-hydroxyl hexyl vinyl ether; The allyl ether series of the hydroxyls such as 2-hydroxyethyl allyl ethers, 4-hydroxybutyl allyl ethers, allylin etc.Among them, from the viewpoint of the solidified nature excellence of polymerisation reactivity, functional group, the preferably vinyl ethers of hydroxyl, particularly preferably 4-hydroxybutyl vinyl ether, 2-hydroxyethyl vinyl ether.
As other hydroxyl monomer, can exemplify the such as acrylic acid hydroxyalkyl acrylate of 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate etc. (methyl) etc.
It should be noted that, carboxyl group-containing monomer described later is not included in above-mentioned hydroxyl monomer.
(1-2) carboxyl group-containing monomer:
As carboxyl group-containing monomer, for example can enumerate general formula (1):
[changing 1]
(in formula, R
1, R
2and R
3identical or different, be hydrogen atom, alkyl, aryl, carboxyl or carbalkoxy; N is 0 or 1) the unsaturated carboxylic acid class such as represented unsaturated monocarboxylic, unsaturated dicarboxylic acid, its monoesters; Or general formula (2):
[changing 2]
(in formula, R
4and R
5identical or different, be saturated or undersaturated straight chain or cyclic alkyl; N is 0 or 1; M is 0 or 1) represented carboxylic vinyl ether monomers etc.
As the concrete example of the represented unsaturated carboxylic acid class of above-mentioned general formula (1), can enumerate such as vinylformic acid, methacrylic acid, vinylacetic acid, butenoic acid, styracin, methylene-succinic acid, methylene-succinic acid monoesters, toxilic acid, toxilic acid monoesters, fumaric acid, fumaric monoalkylester etc.Among them, low for homopolymerization, to be difficult to obtain homopolymer reason, preferably low butenoic acid, methylene-succinic acid, toxilic acid, toxilic acid monoesters, fumaric acid, the fumaric monoalkylester of homopolymerization.
As the concrete example of the represented carboxylic vinyl ether monomers of above-mentioned general formula (2), for example, can enumerate one kind or two or more in 3-allyloxy propionic acid, 3-(2-allyloxy ethoxy carbonyl) propionic acid, 3-(2-allyloxy butoxy carbonyl) propionic acid, 3-(2-vinyloxy group ethoxy carbonyl) propionic acid, 3-(2-vinyloxy group butoxy carbonyl) propionic acid etc.Among them, 3-(2-allyloxy ethoxy carbonyl) propionic acid etc. monomer stability, polymerisation reactivity good aspect favourable, be preferred.
As above-mentioned carboxyl group-containing monomer, except above-mentioned general formula (1) or (2) represented monomer, can also use the alkenyl ester of the such as polycarboxylic acid such as O-phthalic vinyl acetate, pyromellitic acid vinyl acetate etc.
(1-3) anhydride monomers:
As anhydride monomers, can enumerate the acid anhydrides of the unsaturated dicarboxylic acids such as such as maleic anhydride.
(1-4) emulsion stability:
As emulsion stability, can enumerate for example CH
2=CH-O-(CH
2)
x-NH
2the amido vinyl ethers that (x=0～10) are represented; CH
2=CH-O-CO (CH
2)
x-NH
2the amine that (x=1～10) are represented; And amino methyl vinylbenzene, vinyl amine, acrylamide, vinyl acetamide, vinyl formamide etc.
(1-5) silicone-based vinyl monomer:
As silicone-based vinyl monomer, for example can exemplify: CH
2=CHCO
2(CH
2)
3si (OCH
3)
3, CH
2=CHCO
2(CH
2)
3si (OC
2h
5)
3, CH
2=C (CH
3) CO
2(CH
2)
3si (OCH
3)
3, CH
2=C (CH
3) CO
2(CH
2)
3si (OC
2h
5)
3, CH
2=CHCO
2(CH
2)
3siCH
3(OC
2h
5)
2, CH
2=C (CH
3) CO
2(CH
2)
3siC
2h
5(OCH
3)
2, CH
2=C (CH
3) CO
2(CH
2)
3si (CH
3)
2(OC
2h
5), CH
2=C (CH
3) CO
2(CH
2)
3si (CH
3)
2oH, CH
2=CH (CH
2)
3si (OCOCH
3)
3, CH
2=C (CH
3) CO
2(CH
2)
3siC
2h
5(OCOCH
3)
2, CH
2=C (CH
3) CO
2(CH
2)
3siCH
3(N (CH
3) COCH
3)
2, CH
2=CHCO
2(CH
2)
3siCH
3(ON (CH
3) C
2h
5)
2, CH
2=C (CH
3) CO
2(CH
2)
3siC
6h
5(ON (CH
3) C
2h
5)
2deng (methyl) esters of acrylic acid; CH
2=CHSi[ON=C (CH
3) (C
2h
5)]
3, CH
2=CHSi (OCH
3)
3, CH
2=CHSi (OC
2h
5)
3, CH
2=CHSiCH
3(OCH
3)
2, CH
2=CHSi (OCOCH
3)
3, CH
2=CHSi (CH
3)
2(OC
2h
5), CH
2=CHSi (CH
3)
2siCH
3(OCH
3)
2, CH
2=CHSiC
2h
5(OCOCH
3)
2, CH
2=CHSiCH
3(ON (CH
3) C
2h
5)
2, the vinyl silanes class such as vinyl trichloro silane or their partial hydrolystate; The vinyl ethers such as trimethoxysilylethylgroup group vinyl ether, triethoxysilyl ethyl vinyl ether, trimethoxysilyl butyl vinyl ether, methyl dimethoxy oxygen base silyl ethyl vinyl ether, trimethoxy-silylpropyl vinyl ether, triethoxysilylpropyltetrasulfide vinyl ether; Etc..
As fluorochemical monomer,, be used to form and import the monomer of fluoropolymer that has solidified nature functional group, can enumerate for example tetrafluoroethylene, trifluorochloroethylene, vinylidene fluoride, vinyl fluoride and fluorinated ethylene base ether, can use one kind or two or more in them.
Wherein, be preferably at least one in the group of selecting free tetrafluoroethylene, trifluorochloroethylene and vinylidene fluoride composition, more preferably tetrafluoroethylene.
There is the fluoropolymer of solidified nature functional group as importing, according to the polymerized unit that forms this polymkeric substance, can exemplify for example following substances.
(1) the perfluoroolefine based polymer take perfluoroolefine unit as main body:
As concrete example, can enumerate multipolymer (PAVE) etc. of the homopolymer of tetrafluoroethylene (TFE) or TFE and R 1216 (HFP), perfluor (alkyl vinyl ether) and with can with multipolymer of other monomer of their copolymerization etc.
As above-mentioned other monomer that can copolymerization, can enumerate the vinyl esters of carboxylic acids classes such as such as vinyl-acetic ester, propionate, vinyl butyrate, isopropylformic acid vinyl acetate, trimethylacetic acid vinyl acetate, vinyl caproate, tertiary ethylene carbonate, vinyl laurate, stearic acid vinyl ester, hexahydrobenzoic acid vinyl acetate, vinyl benzoate, p-tert-butyl benzoic acid vinyl acetate; The alkyl vinyl ethers such as methylvinylether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether; The non-fluorine such as ethene, propylene, n-butene, iso-butylene are olefines; The fluorine such as vinylidene fluoride (VdF), trifluorochloroethylene (CTFE), vinyl fluoride (VF), fluorovinyl ether are monomer etc., but are not limited in these materials.
Among these, from the viewpoint of pigment-dispersing, weathering resistance, copolymerizable, chemical proofing excellence, the preferably TFE based polymer take TFE as main body.
As the concrete perfluoroolefine based polymer containing solidified nature functional group, can enumerate the multipolymer of such as TFE/ iso-butylene/hydroxybutyl vinyl ether/other monomer, multipolymer, the multipolymer of TFE/VdF/ hydroxybutyl vinyl ether/other monomer etc. of TFE/ tertiary ethylene carbonate/hydroxybutyl vinyl ether/other monomer, particularly preferably multipolymer of the multipolymer of TFE/ iso-butylene/hydroxybutyl vinyl ether/other monomer, TFE/ tertiary ethylene carbonate/hydroxybutyl vinyl ether/other monomer etc.
As the coating curable polymer composition of TFE system, can exemplify the Zeffle GK series of such as Daikin Ind Ltd's manufacture etc.
(2) the CTFE based polymer take trifluorochloroethylene (CTFE) unit as main body:
As concrete example, can enumerate the multipolymer of such as CTFE/ hydroxybutyl vinyl ether/other monomer etc.
As the coating curable polymer composition of CTFE system, can exemplify LUMIFLON, the FLUONATE that Dainippon Ink Chemicals manufactures, Cefral Coat, the Zaffron that Toagosei Co., Ltd manufactures etc. that Central Glass Co., Ltd. manufactures that such as Asahi Glass Co., Ltd manufactures.
(3) the VdF based polymer take vinylidene fluoride (VdF) unit as main body:
As concrete example, can enumerate the multipolymer of such as VdF/TFE/ hydroxybutyl vinyl ether/other monomer etc.
(4) polymkeric substance containing fluoro-alkyl take fluoro-alkyl unit as main body:
As concrete example, can enumerate for example CF
3cF
2(CF
2cF
2)
ncH
2cH
2oCOCH=CH
2(n=3 and 4 mixture)/2-hydroxyethyl methacrylate/stearyl acrylate ester copolymer etc.
As containing the polymkeric substance of fluoro-alkyl, can exemplify ZONYL that UNIDYNE that such as Daikin Ind Ltd manufactures or FTONE, society of Du Pont manufacture etc.
Among them, consider weathering resistance, moisture resistance, preferably perfluoroolefine based polymer.
The above-mentioned fluoropolymer containing solidified nature functional group for example can be manufactured by disclosed method in TOHKEMY 2004-204205 communique.
In coating composition of the present invention, with respect to the total amount 100 quality % of the nonvolatile component in coating composition, the content of the above-mentioned fluoropolymer containing solidified nature functional group is preferably 20 quality %～90 quality %.
Coating composition of the present invention contains carbon black.
Be not particularly limited as above-mentioned carbon black, can enumerate generally well-known carbon black.
From the viewpoint of ultraviolet shielding effect, the median size of above-mentioned carbon black is preferably 10nm～150nm, 20nm～100nm more preferably.
Above-mentioned median size is the value obtaining by the observation under electron microscope.
From the viewpoint of ultraviolet shielding effect, in coating composition, the median size of the carbon black after dispersion step is preferably 50nm～1000nm, more preferably 100nm～700nm, 100nm～500nm more preferably.
Above-mentioned median size is the value that the mensuration by utilizing laser diffraction and scattering formula size-grade distribution meter obtains.
With respect to fluoropolymer 100 mass parts containing solidified nature functional group in coating composition, the content of carbon black is preferably 0.5 mass parts～80 mass parts.The content of carbon black is in above-mentioned scope time, can in coating, disperse well.
With respect to containing fluoropolymer 100 mass parts of solidified nature functional group, the content of carbon black more preferably 3 mass parts above, more preferably more than 10 mass parts, more preferably 60 mass parts following, more preferably below 50 mass parts.
Coating composition of the present invention contains organic solvent.
As above-mentioned organic solvent, for example can enumerate: the ester classes such as ethyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, methyl proxitol acetate; The ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone; The ring-type such as tetrahydrofuran (THF), dioxane ethers; The amides such as DMF, N,N-dimethylacetamide; Dimethylbenzene, toluene, solvent naphtha etc. are aromatic hydrocarbon based; The glycol ethers such as propylene glycol monomethyl ether, ethyl cellosolve; The glycol ether ester classes such as Trivalin SF acetic ester; Skellysolve A, normal hexane, normal heptane, octane, positive nonane, n-decane, n-undecane, n-dodecane, white spirits wet goods aliphatic hydrocarbon; Their mixing etc.
They can use separately or two or more share.
Wherein preferred ester class, preferred butylacetate.
Coating composition of the present invention preferably further contains solidifying agent.By containing solidifying agent, can use coating composition of the present invention to form cured coating film.
Above-mentioned solidifying agent is selected according to the functional group of curable polymer, for example, for the fluoropolymer of hydroxyl, preferably can exemplify isocyanate-based solidifying agent, melamine resin, silicate compound (シ リ ケ ー ト compound), contain the silane compound of isocyanate group etc.In addition,, for carboxylic fluoropolymer, conventionally adopting amino is that solidifying agent, epoxy are solidifying agent; For containing amino fluoropolymer, conventionally adopting the solidifying agent, the epoxy that contain carbonyl is that solidifying agent, acid anhydrides are solidifying agent.
As above-mentioned solidifying agent, be wherein preferably at least one compound in the group of selecting freely following compound composition: derived from the polyisocyanate compound of at least one isocyanic ester in the group of selecting free xylylene diisocyanate (XDI) and two (isocyanato-methyl) hexanaphthene (hydrogenation XDI, H6XDI) to form; Based on the blocked isocyanate compounds of hexamethylene diisocyanate (HDI); Derived from the polyisocyanate compound of hexamethylene diisocyanate (HDI); And derived from the polyisocyanate compound of isophorone diisocyanate (IPDI).
Use derived from least one isocyanic ester in the group of selecting free xylylene diisocyanate (XDI) and two (isocyanato-methyl) hexanaphthene (hydrogenation XDI, H6XDI) to form (hereinafter also referred to as isocyanic ester (i) as solidifying agent.) polyisocyanate compound (hereinafter also referred to as polyisocyanate compound (I).) situation under, the adaptation of the sealing material of the cured coating film being obtained by coating composition of the present invention and solar module is more excellent.Further, in coiling process etc., the resistance to adhesive with the face that the solar cell module back veneer of above-mentioned cured coating film contacts with respect to this cured coating film is more excellent.
As above-mentioned polyisocyanate compound (I), for example can enumerate by above-mentioned isocyanic ester (i) with 3 yuan of above aliphatic polyol addition polymerizations the isocyanurate structure body that adds adult, formed by above-mentioned isocyanic ester (i) (urea acid esters (ヌ レ ー ト) structure) obtaining and the biuret body being formed by above-mentioned isocyanic ester (i).
As the above-mentioned adult that adds, for example, be preferably the material with the represented structure of following general formula (3):
[changing 3]
(in formula, R
6represent the aliphatic alkyl that carbonatoms is 3～20.R
7represent phenylene or cyclohexylidene.K is 3～20 integer.)。
R in above-mentioned general formula (3)
6for the alkyl based on above-mentioned 3 yuan of above aliphatic polyols, the aliphatic alkyl that more preferably carbonatoms is 3～10, the aliphatic alkyl that further preferably carbonatoms is 3～6.
Above-mentioned R
7in situation for phenylene, can be 1,2-phenylene (adjacent phenylene), 1, any in 3-phenylene (metaphenylene) and Isosorbide-5-Nitrae-phenylene (to phenylene).Wherein preferably 1,3-phenylene (metaphenylene).In addition the whole R in above-mentioned general formula (3),
7can be identical phenylene, also can coexist two or more.
Above-mentioned R
7in situation for cyclohexylidene, can be 1,2-cyclohexylidene, 1, any in 3-cyclohexylidene and Isosorbide-5-Nitrae-cyclohexylidene.Wherein preferably 1,3-cyclohexylidene.In addition the whole R in above-mentioned general formula (3),
7can be identical cyclohexylidene, also can coexist two or more.
Above-mentioned k is the number corresponding with first number of more than 3 yuan aliphatic polyols.As above-mentioned k, more preferably 3～10 integer, 3～6 integer more preferably.
Above-mentioned isocyanurate structure body for having the material of more than 1 or 2 as represented in following general formula (4) isocyanurate ring in molecule.
[changing 4]
As above-mentioned isocyanurate structure body, can enumerate: react the tripolymer that obtains, react the pentamer that obtains, react heptamer obtaining etc. by seven dimerizations by five dimerizations by the trimerizing of above-mentioned isocyanic ester.
Wherein, be preferably as follows the represented tripolymer of general formula (5):
[changing 5]
(in formula, R
7with the R in above-mentioned general formula (3)
7identical.)。, above-mentioned isocyanurate structure body is preferably the tripolymer of at least one isocyanic ester in the group of selecting free xylylene diisocyanate and two (isocyanato-methyl) hexanaphthene compositions.
Above-mentioned biuret is for having the compound of the represented structure of following general formula (6):
[changing 6]
(in formula, R
7with the R in above-mentioned general formula (3)
7identical.), it can be by under the condition different from the situation that obtains above-mentioned isocyanurate structure body obtaining above-mentioned isocyanate trimerization.
As above-mentioned polyisocyanate compound (I), the wherein preferred above-mentioned adult that adds, is preferably the material that at least one isocyanic ester in the group of selecting free xylylene diisocyanate and two (isocyanato-methyl) hexanaphthenes compositions obtains with more than 3 yuan aliphatic polyol addition polymerization.
In the situation that adds adult of above-mentioned polyisocyanate compound (I) for above-mentioned isocyanic ester (i) and more than 3 yuan aliphatic polyols, as these 3 yuan above aliphatic polyols, specifically, can enumerate: glycerine, TriMethylolPropane(TMP) (TMP), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxyl-3-hydroxymethyl pentane, 1,1,1-tri-(two hydroxymethyl) propane, 2, the two 3 yuan of alcohol such as (hydroxymethyl) butanols-3 grade of 2-; 4 yuan of alcohol such as tetramethylolmethane, Glycerol dimer; 5 yuan of alcohol (pentitol) such as arabitol, ribitol, Xylitol; 6 yuan of alcohol (hexitol) such as Sorbitol Powder, N.F,USP MANNITOL, melampyrum, A Luo alcohol (ア ロ ズ Le シ ッ ト) etc.Wherein particularly preferably TriMethylolPropane(TMP), tetramethylolmethane.
In addition, for as the above-mentioned xylylene diisocyanate (XDI) that adds the constituent of adult and use, can enumerate 1,3-xylylene diisocyanate (mphenylenedimethylim-vulcabond), 1,2-xylylene diisocyanate (phthalal vulcabond), 1,4-xylylene diisocyanate (terephthalylidene vulcabond), wherein preferably 1,3-xylylene diisocyanate (mphenylenedimethylim-vulcabond).
In addition, for as above-mentioned two (isocyanato-methyl) hexanaphthenes (hydrogenation XDI, H6XDI) that add the constituent of adult and use, can enumerate 1, two (isocyanato-methyl) hexanaphthenes, 1 of 3-, two (isocyanato-methyl) hexanaphthenes, 1 of 2-, two (isocyanato-methyl) hexanaphthenes of 4-, wherein preferably 1, two (isocyanato-methyl) hexanaphthenes of 3-.
By selecting the addition polymerization of at least one isocyanic ester in the group of free xylylene diisocyanate and two (isocyanato-methyl) hexanaphthenes composition and above-mentioned 3 yuan of above aliphatic polyols, can obtain being applicable to the adult that adds in the present invention.
As the adult that adds preferably using in the present invention, specifically, can enumerate for example represented compound of following general formula (7):
[changing 7]
(in formula, R
8represent phenylene or cyclohexylidene.), be by by the polyisocyanate compound that selects at least one isocyanic ester in the group of free xylylene diisocyanate and two (isocyanato-methyl) hexanaphthenes composition and TriMethylolPropane(TMP) (TMP) addition polymerization to obtain.
About the R in above-mentioned general formula (7)
8represented phenylene or cyclohexylidene, as the R in above-mentioned general formula (3)
7described in.
As the commercially available product of the represented polyisocyanate compound of above-mentioned general formula (7), can enumerate Takenate D110N (Mitsui Chemicals, Inc's manufacture, XDI and TMP add adult, NCO content 11.8%), Takenate D120N (Mitsui Chemicals, Inc's manufacture, H6XDI and TMP add adult, NCO content 11.0%) etc.
Be the concrete example in the situation of isocyanurate structure body as above-mentioned polyisocyanate compound (I), can enumerate Takenate D121N (Mitsui Chemicals, Inc's manufacture, H6XDI urea acid esters, NCO content 14.0%), Takenate D127N (Mitsui Chemicals, Inc's manufacture, H6XDI urea acid esters, the tripolymer of H6XDI, NCO content 13.5%) etc.
Blocked isocyanate by use based on hexamethylene diisocyanate (HDI) is (hereinafter also referred to as blocked isocyanate.) as solidifying agent, can make coating composition of the present invention there is sufficient working life (serviceable time).
As above-mentioned blocked isocyanate, be preferably and utilize end-blocking agent to make polyisocyanate compound derived from hexamethylene diisocyanate (hereinafter also referred to as polyisocyanate compound (II).) react and the material that obtains.
As above-mentioned polyisocyanate compound (II), for example can enumerate: hexamethylene diisocyanate and more than 3 yuan aliphatic polyols carry out addition polymerization and the isocyanurate structure body that adds adult, formed by hexamethylene diisocyanate (urea acrylate structure body) obtaining and the biuret being formed by hexamethylene diisocyanate.
As the above-mentioned adult that adds, for example, be preferably the material with the represented structure of following general formula (8):
[changing 8]
(in formula, R
9represent the aliphatic alkyl that carbonatoms is 3～20.K is 3～20 integer.)。
R in above-mentioned general formula (8)
9for the alkyl based on above-mentioned 3 yuan of above aliphatic polyols, the aliphatic alkyl that more preferably carbonatoms is 3～10, the aliphatic alkyl that further preferably carbonatoms is 3～6.
Above-mentioned k is the number corresponding with first number of more than 3 yuan aliphatic polyols.As above-mentioned k, more preferably 3～10 integer, 3～6 integer more preferably.
Above-mentioned isocyanurate structure body for having the material of more than 1 or 2 as represented in following general formula (4) isocyanurate ring in molecule.
[changing 9]
As above-mentioned isocyanurate structure body, can enumerate: react the tripolymer that obtains, react the pentamer that obtains, react heptamer obtaining etc. by seven dimerizations by five dimerizations by the trimerizing of above-mentioned isocyanic ester.
Wherein, be preferably as follows the represented tripolymer of general formula (9).
[changing 10]
Above-mentioned biuret is for having following general formula (10)
[changing 11]
The compound of represented structure, it can be by under the condition different from the situation that obtains above-mentioned isocyanurate structure body obtaining hexamethylene diisocyanate trimerizing.
As above-mentioned end-blocking agent, preferably use the compound with active hydrogen.As the above-mentioned compound with active hydrogen, for example, preferably use at least one in the group of selecting free alcohols, oximes, lactams, activity methene compound and pyrazole compound composition.
Thus, following situation one of is the preferred embodiment of the present invention: above-mentioned blocked isocyanate is to utilize end-blocking agent to make derived from the polyisocyanate compound of the hexamethylene diisocyanate material obtaining that reacts; Above-mentioned end-blocking agent is at least one that select in the group of free alcohols, oximes, lactams, activity methene compound and pyrazole compound composition.
The adding adult for hexamethylene diisocyanate and more than 3 yuan aliphatic polyols at the polyisocyanate compound for obtaining above-mentioned blocked isocyanate (II), as these 3 yuan above aliphatic polyols, specifically, can enumerate: glycerine, TriMethylolPropane(TMP) (TMP), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxyl-3-hydroxymethyl pentane, 1,1,1-tri-(two hydroxymethyl) propane, 2, the two 3 yuan of alcohol such as (hydroxymethyl) butanols-3 grade of 2-; 4 yuan of alcohol such as tetramethylolmethane, Glycerol dimer; 5 yuan of alcohol (pentitol) such as arabitol, ribitol, Xylitol; 6 yuan of alcohol such as Sorbitol Powder, N.F,USP MANNITOL, melampyrum, A Luo alcohol (hexitol) etc.Wherein particularly preferably TriMethylolPropane(TMP), tetramethylolmethane.
By carrying out the addition polymerization of hexamethylene diisocyanate and above-mentioned 3 yuan of above aliphatic polyols, can obtain the above-mentioned adult that adds.
As with above-mentioned polyisocyanate compound (II) compound that react, that there is active hydrogen, specifically, can enumerate: the alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, methoxypropanol; The oximes such as acetoxime, 2-butanone oxime, cyclohexanone-oxime; The lactams such as ε-caprolactam; Methyl acetoacetate, malonic ester isoreactivity methylene compound; 3-methylpyrazole, 3，5-dimethylpyrazole, 3, the pyrazole compounds such as 5-diethyl pyrazoles etc., can use one kind or two or more in them.
Wherein, preferred activity methene compound, oximes, more preferably activity methene compound.
As the commercially available product of above-mentioned blocked isocyanate, (Asahi Chemical Corp manufactures can to enumerate DURANATE K6000, the activity methene compound blocked isocyanate of HDI), DURANATE TPA-B80E (Asahi Chemical Corp's manufacture), DURANATE MF-B60X (Asahi Chemical Corp's manufacture), DURANATE 17B-60PX (Asahi Chemical Corp's manufacture), CORONET2507 (manufacture of Japanese polyurethane Co., Ltd.), CORONET2513 (manufacture of Japanese polyurethane Co., Ltd.), CORONET2515 (manufacture of Japanese polyurethane Co., Ltd.), Sumidur BL-3175 (manufacture of Sumika Bayer Urethane Co., Ltd.), Luxate HC1170 (manufacture of Olin Chemicals society), Luxate HC2170 (manufacture of Olin Chemicals society) etc.
Also can use polyisocyanate compound derived from hexamethylene diisocyanate (HDI) (hereinafter also referred to as polyisocyanate compound (III).) as solidifying agent.As polyisocyanate compound (III), can enumerate the above-mentioned substance as polyisocyanate compound (II).
As the concrete example of polyisocyanate compound (III), can enumerate: (Japanese polyurethane Co., Ltd. manufactures CORONET HX, the isocyanurate structure body of hexamethylene diisocyanate, NCO content 21.1%), (Zhu Hua Bayer society manufactures Sumidur N3300, the isocyanurate structure body of hexamethylene diisocyanate), (Mitsui Chemicals society manufactures Takenate D170N, the isocyanurate structure body of hexamethylene diisocyanate), (Zhu Hua Bayer society manufactures Sumidur N3800, the isocyanurate structure body prepolymer type of hexamethylene diisocyanate) etc.
By using derived from the polyisocyanate compound of isophorone diisocyanate (IPDI) (hereinafter also referred to as polyisocyanate compound (IV).) as solidifying agent, in coiling process etc., there is the resistance to adhesive excellence of the face that the solar cell module back veneer of the cured coating film being obtained by coating composition of the present invention contacts with respect to this cured coating film.
As above-mentioned polyisocyanate compound (IV), for example can enumerate isophorone diisocyanate and 3 yuan of above aliphatic polyol addition polymerizations and the isocyanurate structure body that adds adult, formed by isophorone diisocyanate (urea acrylate structure body) obtaining and the biuret being formed by isophorone diisocyanate.
As the above-mentioned adult that adds, for example, be preferably the material with the represented structure of following general formula (11).
[changing 12]
(in formula, R
10represent the aliphatic alkyl that carbonatoms is 3～20.R
11be expressed as follows the group shown in general formula (12).
[changing 13]
K is 3～20 integer.)。
R in above-mentioned general formula (11)
10for the alkyl based on above-mentioned 3 yuan of above aliphatic polyols, the aliphatic alkyl that more preferably carbonatoms is 3～10, the aliphatic alkyl that further preferably carbonatoms is 3～6.
Above-mentioned k is the number corresponding with first number of more than 3 yuan aliphatic polyols.As above-mentioned k, more preferably 3～10 integer, 3～6 integer more preferably.
Above-mentioned isocyanurate structure body for having the material of more than 1 or 2 as represented in following general formula (4) isocyanurate ring in molecule.
[changing 14]
As above-mentioned isocyanurate structure body, can enumerate: react the tripolymer that obtains, react the pentamer that obtains, react heptamer obtaining etc. by seven dimerizations by five dimerizations by the trimerizing of isophorone diisocyanate.
Wherein, be preferably as follows the represented tripolymer of general formula (13):
[changing 15]
(in formula, R
11with the R in above-mentioned general formula (11)
11identical.)。, above-mentioned isocyanurate structure body is preferably the tripolymer of isophorone diisocyanate.
Above-mentioned biuret is for having the compound of the represented structure of following general formula (14):
[changing 16]
(in formula, R
11with the R in above-mentioned general formula (11)
11identical.), it can be by under the condition different from the situation that obtains above-mentioned isocyanurate structure body obtaining isophorone diisocyanate trimerizing.
As above-mentioned polyisocyanate compound (IV), be wherein preferably at least one in the free above-mentioned group that adds adult and above-mentioned isocyanurate structure body composition of choosing., above-mentioned polyisocyanate compound (IV) is preferably at least one in the group that the isocyanurate structure body that adds adult and formed by isophorone diisocyanate that choosing freely obtains by isophorone diisocyanate and 3 yuan of aliphatic polyol addition polymerizations above forms.
In the situation that adds adult of above-mentioned polyisocyanate compound (IV) for isophorone diisocyanate and more than 3 yuan aliphatic polyols, as these 3 yuan above aliphatic polyols, specifically, can enumerate: glycerine, TriMethylolPropane(TMP) (TMP), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxyl-3-hydroxymethyl pentane, 1,1,1-tri-(two hydroxymethyl) propane, 2, the two 3 yuan of alcohol such as (hydroxymethyl) butanols-3 grade of 2-; 4 yuan of alcohol such as tetramethylolmethane, Glycerol dimer; 5 yuan of alcohol (pentitol) such as arabitol, ribitol, Xylitol; 6 yuan of alcohol such as Sorbitol Powder, N.F,USP MANNITOL, melampyrum, A Luo alcohol (hexitol) etc.Wherein particularly preferably TriMethylolPropane(TMP), tetramethylolmethane.
By by isophorone diisocyanate and above-mentioned 3 yuan of above aliphatic polyol addition polymerizations, can obtain being applicable to the adult that adds in the present invention.
As the adult that adds preferably using in the present invention, specifically, can enumerate for example represented compound of following general formula (15):
[changing 17]
(in formula, R
12be expressed as follows the represented group of general formula (12)),
[changing 18]
It is the polyisocyanate compound by isophorone diisocyanate and TriMethylolPropane(TMP) (TMP) addition polymerization are obtained.
As the commercially available product of the represented polyisocyanate compound of above-mentioned general formula (12) (TMP of isophorone diisocyanate adds adult), can enumerate Takenate D140N (Mitsui Chemicals, Inc's manufacture, NCO content 11%) etc.
As the commercially available product of the isocyanurate structure body being formed by isophorone diisocyanate, can enumerate Desmodur Z4470 (manufacture of Sumika Bayer Urethane Co., Ltd., NCO content 11%) etc.
Wherein, as above-mentioned solidifying agent, more preferably Takenate D120N (Mitsui Chemicals, Inc's manufacture, NCO content 11%), Sumidur N3300 (the isocyanurate structure body of the manufacture of Zhu Hua Bayer society, hexamethylene diisocyanate).
In coating composition of the present invention, with respect to solidified nature functional group 1 equivalent containing in the fluoropolymer of solidified nature functional group, the content of solidifying agent is preferably 0.1 equivalent～5 equivalent, 0.5 equivalent～1.5 equivalent more preferably.
Coating composition of the present invention can further contain other composition as required.As other composition, can enumerate other resin, additive; As above-mentioned additive, can enumerate such as curing catalyst, defoamer, flow agent, UV light absorber, photostabilizer, thickening material, closely sealed modifying agent, matting agent, hydrophilic agent etc.
As curing catalyst, can enumerate the reactant of such as organo-tin compound, phosphate ester acid, phosphate ester acid and amine, saturated or undersaturated polycarboxylic acid or its acid anhydrides, organic titanate compound, amine compound, lead octoate 36 etc.
Curing catalyst can use a kind, also can share two or more.With respect to fluoropolymer 100 mass parts containing solidified nature functional group, the combined amount of curing catalyst is preferably 1.0 × 10
-6mass parts～1.0 × 10
-2the degree of mass parts, more preferably 5.0 × 10
-5mass parts～1.0 × 10
-3the degree of mass parts.
As UV light absorber, any UV light absorber of organic system, inorganic system all can be used.In organic compound system, can enumerate the UV light absorber of such as salicylate system, benzotriazole system, benzophenone series, cyanoacrylate system etc. etc.; In inorganic system, the packing type of preferential oxidation zinc, cerium oxide etc. is inorganic is UV light absorber etc.
As hydrophilic agent, can enumerate on the surface of cured coating film partially and can keep the material of hydroxyl, specifically, can enumerate the GH-701 that Daikin Ind Ltd manufactures.The combined amount of hydrophilic agent is preferably 0.01 quality %～50 quality % in the ratio of the nonvolatile component with respect in coating composition.
Coating composition of the present invention can by by above-mentioned fluoropolymer containing solidified nature functional group, carbon black, dispersion agent and if desired other composition of use mix or be dispersed in organic solvent and prepare.
Above-mentioned mixing and dispersion are not particularly limited, for example, can carry out with known devices such as coating rocker, ball mill, kneaders.
The solid component concentration of coating composition of the present invention is not particularly limited, and can carry out suitable adjustment according to using method.
Be not particularly limited as the method that uses coating composition of the present invention to form cured coating film, on base material, application is combined with the coating composition of the present invention of solidifying agent conventionally, and it is solidified, and forms cured coating film.
Above-mentioned application is not particularly limited, and uses known method, can enumerate such as roller coat, curtain coating, spraying, mould painting, intaglio etc.
Solidify for above-mentioned, according to the suitable selection from dry, heating or radiation exposure etc. of the composition of coating composition.
So, coating composition of the present invention contains specific dispersion agent.Therefore, pigment-dispersing and masking liquid excellent in stability.In addition, use coating composition of the present invention can form the cured coating film of ultraviolet-shielding type excellence.Therefore, coating composition of the present invention can suitably be used as solar cell module back veneer coating agent.
Can use coating composition of the present invention to form cured coating film.By form cured coating film with coating composition of the present invention on the various resin base materials such as vinylchlorid, polycarbonate, acrylic resin, can improve flame retardant resistance, the weathering resistance of above-mentioned resin base material, and then can give hydrophilic surface.
Following solar cell module back veneer is also one of the present invention, and this solar cell module back veneer possesses the cured coating film that uses coating composition of the present invention to form.
That is, the invention still further relates to a kind of solar cell module back veneer, it is characterized in that, it has base material and the fluororesin layer at least one face of above-mentioned base material, and above-mentioned fluororesin layer is by using the cured coating film that aforementioned coating composition forms to form.
Solar cell module back veneer of the present invention has base material and the fluororesin layer at least one face of above-mentioned base material.
As above-mentioned base material, can enumerate the resin sheet conventionally using in solar cell module back veneer.
As above-mentioned resin sheet, for example can enumerate the sheet material by following polymer formation: polyethylene, polypropylene, polystyrene, polymethylmethacrylate, tetrafluoroethylene, polymeric amide, polyacrylonitrile, polyvinyl chloride, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PEN (PEN), polyoxymethylene, polycarbonate, polyphenylene oxide, polyester-polyurethane, poly(isophthaloyl metaphenylene diamine), PPTA etc.
Wherein preferred polyethylene terephthalate (PET).
Above-mentioned base material can also be watertightness sheet material.By using watertightness sheet material, in the situation that using backboard of the present invention to make solar module, can prevent that moisture is thoroughly in sealing material or solar battery cell.
As above-mentioned watertightness sheet material, can enumerate the metal sheets such as such as PET sheet material, silicon oxide evaporation PET sheet material, aluminium or stainless steel etc.
Wherein, from the viewpoint of light weight, low price, be imbued with flexible, preferential oxidation silicon evaporation PET sheet material and PET sheet material.
In addition, for improve with above-mentioned base material on the cementability of fluororesin layer or other layer, sheet material etc., above-mentioned base material can carry out surface treatment.As surface treatment, can exemplify such as Corona discharge Treatment, plasma discharge processing, change into sandblasting in the situation of processing, metal sheet etc.Arbitrary processing all can adopt existing known method.
Above-mentioned surface treatment can form, also can on two faces, form on of a base material face.
The thickness of above-mentioned base material is preferably 10 μ m～500 μ m, 50 μ m～300 μ m more preferably.
Solar cell module back veneer of the present invention at least one mask on above-mentioned base material has fluororesin layer.Above-mentioned fluororesin layer is the cured coating film that uses the coating composition of the invention described above to form.
The formation of above-mentioned fluororesin layer can similarly be carried out with the method for the coating composition formation cured coating film that uses the invention described above.
Above-mentioned application on base material can be by being directly coated on aforementioned coating composition on base material and carrying out, also can be by being coated with to carry out across undercoat etc.
For the formation of above-mentioned undercoat, with existing known priming paint coating by ordinary method.As priming paint coating, can enumerate such as epoxy resin, carbamate resins, acrylic resin, silicone resin, vibrin etc.
Good from the viewpoint of disguise, weathering resistance, chemical proofing, wet fastness, the thickness of preferred above-mentioned fluororesin layer is more than 2 μ m.This thickness more preferably 3 μ m above, more preferably more than 5 μ m.If can not get lightweight effect because thickness is blocked up, thereby the upper limit is preferably 1000 about μ m, 100 μ m more preferably.As above-mentioned thickness, be particularly preferably 5 μ m～40 μ m.
For above-mentioned fluororesin layer, after the Soxhlet of utilizing acetone to carry out is extracted, the degree of crosslinking calculating with the form of gel fraction is preferably 90%～100%, more preferably 95%～100%, more preferably 98%～100%.
Solar cell module back veneer of the present invention can also have above-mentioned fluororesin layer on the two sides of above-mentioned base material.Have fluororesin layer on the two sides of base material, these 2 fluororesin layers are assigned to form by the one-tenth being included in above-mentioned scope, can be the fluororesin layer being formed by identical component, can be also the fluororesin layer being formed by heterogeneity.
In addition,, in order to improve and the cementability of other layer, can impose surface treatment to above-mentioned fluororesin layer.
As surface treatment, can exemplify such as Corona discharge Treatment, plasma discharge processing, change into the coating processing of processing, silane coupling agent etc.
In solar cell module back veneer of the present invention, except above-mentioned base material and fluororesin layer, can also there is other material layer.Above-mentioned backboard has in the situation of other material layer, has preferably carried out lamination according to the order of other material layer, base material, fluororesin layer.
As above-mentioned other material layer, can enumerate the film (other sheet material or film) of the joint compound layer being formed by joint compound, the cured coating film without the fluorocarbon polymer coating of solidified nature functional group, fluoropolymer sheet material, polyester sheet or polyester coating.These layers can carry out lamination across undercoat etc.
As above-mentioned joint compound layer, can enumerate is for example that joint compound, polyester are that joint compound, epoxy are that joint compound, nylon are that joint compound, ethane-acetic acid ethyenyl ester are the layer that the known joint compounds such as joint compound, acrylic acid series joint compound, rubber series joint compound form by carbamate.
As the cured coating film of the above-mentioned fluorocarbon polymer coating without solidified nature functional group, for example can enumerate: the cured coating film that coordinates the coating that tetraalkoxysilane or its partial hydrolystate form in PVdF of recording in TOHKEMY 2004-214342 communique; The cured coating film of VdF/TFE/CTFE multipolymer and the compo of the acrylic resin that contains organoalkoxysilane unit; The cured coating film of the compo of the acrylic resin of VdF/TFE/HFP multipolymer and hydroxyl; In VdF/HFP multipolymer, coordinate cured coating film of the coating that amino silicane coupling agent forms etc.Good from the viewpoint of disguise, weathering resistance, chemical proofing, wet fastness, preferably thickness is generally 5 μ m～300 μ m.More preferably 10 μ m～100 μ m, 10 μ m～50 μ m more preferably.
As above-mentioned fluoropolymer sheet material, can enumerate the fluoropolymer sheet material that PVdF sheet material, PVF sheet material, PCTFE sheet material, TFE/HFP/ ethylene copolymer sheet material, TFE/HFP multipolymer (FEP) sheet material, TFE/PAVE multipolymer (PFA) sheet material, ethene/TFE multipolymer (ETFE) sheet material, ethene/CTFE multipolymer (ECTFE) sheet material etc. use in existing backboard.Good from the viewpoint of weathering resistance, preferably thickness is generally 5 μ m～300 μ m.Thickness is 10 μ m～100 μ m, 10 μ m～50 μ m more preferably more preferably.
As above-mentioned polyester sheet, can directly use the polyester sheet using in existing backboard, bonding acrylic acid series joint compound, the carbamate of utilizing of itself and watertightness sheet material is that joint compound, epoxy are that joint compound, polyester are that joint compound etc. carries out.From the viewpoint of weathering resistance, cost, transparent good, preferably thickness is generally 5 μ m～300 μ m.Thickness is 10 μ m～100 μ m, 10 μ m～50 μ m more preferably more preferably.
As above-mentioned polyester coating, can enumerate: the polyester coating that has used saturated polyester resin (it uses polycarboxylic acid and polyvalent alcohol etc. to form); Use the polyester coating of unsaturated polyester resin (it uses maleic anhydride, fumaric acid etc. to form with glycols) etc., can form film by coating processs such as roller coat, curtain coating, spraying, mould paintings.Good from the viewpoint of disguise, weathering resistance, chemical proofing, wet fastness, preferably thickness is 5 μ m～300 μ m.Thickness is 10 μ m～100 μ m, 10 μ m～50 μ m more preferably more preferably.
In solar cell module back veneer of the present invention, on above-mentioned base material, use aforementioned coating composition utilize aforesaid method to form fluororesin layer or form above-mentioned other material layer or carry out the lamination of sheet material.In addition making desired layer formation by known method manufactures.
The invention still further relates to solar module, it is characterized in that, it possesses above-mentioned solar cell module back veneer.
The sealing material layer that solar module of the present invention preferably has above-mentioned backboard and forms on above-mentioned backboard.
Sealing material layer is the layer for sealed solar energy battery unit, preferably by formations such as ethylene/vinyl acetate (EVA), polyvinyl butyral acetal (PVB), silicone resin, epoxy resin, acrylic resins.Wherein preferably use EVA.
The generalized schematic of one example of the preferred implementation of solar module of the present invention has been shown in Fig. 1 and Fig. 2.
In the 1st structure shown in Fig. 1, the sealed material layer 2 of solar battery cell 1 seals, and sealing material layer 2 is clipped in the middle by upper layer 3 and backboard 4.Backboard 4 is made up of base material 5 and fluororesin layer 6, possesses this fluororesin layer by fluororesin layer 6 for outermost mode.
In the 2nd structure shown in Fig. 2, backboard 4 is the 3-tier architecture that has other material layer 7 on a face of base material 5, have fluororesin layer 6 on another face, possesses this fluororesin layer by fluororesin layer 6 for outermost mode.
Solar module of the present invention can further have terminal box.Above-mentioned terminal box is the casing for receiving following terminal, and this terminal connects for taking out from the electrode of the output power of solar battery cell or distribution (electrode being connected with solar battery cell or distribution), for output power being fetched into the cable of solar module outside.
Terminal box is preferably arranged on solar cell module back veneer side across adhesive linkage.Above-mentioned adhesive linkage can be the layer being formed by known joint compound.
As mentioned above, utilize the present invention, the coating composition that can form the cured coating film with excellent ultraviolet-shielding type can be provided.Use the cured coating film that coating composition of the present invention forms on base material can suitably be used as solar cell module back veneer.
Embodiment
By embodiment, the present invention will be described in more detail, but the present invention is not subject to the restriction of this embodiment.
(embodiment 1)
With respect to Zeffle GK-570 (Daikin Ind Ltd's manufacture) 100 mass parts, add butylacetate 92.7 mass parts, as MA100 (manufactures of society of Mitsubishi Chemical) 13 mass parts of pigment, as the SOLSPERSE76500 of dispersion agent (Japanese Lubrizol society manufacture) 6.5 mass parts, prepare coating composition.
(embodiment 2～6, comparative example 1～4)
With respect to Zeffle GK-570 (Daikin Ind Ltd's manufacture) 100 mass parts, by adding pigment, dispersion agent and butylacetate shown in table 1, in addition, prepare similarly to Example 1 coating composition.
It should be noted that, the each composition in table 1 is as follows.
Fluoropolymer containing solidified nature functional group:
Zeffle GK-570 (in butylacetate, solid component concentration is that 65 quality %, Daikin Ind Ltd manufacture)
Pigment:
Raven420 (carbon black, median size: 86nm, pH:8.3, COLUMBIAN society manufacture)
MA100 (carbon black, median size: 24nm, pH:3.5, society of Mitsubishi Chemical manufacture)
Dispersion agent:
SOLSPERSE76500 (there is ethylene oxide (EO) chain, propylene oxide (PO) chain and urethanes, base number through the quaternised amino of quaternizing agent and be 15.2mgKOH/g, acid number essence and be 0mgKOH/g, weight-average molecular weight and be 50000, EO is PO 10%, effective constituent is 50 quality %, Japanese Lubrizol society manufactures)
Disparlon DA-7301 (polyesteramide amine salt, base number 40mgKOH/g, acid number 15mgKOH/g, weight-average molecular weight 9700, effective constituent 75 quality %, nanmu originally change into society and manufacture)
Disparlon DA-375 (polyether phosphate compound, base number 0mgKOH/g, acid number 14mgKOH/g, weight-average molecular weight 2000～3000, effective constituent >95 quality %, nanmu originally change into society and manufacture)
Carry out following evaluation for obtained coating composition.The results are shown in table 1.
< pigment-dispersing >
(manufacture of Daikin Industries (strain) society, Neoflon PCTFE film, thickness 25 μ are m) as evaluation base material to prepare PCTFE film, utilizing scraping strip coating machine is that 10 μ m are at one side application above-described embodiment 1～6 of this film, the coating composition of comparative example 1～4 by dry film thickness, at 60 ℃, be dried 30 minutes, obtain the coated film of 10 μ m.
Use varied-angle glossmeter (manufacture of Japanese electric look industrial society, VGS-SENSOR) to measure the glossiness of the coated film obtaining.
< masking liquid stability >
The coating composition of above-described embodiment 1～6, comparative example 1～4 is encased in and in the screw socket tubular container that volume is 50ml, carries out airtightly, at 50 ℃, leave standstill, the number of days that does not observe liquid separation after leaving standstill is evaluated.
< ultraviolet-shielding type >
Similarly using scraping strip coating machine with the evaluation method of above-mentioned pigment-dispersing is that 10 μ m are coated with the coating composition of above-described embodiment 1～6, comparative example 1～4 to be contained on PCTFE film according to dry film thickness, at 60 ℃, is dried 30 minutes, obtains the coated film of 10 μ m.
Use spectrophotometer (manufacture of society of Hitachi, U-4100), measure the ultraviolet transmitance of the 400nm wavelength of the coated film obtaining.
Industrial applicibility
Utilize the present invention, can provide and there is the coating composition of excellent pigment-dispersing and masking liquid stability and the solar cell module back veneer of ultraviolet-shielding type excellence.
Nomenclature
1 solar battery cell
2 sealing material layers
3 upper layers
4 backboards
5 base materials
6 fluororesin layers
7 other material layers.
Claims (10)
1. a coating composition, is characterized in that,
It contains containing the fluoropolymer of solidified nature functional group, carbon black, dispersion agent and organic solvent;
The base number of described dispersion agent is more than 12mgKOH/g and acid number is below 12mgKOH/g.
2. coating composition as claimed in claim 1, wherein, the base number of dispersion agent is that 12mgKOH/g～40mgKOH/g and acid number are below 12mgKOH/g.
3. coating composition as claimed in claim 1, wherein, the base number of dispersion agent is that 12mgKOH/g～40mgKOH/g and acid number are essentially 0mgKOH/g.
4. the coating composition as described in claim 1,2 or 3, wherein, dispersion agent is made up of urethanes.
5. coating composition as claimed in claim 4, wherein, urethanes is for to have ethylene oxide chain and/or propylene oxide chain at main chain, and has the urethanes of quaternized dose of quaternised amino.
6. the coating composition as described in claim 1,2,3,4 or 5, wherein, the polymerized unit that contains the polymerized unit based on fluorochemical monomer and the monomer based on containing solidified nature functional group containing the fluoropolymer of solidified nature functional group, the described monomer containing solidified nature functional group is at least one monomer selecting in the group of free hydroxyl monomer, carboxyl group-containing monomer, anhydride monomers, emulsion stability and silicone-based vinyl monomer composition.
7. coating composition as claimed in claim 6, wherein, fluorochemical monomer is at least one that select in the group of free tetrafluoroethylene, trifluorochloroethylene and vinylidene fluoride composition.
8. coating composition as claimed in claim 6, wherein, fluorochemical monomer is tetrafluoroethylene.
9. a solar cell module back veneer, is characterized in that,
It has base material and the fluororesin layer at least one face of described base material,
Described fluororesin layer is the cured coating film that right to use requires the coating composition described in 1,2,3,4,5,6,7 or 8 to form.
10. a solar module, is characterized in that, it possesses solar cell module back veneer claimed in claim 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JP2012-243171 | 2012-11-02 | ||
| JP2012243171 | 2012-11-02 |
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| CN103805002A true CN103805002A (en) | 2014-05-21 |
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| CN (1) | CN103805002A (en) |
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| CN104231701A (en) * | 2014-10-09 | 2014-12-24 | 哈尔滨工业大学 | Infrared radiating coating for photovoltaic module backing plate and preparation method of radiating photovoltaic module backing plate |
| CN104356914A (en) * | 2014-11-28 | 2015-02-18 | 明冠新材料股份有限公司 | Solar back panel transparent polyurethane paint and preparation method thereof |
| CN104362207A (en) * | 2014-11-14 | 2015-02-18 | 无锡中洁能源技术有限公司 | High-resistance solar panel back membrane and preparation method thereof |
| CN106085325A (en) * | 2016-07-14 | 2016-11-09 | 南京大学 | The epoxy adhesive that tertiary-amine modified LNBR is toughness reinforcing |
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| CN104356842A (en) * | 2014-11-14 | 2015-02-18 | 无锡中洁能源技术有限公司 | PCTFE coating material with high water vapor barrier property and preparation method thereof |
| CN112745753B (en) * | 2020-12-30 | 2022-04-01 | 常州威斯敦粘合材料有限责任公司 | Outer layer transparent coating, photovoltaic transparent back plate and preparation method thereof |
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| CN106085325A (en) * | 2016-07-14 | 2016-11-09 | 南京大学 | The epoxy adhesive that tertiary-amine modified LNBR is toughness reinforcing |
| CN106085325B (en) * | 2016-07-14 | 2019-04-02 | 南京大学 | The epoxy adhesive of tertiary-amine modified liquid nitrile rubber toughening |
Also Published As
| Publication number | Publication date |
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| JP6299149B2 (en) | 2018-03-28 |
| JP2014111736A (en) | 2014-06-19 |
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Application publication date: 20140521 |