CN105324853A - Sealing material composition for solar cells, sealing material layer for solar cells, and solar cell module using same - Google Patents
Sealing material composition for solar cells, sealing material layer for solar cells, and solar cell module using same Download PDFInfo
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- CN105324853A CN105324853A CN201480035152.3A CN201480035152A CN105324853A CN 105324853 A CN105324853 A CN 105324853A CN 201480035152 A CN201480035152 A CN 201480035152A CN 105324853 A CN105324853 A CN 105324853A
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- solar batteries
- sealing material
- solar
- material layer
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- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 239000003566 sealing material Substances 0.000 title claims abstract description 67
- -1 amine compound Chemical class 0.000 claims abstract description 76
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims abstract description 30
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 claims abstract description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims description 55
- 239000011347 resin Substances 0.000 claims description 55
- 150000001875 compounds Chemical class 0.000 claims description 50
- 239000011159 matrix material Substances 0.000 claims description 41
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 17
- XOBOCRSRGDBOGH-UHFFFAOYSA-N 5-phenylnonan-5-ol Chemical group CCCCC(O)(CCCC)C1=CC=CC=C1 XOBOCRSRGDBOGH-UHFFFAOYSA-N 0.000 claims description 15
- 229920006163 vinyl copolymer Polymers 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 230000006866 deterioration Effects 0.000 abstract description 21
- 238000003475 lamination Methods 0.000 abstract description 8
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- 230000000694 effects Effects 0.000 description 19
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
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- 150000001412 amines Chemical class 0.000 description 4
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- 239000011248 coating agent Substances 0.000 description 4
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- 239000004698 Polyethylene Substances 0.000 description 3
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- 239000007983 Tris buffer Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000008393 encapsulating agent Substances 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
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- 238000002844 melting Methods 0.000 description 3
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
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- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
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- FZMDRRQLSASXDN-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(2-hydroxyethyl)phenol Chemical compound OCCc1ccc(c(O)c1)-c1nc(nc(n1)-c1ccccc1)-c1ccccc1 FZMDRRQLSASXDN-UHFFFAOYSA-N 0.000 description 1
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- MDBKCNBPGJPWMA-UHFFFAOYSA-N xanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1.C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 MDBKCNBPGJPWMA-UHFFFAOYSA-N 0.000 description 1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
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Abstract
The present invention relates to providing a composition for solar cells, which is capable of forming a sealing material layer for solar cells, said sealing material layer being able to be sufficiently cured and crosslinked during module lamination and being suppressed in deterioration even after exposure to ultraviolet light for a long period of time. The present invention also relates to providing: a sealing material layer for solar cells, which is able to be sufficiently cured and crosslinked during module lamination and is suppressed in deterioration even after exposure to ultraviolet light for a long period of time; and a solar cell module which uses this sealing material layer for solar cells. A sealing material composition for solar cells, which is characterized by containing a dibutyl hydroxy toluene (BHT) derivative and a hindered amine compound having a phenol skeleton in each molecule.
Description
Technical field
The present invention relates to encapsulant layer composition used for solar batteries, sealing material layer used for solar batteries and use the solar cell module of this sealing material layer used for solar batteries.
Background technology
By the utilization to solar energy, the energy source being expected to the fossil fuel replaced in the past can be provided, therefore, to can convert solar energy into electricity device exploitation, such as the exploitation of photovoltaic devices (it is also known as solar cell) etc. is received much concern in recent years.Have developed the photovoltaic devices of some dissimilar maturations, wherein, enumerate some for example, the PN junction device of silicon system device, III-V and II-VI, copper-indium-gallium-selenium (CIGS) film apparatus, organic sensitizer device, organic thin film device and cadmium sulfide/cadmium telluride (CdS/CdTe) film apparatus are included.About the more detailed record of said apparatus is found in document etc. (such as, see non-patent literature 1).But comprise the durability of the said apparatus of encapsulant, photostability etc. and still there is room for improvement, the technology developing to improve its efficiency is the problem that Many researchers is being carried out.
In the sealing material layer of existing solar cell purposes, contain various additive to prevent the oxidative degradation of resin, light deterioration etc.Such as, add antioxidant, light stabilizer, thus the method for the variable color such as gonorrhoea, xanthochromia preventing the deterioration of the resin because Long-Time Service causes, additive and cause is used (such as, see patent documentation 1).
In addition, usually, sealing material layer used for solar batteries is also responsible for the effect of the shape keeping the solar cell module formed by components such as battery unit, glass and backboards, also needs to have sufficient bridging property.But a large amount of antioxidant, light stabilizer added in said method, the bridging property having the matrix resin of sealing material layer significantly reduces, the problem lost as the characteristic of sealing material layer.And on the other hand, if increase the addition of organic peroxide etc. to maintain bridging property, then after cross-linking reaction, residue in organic peroxide in sealing material layer and catabolite will become another reason causing matrix resin deterioration.
In addition, with regard to as antioxidant often by with regard to the phenol antioxidant that uses, found to issue at its Antioxidation Mechanism the look that changes, if be added in a large number in sealing material layer, then may cause xanthochromia.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-243682 publication
The people such as non-patent literature 1:Lin, " HighPhotoelectricConversionEfficiencyofMetalPhthalocyani ne/FullereneHeterojunctionPhotovoltaicDevice " (InternationalJournalofMolecularSciences, 12nd volume, 476 pages, 2011)
Summary of the invention
In view of the foregoing, the object of the present invention is to provide following composition used for solar batteries, described composition used for solar batteries can be formed in module lamination (modulelamination) even if time full cross-linkedly can solidify and be exposed to its deterioration of ultraviolet also repressed sealing material layer used for solar batteries for a long time.
In addition, the object of the present invention is to provide following sealing material layer used for solar batteries and use the solar cell module of this sealing material layer used for solar batteries, described sealing material layer used for solar batteries can full cross-linkedly solidify when module lamination, even if be exposed to ultraviolet for a long time, its deterioration is also suppressed.
In order to solve above-mentioned problem, present inventor has carried out studying with keen determination, found that by hereinafter described Encapulant composition used for solar batteries, sealing material layer used for solar batteries and the solar cell module using this sealing material layer used for solar batteries, can above-mentioned purpose be reached, thus complete the present invention.
The feature of Encapulant composition used for solar batteries of the present invention is, containing dibutyl hydroxy toluene (BHT) derivative and the hindered amine compound in molecule with phenol backbone.
The Encapulant composition used for solar batteries of the application of the invention, is exposed to its deterioration of ultraviolet also repressed sealing material layer used for solar batteries for a long time even if can full cross-linkedly solidify when easily can be formed in module lamination.About presenting of above-mentioned action effect, infer that it presents based on the mechanism hereafter recorded, but be not defined as must via following mechanism.First, infer that above-mentioned dibutyl hydroxy toluene (BHT) derivative easily spreads because molecular weight is low in matrix resin, thus effectively in sealing material layer, inhibit oxidative degradation, but due to its low-molecular-weight, so there is the worry of oozing out (bleedout).On the other hand, the molecular weight inferring above-mentioned hindered amine compound is larger, and the worry of oozing out is reduced, thus is able to easily to maintain long function and presents.With regard to Encapulant composition used for solar batteries of the present invention, by containing above-mentioned dibutyl hydroxy toluene (BHT) derivative and above-mentioned hindered amine compound, oxidative degradation can be prevented in over a long time when there is not crosslinked obstruction, further, light deterioration can be suppressed.
It should be noted that, the dibutyl hydroxy toluene (BHT) in the present invention refers to 2,6-di-tert-butyl-4-methy phenol.Dibutyl hydroxy toluene (BHT) derivative refers to and carries out chemical modification to above-mentioned dibutyl hydroxy toluene and the compound obtained.
In addition, hindered amine (hinderedamine) in the present invention is often referred to the amines with following character, described character is: directly catch the free radical produced in system because of illumination etc., by the stabilisation by the sterically hindered structure of self, the Kinds of Free Radicals caused by conjugation (resonance) structure, (suppression) free radical is stoped to carry out the process of chain reaction.
In addition, in Encapulant composition used for solar batteries of the present invention, above-mentioned hindered amine compound preferably has dibutyl hydroxy toluene skeleton.By using above-mentioned hindered amine compound, can also be given it further also as the function of antioxidant to hindered amine compound self.Thus, the sealing material layer used for solar batteries utilizing above-mentioned composition to be formed more effectively can present the effect preventing oxidative degradation and the effect suppressing light deterioration in over a long time.
In addition, in Encapulant composition used for solar batteries of the present invention, above-mentioned hindered amine compound preferably has 2,2,6,6-tetramethyl-4-piperidinyl structure.By containing said structure, the sealing material layer used for solar batteries utilizing above-mentioned composition to be formed is easy in over a long time, present the effect preventing oxidative degradation and the effect suppressing light deterioration more reliably.
In addition, in Encapulant composition used for solar batteries of the present invention, the molecular weight of above-mentioned hindered amine compound is preferably 400 ~ 4000.By using above-mentioned hindered amine compound, hindered amine compound self can be more effectively suppressed to ooze out.Consequently, the sealing material layer used for solar batteries utilizing above-mentioned composition to be formed can present the effect preventing oxidative degradation and the effect suppressing light deterioration more reliably in over a long time.
In addition, in Encapulant composition used for solar batteries of the present invention, preferably also containing the hindered amine compound in molecule without phenol backbone.By further and use above-mentioned hindered amine compound, the sealing material layer used for solar batteries utilizing above-mentioned composition to be formed likely is easy to present in over a long time and above-mentionedly prevents the effect of oxidative degradation and the effect of suppression light deterioration.
In addition, for Encapulant composition used for solar batteries of the present invention, preferably, the matrix resin of above-mentioned Encapulant composition used for solar batteries take vinyl copolymer as principal component, further, the above-mentioned dibutyl hydroxy toluene derivative containing 0.001 ~ 0.2 weight portion for the above-mentioned matrix resin of 100 weight portions and the above-mentioned hindered amine compound of 0.001 ~ 0.3 weight portion.By being above-mentioned use level, the crosslinked obstruction of matrix resin more effectively can be suppressed.Thus, the sealing material layer used for solar batteries utilizing above-mentioned composition to be formed can present the effect preventing oxidative degradation and the effect suppressing light deterioration when there is not crosslinked obstruction more reliably in over a long time.
It should be noted that, above-mentioned " for principal component " refers to following situation: when above-mentioned matrix resin is the mixture of various kinds of resin, comprise more than 50 % by weight with mass ratio range.Above-mentioned weight ratio is more preferably more than 70 % by weight, and more preferably 90 % by weight.
In addition, in Encapulant composition used for solar batteries of the present invention, preferably also containing ultraviolet absorber compounds.By using above-mentioned ultraviolet absorber compounds, possibility being become to the further suppression, imparting wavelength convert function etc. of UV degradation, the sealing material layer used for solar batteries multifunction more utilizing above-mentioned composition to be formed can be made.
In addition, in Encapulant composition used for solar batteries of the present invention, above-mentioned matrix resin is preferably principal component with vinyl-vinyl acetate copolymer.By making above-mentioned matrix resin be principal component with vinyl-vinyl acetate copolymer, the sealing material layer used for solar batteries of light transmission, excellent in te pins of durability can be formed more reliably.
On the other hand, the feature of sealing material layer used for solar batteries of the present invention is, utilizes above-mentioned Encapulant composition used for solar batteries to be formed.By utilizing above-mentioned composition to form sealing material layer used for solar batteries, even if it is become can full cross-linkedly to solidify when module lamination be exposed to its deterioration of ultraviolet also repressed sealing material layer used for solar batteries for a long time.
On the other hand, the feature of solar cell module of the present invention is, comprises the sealing material layer used for solar batteries utilizing above-mentioned Encapulant composition used for solar batteries to be formed.Above-mentioned solar cell module owing to having above-mentioned sealing material layer used for solar batteries, even if so become can full cross-linkedly to solidify when module lamination and be exposed to its deterioration of ultraviolet also repressed solar cell module for a long time.
In addition, in solar cell module of the present invention, above-mentioned solar battery cell is preferably crystal silicon solar energy battery.For above-mentioned solar cell module, by using the solar cell module of laminated above-mentioned solar battery cell, more effectively can improve photoelectric conversion efficiency further.
Accompanying drawing explanation
Fig. 1 represents the example of the solar cell module employing sealing material layer used for solar batteries of the present invention.
Fig. 2 represents the example of the solar cell module employing sealing material layer used for solar batteries of the present invention.
Embodiment
Below, embodiments of the present invention are described.
(Encapulant composition used for solar batteries)
The feature of Encapulant composition used for solar batteries of the present invention is containing dibutyl hydroxy toluene (BHT) derivative and the hindered amine compound in molecule with phenol backbone.Above-mentioned Encapulant composition used for solar batteries, can be formed by the hindered amine compound etc. at least disperseing dibutyl hydroxy toluene (BHT) derivative and have a phenol backbone in optically transparent matrix resin in molecule.With regard to Encapulant composition used for solar batteries of the present invention, by containing above-mentioned dibutyl hydroxy toluene (BHT) derivative and above-mentioned hindered amine compound, following sealing material layer used for solar batteries can be formed, even if described sealing material layer used for solar batteries is when carrying out module lamination, crosslinkable resin also has sufficient bridging property, even if be exposed to ultraviolet for a long time, the UV barrier of ultraviolet absorber compounds also can be maintained, and the variable color of matrix resin etc. is less likely to occur.
As dibutyl hydroxy toluene (BHT) derivative in the present invention, except dibutyl hydroxy toluene (BHT), also can enumerate the compound that a part or multiple position of above-mentioned dibutyl hydroxy toluene (BHT) are carried out chemical modification and obtained.As above-mentioned dibutyl hydroxy toluene (BHT) derivative, such as can enumerate in the sodium salt of dibutyl hydroxy toluene, sylvite etc. and salt, on phenyl ring or a part for alkyl the derivative etc. that occurs to replace and obtain.Wherein, dibutyl hydroxy toluene (BHT) is preferably used.
The molecular weight of above-mentioned dibutyl hydroxy toluene (BHT) is 220, when using above-mentioned dibutyl hydroxy toluene (BHT) derivative, the molecular weight of said derivative is preferably 220 ~ 500, is more preferably 220 ~ 400, and more preferably 220 ~ 300.It should be noted that, molecular weight determination utilizes mass spectrography (MSspectrum) to carry out.
As the hindered amine compound in molecule with phenol backbone in the present invention, can be used in molecule and there is phenol backbone and the amines with following character, described character is: directly catch the free radical produced in system because of illumination etc., by the stabilisation of the Kinds of Free Radicals caused by self sterically hindered structure and conjugation, (suppression) free radical is stoped to carry out the process of chain reaction.In addition, preferably, above-mentioned hindered amine compound does not show maximum absorption in fact in ultraviolet wavelength (300 ~ 400nm) region.
Above-mentioned hindered amine compound preferably has 2,2,6,6-tetramethyl-4-piperidinyl structure.In addition, such as, such bulky substituent such as there is the tert-butyl group can be enumerated and make other molecules be difficult to the aminated compounds etc. of adjacent part (ortho position etc.) (space steric effect) close to the hydroxyl on phenol backbone.
As above-mentioned hindered amine compound, such as can enumerate [[3,5-two (1,1-dimethyl ethyl)-4-hydroxy phenyl] methyl] butylmalonic acid two (1,2,2,6,6-pentamethyl-4-piperidyl) 685), 1-[2-[3-(3 ester (molecular weight:, 5-di-tert-butyl-hydroxy phenyl) propionyloxy] ethyl]-4-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionyloxy]-2,2,6,6-tetramethyl piperidine (molecular weight: 722) etc.These compounds may be used alone, can also be two or more kinds in combination.
As above-mentioned hindered amine compound, commercially available product can be used aptly.As above-mentioned hindered amine compound, such as, can enumerate Tinuvin144 (molecular weight: 685, BASF AG's system) etc., all in molecule, there is phenol backbone.These compounds may be used alone, can also be two or more kinds in combination.
In addition, in above-mentioned Encapulant composition used for solar batteries, the molecular weight of above-mentioned hindered amine compound is preferably 400 ~ 4000, is more preferably 500 ~ 2000, and more preferably 600 ~ 1000.If molecular weight is less than 400, then above-mentioned hindered amine compound self easily oozes out.On the other hand, if molecular weight is more than 4000, then sometimes produce and the problem such as the compatibility of matrix resin.It should be noted that, molecular weight determination utilizes mass spectrography to carry out.
In addition, in Encapulant composition used for solar batteries of the present invention, the matrix resin of above-mentioned Encapulant composition used for solar batteries is principal component with vinyl copolymer and above-mentioned dibutyl hydroxy toluene derivative containing 0.001 ~ 0.2 weight portion for the above-mentioned matrix resin of 100 weight portions is preferred, be more preferably 0.01 ~ 0.15 weight portion, more preferably 0.02 ~ 0.1 weight portion.By coordinating with above-mentioned scope, the function mainly as antioxidant can be obtained suitably.
In addition, in Encapulant composition used for solar batteries of the present invention, the matrix resin of above-mentioned Encapulant composition used for solar batteries is principal component with vinyl copolymer and above-mentioned hindered amine compound containing 0.001 ~ 0.3 weight portion for the above-mentioned matrix resin of 100 weight portions is preferred, be more preferably 0.005 ~ 0.1 weight portion, more preferably 0.01 ~ 0.05 weight portion.By coordinating with above-mentioned scope, the function mainly as light stabilizer can be obtained suitably.
In addition, in Encapulant composition used for solar batteries of the present invention, preferably, the matrix resin of above-mentioned Encapulant composition used for solar batteries take vinyl copolymer as principal component, further, the above-mentioned dibutyl hydroxy toluene derivative containing 0.001 ~ 0.2 weight portion for the above-mentioned matrix resin of 100 weight portions and the above-mentioned hindered amine compound of 0.001 ~ 0.3 weight portion.In addition, can the above-mentioned dibutyl hydroxy toluene derivative of 0.001 ~ 0.2 weight portion and the above-mentioned hindered amine compound of 0.005 ~ 0.1 weight portion be contained, also can contain the above-mentioned dibutyl hydroxy toluene derivative of 0.001 ~ 0.2 weight portion and the above-mentioned hindered amine compound of 0.01 ~ 0.05 weight portion.In addition, the above-mentioned dibutyl hydroxy toluene derivative of 0.01 ~ 0.15 weight portion and the above-mentioned hindered amine compound of 0.001 ~ 0.3 weight portion can be contained, also can contain the above-mentioned dibutyl hydroxy toluene derivative of 0.01 ~ 0.15 weight portion and the above-mentioned hindered amine compound of 0.005 ~ 0.1 weight portion, can also the above-mentioned dibutyl hydroxy toluene derivative of 0.01 ~ 0.15 weight portion and the above-mentioned hindered amine compound of 0.01 ~ 0.05 weight portion be contained.In addition, the above-mentioned dibutyl hydroxy toluene derivative of 0.02 ~ 0.1 weight portion and the above-mentioned hindered amine compound of 0.001 ~ 0.3 weight portion can be contained, also can contain the above-mentioned dibutyl hydroxy toluene derivative of 0.02 ~ 0.1 weight portion and the above-mentioned hindered amine compound of 0.005 ~ 0.1 weight portion, can also the above-mentioned dibutyl hydroxy toluene derivative of 0.02 ~ 0.1 weight portion and the above-mentioned hindered amine compound of 0.01 ~ 0.05 weight portion be contained.By being above-mentioned use level, can more effectively suppress to hinder the crosslinked of matrix resin.Consequently, the sealing material layer used for solar batteries utilizing above-mentioned composition to be formed can present the effect preventing oxidative degradation and the effect suppressing light deterioration when there is not crosslinked obstruction more reliably in over a long time.Compared with adding separately the situation of each composition, above-mentioned action effect is not limited in Overlay, can also obtain synergy.
In addition, in above-mentioned Encapulant composition used for solar batteries, preferably also containing the hindered amine compound in molecule without phenol backbone.By further and use above-mentioned hindered amine compound, the sealing material layer used for solar batteries utilizing above-mentioned composition to be formed sometimes becomes easily to present in over a long time and above-mentionedly prevents the effect of oxidative degradation and the effect of suppression light deterioration.
As the above-mentioned hindered amine compound in molecule without phenol backbone, commercially available product can be used aptly.As the above-mentioned hindered amine compound in molecule without phenol backbone, such as, two (the 1-octyloxy-2 of decanedioic acid can be enumerated, 2, 6, 6-tetramethyl-4-piperidyl) ester (Tinuvinl23, BASF AG's system, molecular weight is 737), 1, 2, 3, 4-ethylene-dimalonic acid four (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) ester (LA-52, ADEKA Inc., molecular weight is 847), 1, 2, 3, 4-ethylene-dimalonic acid four (2, 2, 6, 6-pentamethyl-4-piperidyl) ester (LA-57, ADEKA Inc., molecular weight is 791), 1, 2, 3, 4-ethylene-dimalonic acid four methyl esters 1, 2, 2, 6, 6-pentamethyl-4-piperidine alcohols β, β, β ', β '-tetramethyl-2, 4, 8, 10-tetra-oxaspiro [5, 5] hendecane-3, 9-glycol (LA-63P, ADEKA Inc., molecular weight is about 2000), 1, 2, 3, 4-ethylene-dimalonic acid four methyl esters 2, 2, 6, 6-pentamethyl-4-piperidine alcohols β, β, β ', β '-tetramethyl-2, 4, 8, 10-tetra-oxaspiro [5, 5] hendecane-3, 9-diethanol amine (LA-68, ADEKA Inc., molecular weight is about 1900), decanedioic acid two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) ester (LA-72, ADEKA Inc., molecular weight is 509), decanedioic acid two (2, 2, 6, 6-tetramethyl-4-piperidyl) ester (LA-77Y, ADEKA Inc., molecular weight is 481), decanedioic acid two (2, 2, 6, 6-tetramethyl-4-piperidyl) ester (LA-77G, ADEKA Inc., molecular weight is 481), two (the 1-hendecane oxygen base-2 of carbonic acid, 2, 6, 6-tetramethyl piperidine-4-base) ester (LA-81, ADEKA Inc., molecular weight is 681), methacrylic acid-1, 2, 2, 6, 6-pentamethyl-4-piperidyl ester (LA-82, ADEKA Inc., molecular weight is 239), methacrylic acid-2, 2, 6, 6-tetramethyl-4-piperidyl ester (LA-87, ADEKA Inc., molecular weight is 225), SONGLIGHT1190 (SONGWON Inc., molecular weight is 2286), SONGLIGHT1230 (SONGWON Inc., molecular weight is 737), decanedioic acid two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) ester (SONGLIGHT2920, SONGWON Inc., molecular weight is 509), decanedioic acid two (2, 2, 6, 6-tetramethyl-4-piperidyl) ester (SONGLIGHT7700, SONGWON Inc., molecular weight is 481), poly-(4-hydroxyl-2, 2, 6, 6-tetramethyl-1-piperidine ethanol-alt-1, 4-succinic acid) (poly (4-hydroxyl-2, 2, 6, 6-tetramethyl-1-piperidineethanol-alt-1, 4-butanedioicacid)) (Uvinul5062H, BASF AG's system, molecular weight is 3100-4000), Uvinul5050H (BASF AG's system, molecular weight is 3000-4000), N, N '-diformyl-N, N '-bis-(2, 2, 6, 6-tetramethyl-4-piperidyl)-1, 6-hexamethylene diamine (Uvinul4050H, BASF AG's system, molecular weight is 450), decanedioic acid two (2, 2, 6, 6-tetramethyl-4-piperidyl) ester (Uvinul4077H, BASF AG's system, molecular weight is 481) etc.These compounds may be used alone, can also be two or more kinds in combination.
In addition, in Encapulant composition used for solar batteries of the present invention, the matrix resin of above-mentioned Encapulant composition used for solar batteries is principal component with vinyl copolymer and the above-mentioned hindered amine compound in molecule without phenol backbone containing 0.001 ~ 0.3 weight portion for the above-mentioned matrix resin of 100 weight portions is preferred, be more preferably 0.005 ~ 0.1 weight portion, more preferably 0.01 ~ 0.05 weight portion.By coordinating with above-mentioned scope, sometimes become the function easily more suitably obtained mainly as light stabilizer.
As above-mentioned Encapulant composition used for solar batteries, preferably use optically transparent matrix resin.As above-mentioned matrix resin, such as, can enumerate TPO, polyimides, amorphous poly carbonic ester, siloxane sol-gel, polyurethane, polystyrene, polyether sulfone, polyarylate, epoxy resin, the organic siliconresin etc. such as PETG, poly-(methyl) acrylate, polyvinyl acetate, polyethylene tetrafluoroethene.These matrix resins may be used alone, can also be two or more kinds in combination.
As above-mentioned poly-(methyl) acrylate, comprise polyacrylate and polymethacrylates, such as, can enumerate (methyl) acrylate etc.As vistanex, polyethylene, polypropylene, polybutadiene etc. can be enumerated.As polyvinyl acetate, polyvinyl formal, polyvinyl butyral resin (PVB resin), modification PVB etc. can be enumerated.
As the formation monomer of above-mentioned (methyl) acrylate, such as, can enumerate (methyl) alkyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate, the benzyl methacrylate etc. such as methyl acrylate, methyl methacrylate, ethyl acrylate, EMA, butyl acrylate, butyl methacrylate, acrylic acid-2-ethyl caproite, methacrylic acid-2-Octyl Nitrite.In addition, (methyl) alkyl acrylate etc. that abovementioned alkyl is replaced by hydroxyl, epoxy radicals, halogen group etc. can be enumerated.These compounds may be used alone, can also be two or more kinds in combination.
In above-mentioned (methyl) acrylate, the carbon number of the alkyl of esteratic site is preferably 1 ~ 20, and more preferably carbon number is 1 ~ 10.
As above-mentioned (methyl) acrylate, except (methyl) acrylate, can also use and can form copolymer with the unsaturated monomer of its copolymerization.
As above-mentioned unsaturated monomer, such as, can enumerate the unsaturated organic acid such as methacrylic acid, acrylic acid, styrene, AMS, acrylamide, diacetone acrylamide, acrylonitrile, methacrylonitrile, maleic anhydride, phenyl maleimide, N-cyclohexylmaleimide etc.These unsaturated monomers may be used alone, can also be two or more kinds in combination.
For above-mentioned (methyl) acrylate, wherein preferably use (methyl) alkyl acrylate etc. that methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, acrylic acid-2-ethyl caproite, methyl methacrylate, isobutyl methacrylate, n-BMA, methacrylic acid-2-Octyl Nitrite and functional group are substituted, from the viewpoint of durability, versatility, methyl methacrylate can be enumerated as preferred example.
As the copolymer of above-mentioned (methyl) acrylate and above-mentioned unsaturated monomer, such as, can enumerate (methyl) acrylic styrene copolymer, vinyl-vinyl acetate copolymer etc.But wherein, from the viewpoint of moisture-proof, versatility, cost aspect, be preferably vinyl copolymer, wherein be more preferably vinyl-vinyl acetate copolymer, in addition, consider from durability and this point of case hardness, be preferably (methyl) acrylate.In addition, consider from above-mentioned each viewpoint, vinyl-vinyl acetate copolymer and (methyl) acrylate and with being preferred.
As above-mentioned vinyl-vinyl acetate copolymer, for the vinyl-vinyl acetate copolymer of 100 weight portions, the containing ratio of vinyl acetate monomer units is preferably 20 ~ 40 weight portions, be more preferably 25 ~ 35 weight portions, consider from uniformly dispersed viewpoints matrix resin such as terres rares complexs (raremetalcomplex), above-mentioned containing ratio is preferred.
When using above-mentioned vinyl-vinyl acetate copolymer as optically transparent matrix resin, commercially available product can be used aptly.As the commercially available product of above-mentioned vinyl-vinyl acetate copolymer, such as, can enumerate ULTRATHENE (TOSOH Co., Ltd. system), EVAFLEX (Mitsui Du Pont Polychemical's system), SUNTECEVA (AsahiKaseiChemicals Inc.), UBEEVA copolymer (Yu Buwanshan polyethylene Inc.), EVATATE (sumitomo chemical company system), NOVATECEVA (Japanese polyethylene Inc.) etc.They may be used alone, can also be two or more kinds in combination.
In above-mentioned matrix resin, can also cross-linkable monomer be added, thus make the resin with cross-linked structure.
As above-mentioned cross-linkable monomer, such as, (methyl) acrylic acid dicyclopentenyl ester can be enumerated, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) benzyl acrylate, make α, beta-unsaturated carboxylic acid and polyol reaction and compound (such as, polyethylene glycol two (methyl) acrylate (number of ethylidene is 2 ~ 14) obtained, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane ethyoxyl three (methyl) acrylate, trimethylolpropane propoxyl group three (methyl) acrylate, tetramethylol methane three (methyl) acrylate, tetramethylol methane four (methyl) acrylate, polypropylene glycol two (methyl) acrylate (number of propylidene is 2 ~ 14), dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, bisphenol A polyethenoxy two (methyl) acrylate, bisphenol-A bis oxyethylene two (methyl) acrylate, bisphenol-A three oxygen ethene two (methyl) acrylate, bisphenol-A ten oxygen ethene two (methyl) acrylate etc.), addition α in containing the compound of glycidyl, beta-unsaturated carboxylic acid and compound (such as, the trimethylolpropane tris glycidyl ether triacrylate obtained, bisphenol-A diglycidyl ether diacrylate etc.), the carboxylate that polybasic carboxylic acid (such as, phthalic anhydride) is formed with the material (such as, (methyl) senecioate-hydroxy methacrylate) with ethene unsaturated group with hydroxyl, Arrcostab (such as, (methyl) methyl acrylate of acrylic or methacrylic acid, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid-2-ethyl caproite), (methyl) propenoic methyl carbamate (urethane (meth) acrylate) (such as, the reactant of toluene di-isocyanate(TDI) and (methyl) 2-Hydroxy ethyl acrylate, trimethyl-1, hexamethylene-diisocyanate, the reactant etc. of cyclohexanedimethanol and (methyl) 2-Hydroxy ethyl acrylate) etc.These cross-linkable monomers may be used alone, can also be two or more kinds in combination.Wherein, in above-mentioned cross-linkable monomer, as preferred cross-linkable monomer, trimethylolpropane tris (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, bisphenol A polyethenoxy dimethylacrylate can be enumerated.
When using the matrix resin containing above-mentioned cross-linkable monomer, such as can add thermal polymerization or Photoepolymerizationinitiater initiater in above-mentioned cross-linking monomer, make its polymerization crosslinking by heating or illumination thus form cross-linked structure.
As above-mentioned thermal polymerization, known peroxide can be used aptly.As above-mentioned thermoplastic resin polymerization initiator, such as can enumerate 2, 5-dimethyl-2, 5-peroxidating dihydro hexane, 2, 5-dimethyl-2, own-3-the alkynes of 5-bis-(tert-butyl hydroperoxide), di-tert-butyl peroxide, cumyl peroxide, 2, 5-dimethyl-2, 5-bis-(tert-butyl hydroperoxide) hexane, cumyl peroxide, α, α '-bis-(t-butylperoxyisopropyl) benzene, normal-butyl-4, two (tert-butyl hydroperoxide) butane of 4-, 2, two (tert-butyl hydroperoxide) butane of 2-, 1, two (tert-butyl hydroperoxide) cyclohexane of 1-, 1, two (tert-butyl hydroperoxide)-3 of 1-, 3, 5-trimethyl-cyclohexane, peroxidized t-butyl perbenzoate, benzoyl peroxide etc.These compounds may be used alone, can also be two or more kinds in combination.
Such as, about the use level of above-mentioned thermal polymerization, for the above-mentioned matrix resin of 100 weight portions, 0.1 ~ 5 weight portion can be used.
As above-mentioned Photoepolymerizationinitiater initiater, the known light trigger being generated free free radical by ultraviolet or luminous ray can be used aptly.As above-mentioned Photoepolymerizationinitiater initiater, such as, benzoin methyl ether can be enumerated, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, the benzoin ethers such as benzoin phenyl ether, benzophenone, N, N '-tetramethyl-4,4 '-diaminobenzophenone (Michler's keton), N, N ' benzophenone such as-tetraethyl-4,4 '-diaminobenzophenone, benzil dimethyl ketal (CibaJapanChemicals Inc., IRGACURE651), the benzyl ketals classes such as benzyl diethyl ketal, 2,2-dimethoxy-2-phenyl acetophenone, to tert-butyl group dichloroacetophenone, to acetophenones such as dimethylamino benzoylformaldoximes, 2,4-dimethyl thioxanthone, xanthone (xanthone) classes such as 2,4-diisopropylthioxanthone, or hydroxycyclohexylphenylketone (CibaSpecialtyChemicals Inc., IRGACURE184), 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone (CibaJapanChemicals Inc., DAROCUR1116), 2-hydroxy-2-methyl-1-phenyl third-1-ketone (Merck Inc., DAROCUR1173) etc.They may be used alone, can also be two or more kinds in combination.
In addition, as above-mentioned Photoepolymerizationinitiater initiater, such as, the combination etc. of 2,4,5-triallyl imidazole dimer and 2-mercaptobenzoxazole, leuco crystal violet, three (4-diethylamino-2-aminomethyl phenyl) methane etc. can be enumerated.In addition, such as, as the tertiary amines such as benzophenone use triethanolamine, known additive can be used aptly.
Such as, about the use level of above-mentioned Photoepolymerizationinitiater initiater, for the above-mentioned matrix resin of 100 weight portions, 0.1 ~ 5 weight portion can be used.
As the refractive index of above-mentioned matrix resin, be such as the scope of 1.4 ~ 1.7, the scope of 1.45 ~ 1.65 or 1.45 ~ 1.55 scope.In some embodiments, the refractive index of polymeric matrix material is 1.5.
In addition, in Encapulant composition used for solar batteries of the present invention, preferably also containing ultraviolet absorber compounds.As above-mentioned ultraviolet absorber compounds, except suppressing the ultraviolet absorber compounds of UV degradation, the ultraviolet absorber compounds etc. can giving wavelength convert function can also be used, only otherwise damage the bridging property of above-mentioned sealing material layer used for solar batteries, UV barrier and Anti-tarnishing function.
As above-mentioned ultraviolet absorber compounds, known ultraviolet absorber compounds can be used aptly.As above-mentioned ultraviolet absorber compounds, such as, can enumerate benzophenone, benzotriazole, triazines, salicylic acid, cyanoacrylate etc.These compounds may be used alone, can also be two or more kinds in combination.
As above-mentioned benzophenone ultraviolet absorption compound, such as can enumerate 2, 2 '-dihydroxy-4, 4 '-two (hydroxymethyl) benzophenone, 2, 2 '-dihydroxy-4, 4 '-two (2-hydroxyethyl) benzophenone, 2, 2 '-dihydroxy-3, 3 '-dimethoxy-5, 5 '-two (hydroxymethyl) benzophenone, 2, 2 '-dihydroxy-3, 3 '-dimethoxy-5, 5 '-two (2-hydroxyethyl) benzophenone, 2, 2 '-dihydroxy-3, 3 '-two (hydroxymethyl)-5, 5 '-dimethoxy-benzophenone, 2, 2 '-dihydroxy-3, 3 '-two (2-hydroxyethyl)-5, 5 '-dimethoxy-benzophenone, 2, 2-dihydroxy-4, 4-dimethoxy-benzophenone etc.
As above-mentioned benzotriazole ultraviolet absorber compounds, such as can enumerate 2-(2 '-hydroxyl-5 '-(hydroxymethyl) phenyl)-2H-BTA, 2-(2 '-hydroxyl-5 '-(2-hydroxyethyl) phenyl)-2H-BTA, 2-(2 '-hydroxyl-5 '-(3-hydroxypropyl) phenyl)-2H-BTA, 2-(2 '-hydroxyl-3 '-methyl-5 '-(hydroxymethyl) phenyl)-2H-BTA, 2-(2 '-hydroxyl-3 '-methyl-5 '-(2-hydroxyethyl) phenyl)-2H-BTA, 2-(2 '-hydroxyl-3 '-methyl-5 '-(3-hydroxypropyl) phenyl)-2H-BTA, 2-(2 '-hydroxyl-3 '-the tert-butyl group-5 '-(hydroxymethyl) phenyl)-2H-BTA, 2-(2 '-hydroxyl-3 '-the tert-butyl group-5 '-(2-hydroxyethyl) phenyl)-2H-BTA, 2-(2 '-hydroxyl-3 '-the tert-butyl group-5 '-(2-hydroxyethyl) phenyl) the chloro-2H-BTA of-5-, 2-(2 '-hydroxyl-3 '-the tert-butyl group-5 '-(3-hydroxypropyl) phenyl)-2H-BTA, 2-(2 '-hydroxyl-3 '-tertiary octyl group-5 '-(hydroxymethyl) phenyl)-2H-BTA, 2-(2 '-hydroxyl-3 '-tertiary octyl group-5 '-(2-hydroxyethyl) phenyl)-2H-BTA, 2-(2 '-hydroxyl-3 '-tertiary octyl group-5 '-(3-hydroxypropyl) phenyl)-2H-BTA etc., or 2, 2 '-di-2-ethylhexylphosphine oxide (6-(2H-BTA-2-base)-4-(hydroxymethyl) phenol), 2, 2 '-di-2-ethylhexylphosphine oxide (6-(2H-BTA-2-base)-4-(2-hydroxyethyl) phenol), 2, 2 '-di-2-ethylhexylphosphine oxide (6-(the chloro-2H-BTA of 5--2-base)-4-(2-hydroxyethyl) phenol), 2, 2 '-di-2-ethylhexylphosphine oxide (6-(the bromo-2H-BTA of 5--2-base)-4-(2-hydroxyethyl) phenol), 2, 2 '-di-2-ethylhexylphosphine oxide (6-(2H-BTA-2-base)-4-(3-hydroxypropyl) phenol), 2, 2 '-di-2-ethylhexylphosphine oxide (6-(the chloro-2H-BTA of 5--2-base)-4-(3-hydroxypropyl) phenol), 2, 2 '-di-2-ethylhexylphosphine oxide (6-(the bromo-2H-BTA of 5--2-base)-4-(3-hydroxypropyl) phenol), 2, 2 '-di-2-ethylhexylphosphine oxide (6-(2H-BTA-2-base)-4-(4-hydroxybutyl) phenol), 2, 2 '-di-2-ethylhexylphosphine oxide (6-(the chloro-2H-BTA of 5--2-base)-4-(4-hydroxybutyl) phenol), 2, 2 '-di-2-ethylhexylphosphine oxide (6-(the bromo-2H-BTA of 5--2-base)-4-(4-hydroxybutyl) phenol), 3, 3-{2, 2 '-bis-(6-(2H-BTA-2-base)-1-hydroxyl-4-(2-hydroxyethyl) phenyl) } propane, 2, 2-{2, 2 '-bis-(6-(2H-BTA-2-base)-1-hydroxyl-4-(2-hydroxyethyl) phenyl) } butane, 2, 2 '-bis oxide (6-(2H-BTA-2-base)-4-(2-hydroxyethyl) phenol), 2, 2 '-bis-(6-(2H-BTA-2-base)-4-(2-hydroxyethyl) phenol) thioether, 2, 2 '-bis-(6-(2H-BTA-2-base)-4-(2-hydroxyethyl) phenol) sulfoxide, 2, 2 '-bis-(6-(2H-BTA-2-base)-4-(2-hydroxyethyl) phenol) sulfone, 2, 2 '-bis-(6-(2H-BTA-2-base)-4-(2-hydroxyethyl) phenol) amine etc.
As above-mentioned triazine-based ultraviolet absorption compound, such as can enumerate 2-(2-hydroxy-4-hydroxymethyl yhnethylphenyl)-4, 6-diphenyl-s-triazine, 2-(2-hydroxy-4-hydroxymethyl yhnethylphenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-s-triazine, 2-(2-hydroxyl-4-(2-hydroxyethyl) phenyl)-4, 6-diphenyl-s-triazine, 2-(2-hydroxyl-4-(2-hydroxyethyl) phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-s-triazine, 2-(2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl)-4, 6-diphenyl-s-triazine, 2-(2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-s-triazine, 2-(2-hydroxyl-4-(3-hydroxypropyl) phenyl)-4, 6-diphenyl-s-triazine, 2-(2-hydroxyl-4-(3-hydroxypropyl) phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-s-triazine, 2-(2-hydroxyl-4-(3-hydroxy propyloxy group) phenyl)-4, 6-diphenyl-s-triazine, 2-(2-hydroxyl-4-(3-hydroxy propyloxy group) phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-s-triazine, 2-(2-hydroxyl-4-(4-hydroxybutyl) phenyl)-4, 6-diphenyl-s-triazine, 2-(2-hydroxyl-4-(4-hydroxybutyl) phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-s-triazine, 2-(2-hydroxyl-4-(4-hydroxybutoxy) phenyl)-4, 6-diphenyl-s-triazine, 2-(2-hydroxyl-4-(4-hydroxybutoxy) phenyl)-4, 6-two (2, 4-3,5-dimethylphenyl)-s-triazine, 2-(2-hydroxy-4-hydroxymethyl yhnethylphenyl)-4, two (2-hydroxy-4-methyl the phenyl)-s-triazine of 6-, 2-(2-hydroxyl-4-(2-hydroxyethyl) phenyl)-4, two (2-hydroxy-4-methyl the phenyl)-s-triazine of 6-, 2-(2-hydroxyl-4-(2-hydroxyl-oxethyl) phenyl)-4, two (2-hydroxy-4-methyl the phenyl)-s-triazine of 6-, 2-(2-hydroxyl-4-(3-hydroxypropyl) phenyl)-4, two (2-hydroxy-4-methyl the phenyl)-s-triazine of 6-, 2-(2-hydroxyl-4-(3-hydroxy propyloxy group) phenyl)-4, two (2-hydroxy-4-methyl the phenyl)-s-triazine of 6-, 2-[4, 6-two (2, 4-3,5-dimethylphenyl)-1, 3, 5-triazine-2-base]-5-(octyloxy) phenol, 2-(4, 6-diphenyl-1, 3, 5-triazine-2-base)-5-[(hexyl) oxygen base]-phenol etc.
As above-mentioned salicylic acid ultraviolet absorber compounds, such as, can enumerate phenyl salicylate, salicylic acid to tert-butyl-phenyl ester, salicylic acid to octyl phenyl ester etc.
As above-mentioned cyanoacrylate ultraviolet absorption compound, such as, can enumerate 2-cyano group-3,3 '-diphenylacrylate-2-Octyl Nitrite, 2-cyano group-3,3 '-diphenyl-ethyl acrylate etc.
In addition, when above-mentioned ultraviolet absorber compounds uses and has the compound of wavelength convert function, as above-mentioned ultraviolet absorber compounds, such as, can enumerate the fluorescent chemicals of the light light of absorbing wavelength region 350 ~ 400nm more than the wavelength region may being greater than 400nm.As above-mentioned fluorescent chemicals, organic fluorescent compounds and inorganic fluorescent compound etc. can be enumerated.
As above-mentioned organic fluorescent compounds, known organic dyestuff compound (organic fluorescent dye etc.) can be used.As above-mentioned organic fluorescent compounds, such as, can enumerate naphthalimide, perylene, anthraquinone, cumarin, benzo cumarin, xanthene, phenoxazine, benzo [a] phenoxazine, benzo [b] phenoxazine, benzo [c] phenoxazine, naphthalimide, naphthalene lactim (naphtholactam), azlactone, methine (methine), oxazine, thiazine, diketopyrrolopyrrolecocrystals, quinacridone, benzodiphenylene oxide, sulfydryl table indoline (thioepiindoline; チ オ mono-エ ピ Application De リ Application), lactams acid imide (lactamimide), diphenylmaleimide, aceto-acetamide, imidazo thiazine, benzanthrone, perylene list acid imide, phthalimide, BTA, diazosulfide (benzothiadiazole), benzoxazole, pyrimidine, pyrazine, triazole, dibenzofurans, triazine and barbituric acid derivatives etc.These compounds may be used alone, can also be two or more kinds in combination.
As above-mentioned inorganic fluorescent compound, such as, can enumerate and there is europium, samarium as the complex etc. of luminescence center.These compounds may be used alone, can also be two or more kinds in combination.
As the absorbance of above-mentioned fluorescent chemicals, such as, be preferably 0.1 ~ 6, be more preferably 0.5 ~ 4, more preferably 0.8 ~ 3.
In addition, above-mentioned ultraviolet absorber compounds preferably has maximum absorption wavelength in the scope of 200 ~ 400nm, especially 280 ~ 380nm.By using above-mentioned ultraviolet absorber compounds, the ultraviolet that may cause the vinyl copolymer light deteriorations such as especially vinyl-vinyl acetate copolymer more effectively can be absorbed in the ultraviolet irradiating in light and comprise.It should be noted that, for the maximum absorption wavelength of above-mentioned ultraviolet absorber compounds, any means known can be adopted to use commercially available ultraviolet determinator etc. to measure.
In above-mentioned ultraviolet absorber compounds, especially from the viewpoint of preventing the deterioration of vinyl-vinyl acetate copolymer light, preferred use benzophenone ultraviolet absorption compound, particularly preferably uses the benzophenone ultraviolet absorption compound containing the hydroxyl of less than 2 in a molecule.As above-mentioned ultraviolet absorber compounds, such as, can enumerate ESCALOL 567,2,4-DihydroxyBenzophenone and UV-531 etc.Above-claimed cpd has maximum absorption wavelength in the scope of 320 ~ 350nm, can more effectively ethene suppressing-vinyl acetate copolymer light deterioration.
About the content of above-mentioned ultraviolet absorber compounds, for the above-mentioned matrix resin of 100 mass parts, preferably containing 0.001 ~ 1 weight portion, be more preferably 0.01 ~ 0.8 weight portion, more preferably 0.02 ~ 0.5 weight portion.
In above-mentioned Encapulant composition used for solar batteries, in above-mentioned matrix resin, mixing is dispersed with above-mentioned each composition (compound).In above-mentioned Encapulant composition used for solar batteries, in the scope not damaging desired performance, can be suitable for comprising known additive.As above-mentioned additive, such as, can enumerate thermoplastic polymer, antioxidant, ultraviolet (UV) resistant agent, light stabilizer, organic peroxide, filler, plasticizer, silane coupler, acid-acceptor, clay etc.They may be used alone, can also be two or more kinds in combination.
(sealing material layer used for solar batteries)
On the other hand, the feature of sealing material layer used for solar batteries of the present invention is, utilizes above-mentioned Encapulant composition used for solar batteries to be formed.
When manufacturing above-mentioned sealing material layer used for solar batteries, carry out in accordance with known methods.Such as, can be manufactured aptly by following method: utilize and add hot milling, super blender (flow at high speed mixer), edge runner, plastics processing mill (PLASTOMILL) etc., known method is adopted to be mixed and made into composition to above-mentioned Encapulant composition used for solar batteries (or its each material), by common extrusion molding, calendering formation (calendering), vacuum hotpressing etc., said composition is shaping, obtain tablet.In addition, can by after form above-mentioned layer in PET film etc., the method that is transferred to sealer manufactures.In addition, the method for simultaneously being carried out mixing melting and coating by hot melt application machine can be adopted.
More specifically; such as; Encapulant composition above-mentioned used for solar batteries containing above-mentioned matrix resin, dibutyl hydroxy toluene derivative and above-mentioned hindered amine compound etc. directly can be coated with and be formed at sealer or barrier film etc., carry out coating after also above-mentioned material and other materials can being made blend compositions and formed.
When being coated with the form of above-mentioned Encapulant composition used for solar batteries, based on the consideration of processability, the fusing point of above-mentioned matrix resin is preferably 50 ~ 120 DEG C, is more preferably 50 ~ 100 DEG C, more preferably 50 ~ 80 DEG C.In addition, such as, when the fusing point of above-mentioned Encapulant composition used for solar batteries is 50 ~ 120 DEG C, for the mixing melting of above-mentioned composition and coating temperature, add that the temperature of 30 ~ 100 DEG C carries out being preferred with above-mentioned fusing point.
In addition, in some embodiments, by following operation, sealing material layer used for solar batteries is fabricated to thin-film structure: operation (i), by polymer (matrix resin) powder with the ratio solvent of regulation in solvent (such as, tetrachloro-ethylene (TCE), cyclopentanone, dioxane etc.) in, prepare polymer solution; Operation (ii), mixes polymer solution with luminescent dye with the weight ratio of regulation, obtains the polymer solution containing dyestuff, thus the luminescent dye (fluorescent chemicals) of preparation containing polymeric blends; Operation (iii), polymer solution containing dyestuff is directly poured on glass substrate, then substrate is carried out to the heat treatment (from room temperature to maximum temperature 100 DEG C) of 2 hours, by carrying out the heating in vacuum at a night in 130 DEG C and remove residual solvent completely further, form dyestuff/thin polymer film thus; And operation (iv), before use, in water, dyestuff/thin polymer film is peeled off, then by self-supporting (free-standing) polymer film bone dry; V (), can the thickness of controlling diaphragm by changing the concentration of dyestuff/polymer solution and evaporation rate.
The thickness of above-mentioned sealing material layer used for solar batteries is preferably 20 ~ 2000 μm, is more preferably 50 ~ 1000 μm, more preferably 100 ~ 800 μm.If thinner than 20 μm, be then difficult to present encapsulant function.On the other hand, if thicker than 2000 μm, then the thickness of solar cell module becomes large, is also disadvantageous in cost.
Above-mentioned sealing material layer used for solar batteries is generally used for the sealing to solar battery cell, but as required, also can laminated in inner connecting material (interconnectormaterial), electrode etc. with by its Suitable closure.Only otherwise damage the above-mentioned functions of above-mentioned sealing material layer used for solar batteries, then as required, also can wait between the layers aptly and be situated between at other layers.
(solar cell module)
The feature of solar cell module 1 of the present invention is to comprise sealer 10, above-mentioned sealing material layer 20 used for solar batteries and solar battery cell 30.As an example, easy schematic diagram shown in Fig. 1,2, but the present invention is not limited thereto.In addition, in the rear side of solar battery cell, also sealing material layer 40, backboard 50 can be possessed further aptly.In addition, between above-mentioned each layer, only otherwise damage the above-mentioned functions of above-mentioned sealing material layer used for solar batteries, then also can be situated between aptly at other layers such as layer of adhesive material, adhesive phase.In addition, as the sealing material layer at the above-mentioned back side, sealing material layer used for solar batteries of the present invention can be used aptly.
As above-mentioned solar battery cell, such as, cadmium sulfide/cadmium telluride solar cell, Copper indium gallium selenide solar cell, non-crystal silicon solar cell, microcrystalline silicon solar cell or crystal silicon solar energy battery can be used.As above-mentioned solar battery cell, be preferably crystal silicon solar energy battery.
In the manufacture of above-mentioned solar cell module, above-mentioned sealing material layer used for solar batteries can be transferred to above-mentioned solar battery cell etc., also can directly coating formation on above-mentioned solar battery cell.In addition, also can form above-mentioned sealing material layer used for solar batteries and other layers simultaneously.
embodiment
Below, to illustrating that the embodiment etc. of formation of the present invention and effect is described particularly.
(compound in table)
In embodiment comparative example, employ following compound.
Matrix resin: SUMITATEKA-30, ethylene vinyl acetate resin (sumitomo chemical company system)
Two (4-isobutyl group oxygen base the phenyl)-2-isobutyl group-2H-BTA of organic compound A:4,7-
Peroxide: peroxidating-2-ethylhexyl list t-butyl carbonate (You Inc., PerbutylE)
Crosslinking coagent: cyanacrylate (Japan changes into Inc., TAIC)
BHT: dibutyl hydroxy toluene (Tokyo changes into Inc.)
Two (1,1-the dimethyl ethyl)-4-hydroxy phenyl of Tinuvin144:[[3,5-] methyl] two (1,2,2,6, the 6-pentamethyl-4-piperidyl) ester (BASF AG's system, molecular weight is 685) of butylmalonic acid
Tinuvin770DF: two (2,2,6, the 6-tetramethyl-4-piperidyl) ester (BASF AG's system, molecular weight is 481) of decanedioic acid
KBM503:3-methacryloxypropyl trimethoxy silane (Shin-EtsuSiliconeCo., Ltd. system)
(making of resin sheet)
In embodiment comparative example, each compound is coordinated according to table 1, manufacture each sealing material layer (seal stock and back side seal stock) by following method.
In each embodiment comparative example, take the EVA resin (SUMITATEKA-30) of 100 weight portions and each compound, be dry mixed rear use single axle extruding machine and carry out melting mixing, obtain the pill of ethylene copolymer composition.Use pressure forming machine, make sealing material layer resin sheet (thickness: about 400 μm) from above-mentioned pill.
(mensuration of gel fraction)
The two sides of the sealing material layer resin sheet obtained (thickness: 400 μm) attaches PET system mold release film thus obtained sample, by this specimen holder in glass and backboard, 80 DEG C, pressurize under the condition of 100kN, preserve 20 minutes in drying oven under the condition of 150 DEG C.Then, W is cut
1g is also accurately weighed, impregnated in (110 DEG C, 24 hours) in 100cc dimethylbenzene.Then, the weight W of (80 DEG C, 6 hours) after accurately weighed filtration residue drying
2g, will with (W
2/ W
1the value that the mode of) × 100 calculates is as gel fraction (% by weight).Metewand is as described below.
Mean value (measuring number the is 2) value of gel fraction is the situation of more than 80%: zero
The situation that the mean value of gel fraction (measuring number is 2) value is less than 80%: ×
(initial xanthochromia evaluation)
80 DEG C, under the condition of 100kN, the sealing material layer resin sheet obtained (thickness: 400 μm) is fitted with the state be clipped in glass and backboard, preserves 20 minutes in drying oven under the condition of 150 DEG C.Then, use UV irradiator (Panasonic electrician Heat & Control Pty Ltd. system, UJ35) and lens (Panasonic electrician Heat & Control Pty Ltd. system, ANUJ6426), irradiate 1W/cm with official hour (180 minutes)
2uV light (365nm).Utilize MCPD (great mound electronics corporation system) measure the reflectance spectrum that the sample of front and back is penetrated in UV illumination.According to the reflectance spectrum information obtained, calculate yellow colour index (YI:YellowIndex, ASTMD1925), implement xanthochromia evaluation.Metewand is as described below.
The situation that the mean value of the measured value that end is 4 is less than 7.5: zero
The mean value of the measured value that end is 4 is more than 7.5 and is less than the situation of 10: △
The mean value of the measured value that end is 4 is the situation of more than 10: ×
(photo-stability testing)
80 DEG C, under the condition of 100kN, the sealing material layer resin sheet obtained (thickness: 400 μm) is fitted with the state be clipped in glass and PET mold release film, preserves 20 minutes in drying oven under the condition of 150 DEG C.Then, mold release film is peeled off, uses UV irradiator (Panasonic electrician Heat & Control Pty Ltd. system, UJ35) and lens (Panasonic electrician Heat & Control Pty Ltd. system, ANUJ6426), 1W/cm is irradiated from sheet material both sides with official hour (120 minutes)
2uV light (365nm).Utilize spectrophotometer (Japanese light splitting Inc., V560) measure illumination penetrate before and after the absorption spectrum of sample.According to the spectral information obtained, organic absorbance change is evaluated.Metewand is as described below.
Absorbance after Ultraviolet radiation is changed to more than-0.8 situation: zero
Absorbance after Ultraviolet radiation to be changed to more than-0.9 and to be less than the situation of-0.8: △
The situation that absorbance change after Ultraviolet radiation is less than-0.9: ×
The each measurement result during sealing material layer resin sheet obtained is used to be shown in following table 1.
From the result measured, in a comparative example, when only to the addition of in dibutyl hydroxy toluene or Tinuvin144 either party situation and containing dibutyl hydroxy toluene and Tinuvin144 in either party, the xanthochromia that easy generation is caused by Ultraviolet radiation, organic photostability is also low.And on the other hand, in the embodiment of the present application, due to and used dibutyl hydroxy toluene or Tinuvin144, so be less likely to occur xanthochromia most, photostability also uprises.Compared with adding separately the situation of each composition, above-mentioned action effect is not limited in Overlay, can also obtain synergy.
Description of reference numerals
1 solar cell module
10 sealers
20 sealing material layers used for solar batteries
30 solar battery cells
40 back side sealing material layers
50 backboards
Claims (11)
1. Encapulant composition used for solar batteries, is characterized in that, containing dibutyl hydroxy toluene (BHT) derivative and the hindered amine compound in molecule with phenol backbone.
2. Encapulant composition used for solar batteries as claimed in claim 1, described hindered amine compound has dibutyl hydroxy toluene skeleton.
3. Encapulant composition used for solar batteries as claimed in claim 1 or 2, the molecular weight of described hindered amine compound is 400 ~ 4000.
4. the Encapulant composition used for solar batteries according to any one of claims 1 to 3, described hindered amine compound has 2,2,6,6-tetramethyl-4-piperidinyl structure.
5. the Encapulant composition used for solar batteries according to any one of Claims 1 to 4, is characterized in that, also containing the hindered amine compound in molecule without phenol backbone.
6. the Encapulant composition used for solar batteries according to any one of Claims 1 to 5, the matrix resin of described Encapulant composition used for solar batteries take vinyl copolymer as principal component, further, the described dibutyl hydroxy toluene derivative containing 0.001 ~ 0.2 weight portion for the described matrix resin of 100 weight portions and the described hindered amine compound of 0.001 ~ 0.3 weight portion.
7. the Encapulant composition used for solar batteries according to any one of claim 1 ~ 6, also containing ultraviolet absorber compounds.
8. the Encapulant composition used for solar batteries according to any one of claim 1 ~ 7, described matrix resin take vinyl-vinyl acetate copolymer as principal component.
9. sealing material layer used for solar batteries, it utilizes the Encapulant composition used for solar batteries according to any one of claim 1 ~ 8 to be formed.
10. solar cell module, it comprises the sealing material layer used for solar batteries utilizing the Encapulant composition used for solar batteries according to any one of claim 1 ~ 8 to be formed.
11. solar cell modules as claimed in claim 10, wherein, described solar battery cell is crystal silicon solar energy battery.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013129391A JP6173789B2 (en) | 2013-06-20 | 2013-06-20 | Solar cell encapsulant composition, solar cell encapsulant layer, and solar cell module using the same |
| JP2013-129391 | 2013-06-20 | ||
| PCT/JP2014/064944 WO2014203740A1 (en) | 2013-06-20 | 2014-06-05 | Sealing material composition for solar cells, sealing material layer for solar cells, and solar cell module using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105324853A true CN105324853A (en) | 2016-02-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480035152.3A Pending CN105324853A (en) | 2013-06-20 | 2014-06-05 | Sealing material composition for solar cells, sealing material layer for solar cells, and solar cell module using same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6173789B2 (en) |
| KR (1) | KR20160021805A (en) |
| CN (1) | CN105324853A (en) |
| WO (1) | WO2014203740A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116535965A (en) * | 2022-12-29 | 2023-08-04 | 苏州弘道新材料有限公司 | Barrier buffer layer coating liquid for solar cell backboard |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5447576A (en) * | 1992-08-03 | 1995-09-05 | Siemens Solar Industries International, Inc. | Composition and method for encapsulating a solar cell which minimizes thermal discoloration |
| JP2003243682A (en) | 2002-02-19 | 2003-08-29 | Sumitomo Bakelite Co Ltd | Solar cell |
| JP2008069210A (en) * | 2006-09-12 | 2008-03-27 | Shin Etsu Chem Co Ltd | Polycyclic hydrocarbon group-containing silicone-based curable composition |
| JP2009191182A (en) * | 2008-02-15 | 2009-08-27 | Denki Kagaku Kogyo Kk | Chloroprene-based polymer composition, adhesive composition and method for producing the chloroprene-based polymer composition |
| JP5361693B2 (en) * | 2009-12-11 | 2013-12-04 | 株式会社Ａｄｅｋａ | Sealing film for solar cell |
| JP5567896B2 (en) * | 2010-05-10 | 2014-08-06 | 株式会社ブリヂストン | Solar cell sealing film and solar cell using the same |
| JP2013077705A (en) * | 2011-09-30 | 2013-04-25 | Hitachi Chemical Co Ltd | Wavelength conversion solar cell module and method of manufacturing the same |
| CN102559080B (en) * | 2012-02-16 | 2014-03-12 | 太阳能光伏北京市工程研究中心有限公司 | Ethylene-vinylacetate adhesive film |
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2013
- 2013-06-20 JP JP2013129391A patent/JP6173789B2/en active Active
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2014
- 2014-06-05 KR KR1020167000064A patent/KR20160021805A/en not_active Application Discontinuation
- 2014-06-05 CN CN201480035152.3A patent/CN105324853A/en active Pending
- 2014-06-05 WO PCT/JP2014/064944 patent/WO2014203740A1/en active Application Filing
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116535965A (en) * | 2022-12-29 | 2023-08-04 | 苏州弘道新材料有限公司 | Barrier buffer layer coating liquid for solar cell backboard |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015005594A (en) | 2015-01-08 |
| WO2014203740A1 (en) | 2014-12-24 |
| JP6173789B2 (en) | 2017-08-02 |
| KR20160021805A (en) | 2016-02-26 |
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Application publication date: 20160210 |