CN101065849A - Easily adhesive polyester film for solar cell back surface-protecting film and solar cell back surface-protecting film obtained using the same - Google Patents

Easily adhesive polyester film for solar cell back surface-protecting film and solar cell back surface-protecting film obtained using the same Download PDF

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Publication number
CN101065849A
CN101065849A CNA2005800404288A CN200580040428A CN101065849A CN 101065849 A CN101065849 A CN 101065849A CN A2005800404288 A CNA2005800404288 A CN A2005800404288A CN 200580040428 A CN200580040428 A CN 200580040428A CN 101065849 A CN101065849 A CN 101065849A
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polyester film
film
highly adhesive
solar cell
resin
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久保耕司
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Toyobo Film Solutions Ltd
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Teijin DuPont Films Japan Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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Abstract

Disclosed is a highly adhesive polyester film which is used for protecting the back side of a solar cell and composed of a polyester film and a resin coating arranged on one side of the polyester film. This highly adhesive polyester film is characterized in that the resin coating is made of a crosslinking agent and a resin selected from polyester resins having a glass transition point of 20-100 DEG C, acrylic resins having a glass transition point of 20-100 DEG C, combinations of those resins, and combinations of at least one of those resins and a polyvinyl alcohol having a saponification degree of 70-90 mol%. This highly adhesive polyester film is excellent in adhesion to EVA while achieving excellent mechanical properties, heat resistance and moisture resistance.

Description

Highly adhesive polyester film and use its back protection film of solar cell
Technical field
The present invention relates to highly adhesive film and back protection film of solar cell.More specifically; relate to and form the highly adhesive contain particular composition by one side at least and film at polyester film, show with as the excellent bonding highly adhesive polyester film of the vinyl-vinyl acetate copolymer (being designated hereinafter simply as EVA) of solar cell sealing resin and use its back protection film of solar cell.
Background technology
In recent years, photovoltaic power generation system is constantly popularized as one of generating means of utilizing pollution-free energy.The structure of solar cell module such as Japan real open in the flat 6-38264 communique record; generally speaking form following structure: between the diaphragm of the glass substrate of sensitive side and rear side; accompany a plurality of plate-shaped solar cell devices, in the gap of inside, be filled with the structure of sealing resin.As sealing resin,, use EVA owing to reasons such as transparency height, excellent moisture resistance.
The diaphragm use polyvinyl resin at the back side or mylar sheet, fluorine resin film (with reference to Japanese kokai publication hei 11-261085 communique and Japanese kokai publication hei 11-186575 communique).Yet such diaphragm and the adhesiveness of EVA may not be abundant, and be worrying aspect long-term persistence.
On the other hand, the polyester film that the polyester sheet stretching is got has excellent engineering properties, thermal endurance, moisture-proof.Yet for polyester film, particularly through polyester film biaxial stretch-formed, height-oriented crystallization, its surface is an inertia, with the adhesiveness extreme difference of EVA.In order to improve the adhesiveness of this polyester film and EVA, in TOHKEMY 2003-60218 communique, proposed to contain the scheme of the thermal adhesive layer lamination of styrene-olefin copolymer resin.Yet its effect is abundant inadequately, when constructing the large-sized solar batteries electricity generation system, is out of use particularly.
Summary of the invention
The purpose of this aspect is to solve described technical problem in the past, provides to have excellent engineering properties, thermal endurance, moisture-proof, simultaneously, the highly adhesive polyester film of using with the back protection film of solar cell of the adhesiveness of EVA, adaptation excellence.
Other purposes of the present invention are to provide the back protection film of solar cell that contains above-mentioned highly adhesive polyester film of the present invention.
Further other purposes of the present invention and advantage are illustrated according to the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 1st reaches by following highly adhesive polyester film, it is characterized in that, contains polyester film and the resin coating on this polyester film one side,
This resin coating contains following resin and crosslinking agent; described resin is selected from that one of any and saponification degree are the combination of the polyvinyl alcohol of 79～90 moles of % in combination that vitrifying point is 20～100 ℃ mylar, acrylic resin that vitrifying point is 20～100 ℃, these resins and these resins; and, can be used in the protection rear surface of solar cell.
In addition, according to the present invention, above-mentioned purpose of the present invention and advantage, the 2nd is to reach by the back protection film of solar cell that contains above-mentioned highly adhesive polyester film of the present invention.
Embodiment
Below, explain the present invention.
[polyester film]
As the polyester that constitutes highly adhesive polyester film of the present invention, for example, can enumerate by as terephthalic acid (TPA), M-phthalic acid, 2,6-naphthalenedicarboxylic acid, 4, the aromatic dicarboxylic acid composition of 4 '-diphenyl dioctyl phthalate with as ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1, the aromatic polyester that the aliphatic dihydroxy alcohol composition of 6-hexylene glycol constitutes.These polyester can be copolyesters.Wherein, preferred PETG, poly-2,6-(ethylene naphthalate), preferred especially especially polyethylene glycol-2,6-naphthalate.
For polyester, the coiling of film, the film delivery in the used for solar batteries back protection film manufacturing procedure etc. can make its particulate that contains organic or inorganic as lubricant as required when making film in order to improve.As described particulate, for example can enumerate calcium carbonate, calcium oxide, aluminium oxide, kaolin, silica, zinc oxide, crosslinked acrylic resin particle, crosslinked styrene resin beads, urea resin particle, melmac particle, crosslinked organic siliconresin particle.
Described atomic average grain diameter for example can be 0.05～10 μ m, with respect to polyester, preferably makes it contain for example 0.005～1 weight %.
From as the raising of the surface reflectivity of solar energy back protection film and the viewpoint of design, can be coloured to white or black or other colors, and, can also contain ultra-violet absorber described later.
[resin coating]
In the present invention, the resin coating on the polyester film contains resin and crosslinking agent.As crosslinking agent, for example can use the polymer, epoxy resin, urea resin, the melmac that contain  azoles quinoline base.These materials can use separately or more than 2 kinds together.
As the above-mentioned polymer that contains  azoles quinoline base, can enumerate the polymer in Japanese Patent Publication 63-48884 communique, Japanese kokai publication hei 2-60941 communique or Japanese kokai publication hei 2-99537 communique, put down in writing or their similar polymer.Particularly, can enumerate with the addition polymerization  azoles quinoline (a) of following formula (III) expression and make itself and other monomer (b) polymerization as required and must polymer.
Figure A20058004042800061
At this, R 1, R 2, R 3And R 4Represent hydrogen atom, halogen atom, alkyl, aralkyl, phenyl or substituted-phenyl separately, R 5Expression has the non-annularity organic group of addition polymerization unsaturated bond group.
As the object lesson of the addition polymerization  azoles quinoline of representing with above-mentioned formula (a), can enumerate 2-vinyl-2- azoles quinoline, 2-vinyl-4-methyl-2- azoles quinoline, 2-vinyl-5-methyl-2- azoles quinoline, 2-isopropenyl-2- azoles quinoline, 2-isopropenyl-4-methyl-2- azoles quinoline, 2-isopropenyl-5-methyl-2- azoles quinoline etc.These materials can use a kind or use as the mixture more than 2 kinds.Wherein, 2-isopropenyl-2- azoles quinoline is in industrial easy acquisition and preferred.
As above-mentioned other monomers (b) beyond the addition polymerization  azoles quinoline, so long as can just have no particular limits with the monomer of addition polymerization  azoles quinoline (a) copolymerization, for example, can enumerate acrylate such as methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate; Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid; Unsaturated nitrile such as acrylonitrile, methacrylonitrile; Unsaturated amides such as acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide; Vinyl esters such as vinyl acetate, propionate; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether; Alpha-olefin such as ethene, propylene; Halogen-containing α such as vinyl chloride, vinylidene chloride, fluorinated ethylene, β-unsaturated monomer; α such as styrene, AMS, β-unsaturated aromatic monomer etc.These materials can use a kind or use as the mixture more than 2 kinds.
The polymer of above-mentioned addition polymerization  azoles quinoline (a) and as required at least a above other monomers (b), can by with the polymerization of always knowing with their polymerizations and or.As described polymerization, for example, can adopt the whole bag of tricks such as emulsion polymerization (method of carrying out polymerization after polymerization catalyst, water, surfactant and monomer be mixed together), monomer dropping method, multi-stage polymeric method, pre-emulsion process.
As polymerization catalyst, can use the material of always knowing.For example, can enumerate hydrogen peroxide, potassium peroxydisulfate, 2, common radical polymerization initiators such as two (2-aminopropane) 2 hydrochlorides of 2 '-azo.
In addition, as surfactant, can enumerate anion system, nonionic system, cation system and amphoteric surfactant and the reactive surfactant known always.
Polymerization temperature is 0～100 ℃ for example, is preferably 50～80 ℃.Polymerization time for example is 1～10 hour.
Use addition polymerization  azoles quinoline (a) and at least a above other monomers (b) when obtaining polymer, the use amount of addition polymerization  azoles quinoline (a) is preferably more than the 0.5 weight % with respect to whole monomers.The use amount of addition polymerization  azoles quinoline (a) can be difficult to reach purpose of the present invention during less than 0.5 weight %.
As epoxy resin, particularly, can enumerate polyepoxides, di-epoxy compounds, mono-epoxy compounds etc. as above-mentioned crosslinking agent.As this polyepoxides, for example, can enumerate sorbitol polyglycidylether, polyglycereol polyglycidyl ether, pentaerythrite polyglycidyl ether, two glycerine polyglycidyl ethers, three-glycidyl three (2-hydroxyethyl) isocyanates, glycerine polyglycidyl ether, trimethylolpropane polyglycidylether, N, N, N, N '-four glycidyl group m-xylene diamine, N, N, N ', N '-four glycidyl ether-4,4 '-diaminodiphenyl-methane, N, N, N ', N '-four glycidyl ether-1, the two amino methyl cyclohexanes of 3-etc.As di-epoxy compounds, for example can enumerate neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinolformaldehyde resin, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether etc.In addition, as mono-epoxy compounds, for example can enumerate allyl glycidyl ether, 2-ethylhexyl glycidol ether, phenyl glycidyl ether etc.Wherein, preferred N, N, N ', N '-four glycidyl group m-xylene diamine, N, N, N ', N '-four glycidyl ether-4,4 '-diaminodiphenyl-methane, N, N, N ', N '-four glycidyl ether-1, the two amino methyl cyclohexanes of 3-.
As urea resin, for example can preferably enumerate dimethylol urea, dihydroxymethyl ethylene urea, dihydroxymethyl propylene urea, tetra methylol acetylene urea, 4-methoxyl group-5-dimethyl allene urea dihydroxymethyl etc. as above-mentioned crosslinking agent.
As the melmac of above-mentioned crosslinking agent, for example, can preferably enumerate to make melamine and formaldehyde condensation are obtained
The melamine methylol derivative with as reaction such as the methyl alcohol of lower alcohol, ethanol, isopropyl alcohol and compound that etherificate obtains and their mixture.
As the melamine methylol derivative, for example, can enumerate monomethylol melamine, dihydroxymethyl melamine, trimethylol melamine, tetra methylol melamine, pentamethylol melamine, hexamethylolmelamine etc.
In these crosslinking agents, preferably contain the polymer of  azoles quinoline base, because it shows excellent especially highly adhesive.Crosslinking agent can use separately that also two or more kinds may be used.
As the resin that forms resin coating with these crosslinking agents, can use vitrifying point be in the combination of 20～100 ℃ mylar, acrylic resin that vitrifying point is 20～100 ℃, these resins and these resins arbitrary resin or with saponification degree be the combination of the polyvinyl alcohol of 70～90 moles of %.
The vitrifying point of mylar or acrylic resin preferably all is 30～90 ℃.If vitrifying point is less than 20 ℃, then the adhesion between the film takes place sometimes, thereby not preferred; If surpass 100 ℃, then coating layer becomes fragile, and can not keep adaptation, thereby not preferred.
As vitrifying point is 20～100 ℃ mylar, can use to form derivative and polyalcohol or its ester by following such polyacid or its ester and form the formed polyester of derivative.That is to say, as the polyacid composition, can enumerate terephthalic acid (TPA), M-phthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexyl dicarboxylic acid, adipic acid, decanedioic acid, trimellitic acid, pyromellitic acid, dimeric dibasic acid, 5-5-sodium sulfo isophthalate etc.Can use these sour synthetic copolymer polyester resins that become to assign to more than 2 kinds.In addition, can use certain tittle, for example can use the maleic acid of 10 moles of unsaturated polyacid compositions of the conduct below the %, the hydroxycarboxylic acid of itaconic acid etc. and P-hydroxybenzoic acid etc. and so on respect to above-mentioned polyacid composition.In addition, as polyol component, can enumerate ethylene glycol, 1,4-butanediol, diethylene glycol, DPG, 1,6-hexylene glycol, 1,4-cyclohexanedimethanol, Xylene glycol, dihydroxy methylpropane, poly-(oxirane) glycol, poly-(four methylene oxygen ether) glycol etc.In addition, can enumerate their monomer.
In addition, be 20～100 ℃ acrylic resin as vitrifying point, can enumerate with as the polymerizable acrylic monomer of following example and the acrylic resin that obtains.As this acrylic monomers, can enumerate alkyl acrylate, alkyl methacrylate (, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, 2-ethylhexyl, cyclohexyl etc. being arranged) as alkyl; Acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxy propyl ester etc. contain the monomer of hydroxyl; Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether etc. contain the monomer of epoxy radicals; Acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid and salt thereof (sodium salt, sylvite, ammonium salt, tertiary ammonium salt etc.) etc. contain the monomer of carboxyl or its salt; Acrylamide, Methacrylamide, the N-alkyl acrylamide, N-alkyl methyl acrylamide, N, N-dialkyl group acrylamide, N, N-dialkyl methyl acrylate is (as alkyl, methyl is arranged, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, the 2-ethylhexyl, cyclohexyl etc.), N-alkoxy propone acid amides, the N-alkoxy methyl acrylamide, N, N-dialkoxy acrylamide, N, N-dialkoxy Methacrylamide (as alkoxyl, has methoxyl group, ethyoxyl, butoxy, isobutoxy etc.), the acryloxy morpholine, N hydroxymethyl acrylamide, the N-methylol methacrylamide, N phenyl acrylamide, N-phenyl methyl acrylamide etc. contains the monomer of amide groups; The monomer of acid anhydrides such as maleic anhydride, itaconic anhydride; Monomers such as isocyanic acid vinyl acetate, allyl isocyanate, styrene, AMS, vinyl methyl ether, EVE, vinyl trialkyl oxysilane, alkyl maleic acid monoesters, alkyl fumaric monoalkylester, alkyl itaconic acid monoesters, acrylonitrile, methacrylonitrile, vinylidene chloride, ethene, propylene, vinyl chloride, vinyl acetate, butadiene.
Wherein, the monomer that contains hydroxyl, for example acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxy propyl ester, N hydroxymethyl acrylamide, N-methylol methacrylamide etc., preferably contain 2～20 moles of %, more preferably contain 4～15 moles of %.
The saponification degree of polyvinyl alcohol is 70～90 moles of %.If surpass 90 moles of %, then can not fully obtain the adhesiveness with EVA, not preferred; If be less than 70 moles of %, then moisture-proof meeting variation is not preferred.
Resin coating preferably contains the resin of 20～95 weight % and the crosslinking agent of 5～80 weight %, more preferably contains the resin of 40～90 weight %.
In resin coating, for the operability that improves film, prevent the adhesion between the film, can add the particulate of inertia.As described particulate, can use the particulate of organic or inorganic, as its example, can enumerate calcium carbonate, calcium oxide, aluminium oxide, kaolin, silica, zinc oxide, crosslinked acrylic resin particle, crosslinked styrene resin beads, melmac particle, crosslinked organic siliconresin particle.
Described atomic average grain diameter is preferably 20～200nm, more preferably 30～120nm.With respect to resin coating, its use level is preferably 1～20 weight %, more preferably 2～15 weight %.
In order to obtain more excellent easy to be sliding property, in resin coating, can further add wax.Concrete example as this wax, can enumerate plant class waxes such as Brazil wax, candelila wax, rice wax, haze tallow, Jojoba wax, palm wax, Abietyl modified wax, ouricury wax, sugarcane wax, esparto wax, bark wax, animal class waxes such as beeswax, lanolin, spermaceti, Chinese wax, shellac wax, mineral substance waxes such as montan wax, paraffin, ceresine, petroleum-type waxes such as solid paraffin, microwax, petrolatum wax, Synthin waxes such as Fischer-Tropsch wax, Tissuemat E, OPE, polypropylene wax, its chlorinated polypropylene wax etc.Wherein, since good to the highly adhesive and the lubrification of hard conating and adhesive, preferred Brazil wax, solid paraffin, Tissuemat E.From reducing the easiness of carrying capacity of environment and processing, preferably wax is made aqueous dispersion and use.
Composition as forming resin coating can also cooperate for example antistatic agent, colouring agent, surfactant, ultra-violet absorber.
[manufacturing of highly adhesive polyester film]
Highly adhesive polyester film of the present invention is to smear to have used the resin coating of mentioned component to make on the one side at least of polyester film.The smearing to be preferably as follows of resin coating carried out: on the polyester film before crystalline orientation finishes, that can stretch, coating contains after the waterborne liquid of the composition that forms tunicle, carries out drying, stretching, heat treatment.The solid formation branch concentration of this waterborne liquid is preferably below the 30 weight %, more preferably below the 10 weight %.
With respect to the solid branch 100 weight % that form, masking liquid contains the crosslinking agent of preferred 10～80 weight % and the crosslinking agent resinous principle in addition of preferred 20～90 weight %.If the resinous principle beyond the crosslinking agent is less than 20 weight %, then be difficult to form tunicle, the result is bonding insufficient, not preferred with EVA sometimes.If surpass 90 weight %, then because the use level of crosslinking agent (A) is not enough, so the cohesiveness of coating layer reduces, particularly the bonding persistence under high humidity reduces, and is not preferred.
The above-mentioned polyester film that can stretch is polyester film, the polyester film of uniaxial tension or the biaxial stretch-formed polyester film that does not stretch.Wherein, extrude the vertical oriented polyester film of direction (longitudinal direction) particularly preferably in film through uniaxial tension.
When being applied to the water-based masking liquid on the film, as the preliminary treatment that is used to improve coating, preferably implement physical treatments such as Corona Surface Treatment, flame treatment, plasma treatment, perhaps with composition and use and be chemically inert surfactant with it at film surface.
Described surfactant is for promoting the water-based masking liquid material wetting to polyester film, for example, can enumerate anionic, nonionic surface active agent such as polyethylene glycol oxide alkyl phenyl ether, polyethylene glycol oxide-fatty acid ester, sorbitan aliphatic ester, fatty acid glyceride, fatty acid metal soap, alkyl sulfate, alkylsulfonate, alkyl-thio-succinate.In the composition that formation is filmed, preferably contain the surfactant of 1～10 weight %.So long as this scope just can be located at below the 40mN/m, can prevent the shrinkage cavity of coating layer.
When waterborne liquid is applied to polyester film,, promptly when carrying out in the operation of the polyester film that gets through biaxial stretch-formed fixing being carried out the manufacturing process of this film and severing, then be easy to be involved in rubbish, dust etc., so not preferred if at common coating process.From then on viewpoint is set out, and preferably is coated with in the atmosphere gas of cleaning, promptly is coated with in the thin film fabrication operation.So,, be further enhanced as the adaptation of the resin coating of filming to polyester film by this coating.
As coating process, any rubbing method that can application of known.For example, can be used alone or in combination rolling method, version is coated with method, roller brush method, spraying process, air knife and is coated with method, impregnation method and curtain coating method etc.With respect to the film 1m that moves 2, coating weight is preferably 0.5～20g, more preferably 1～10g.Waterborne liquid preferably makes dispersion liquid or emulsion uses, and only smears and carries out in the one side of film.
As required, the polyester film that can stretch that has been coated with waterborne liquid is directed in drying process, the stretch processing operation.Described processing can carried out under the condition of accumulation all the time in the art.As preferred condition, drying condition is 90～130 ℃ * 2～10 seconds, and draft temperature is 90～150 ℃, stretching ratio is 3～5 times of longitudinal directions, 3～5 times of transverse directions, if desired, stretches 1～3 times at longitudinal direction again, during heat fixation, it is 180～250 ℃ * 2～60 seconds.
The thickness of the Biaxially oriented polyester film after the described processing is preferably 50～250 μ m, and coating thickness is preferably 0.01～1 μ m.
In order to improve the weatherability of film, above-mentioned polyester film can contain ultra-violet absorber.As described ultra-violet absorber, preferably use at least a kind of compound that is selected from the cyclic imide base ester shown in cyclic imide base ester shown in the following formula (I) and the following formula (II) with unreacted form.
Figure A20058004042800121
(at this, X 1Be to come from the X shown in the above-mentioned formula 12 connecting keys be positioned at 1, the divalent aromatic residue of 2 bit positions relations; N is 1,2 or 3; R 1Be the hydrocarbon residue of n valency, it can further contain hetero-atom, perhaps R during n=2 1It can be Direct Bonding.)
(at this, A is the group shown in the group shown in following formula (II)-a or following formula (the II)-b; R 2And R 3Identical or different, be the hydrocarbon residue of 1 valency; X 2Be the aromatic residue of 4 valencys, it can further contain hetero-atom.
Described cyclic imide base ester is as the known compound of ultra-violet absorber, for example is recorded in the Japanese kokai publication sho 59-12952 communique.
In above-mentioned formula (I), X 1Be to come from the X shown in the formula (I) 12 connecting keys be positioned at 1, the divalent aromatic residue of 2 bit positions relations; N is 1,2 or 3; R 1Be the hydrocarbon residue of n valency, it can further contain hetero-atom, perhaps R during n=2 1It can be Direct Bonding.
As X 1, preferred example can enumerate 1,2-phenylene, 1,2-naphthylene, 2,3-naphthylene, the group of representing respectively with following formula (a) and (b).
Figure A20058004042800131
(in the formula, R is-O-,-CO-,-S-,-SO 2-,-CH 2-,-(CH 2)-or-C (CH 3) 2-.)
Wherein, preferred especially 1, the 2-phenylene.
For X 1Illustrated above-mentioned aromatic residue, can replace with following substituting group: for example carbon number is 1～10 alkyl, for example methyl, ethyl, propyl group, hexyl, decyl etc.; Carbon number is 6～12 aryl, for example phenyl, naphthyl etc.; Carbon number is 5～12 cycloalkyl, for example cyclopenta, cyclohexyl etc.; Carbon number is 8～20 aralkyl, for example phenylethyl etc.; Carbon number is 1～10 alkoxyl, for example methoxyl group, ethyoxyl, the last of the ten Heavenly stems oxygen base etc.; Nitro; Halogen, for example chlorine, bromine etc.; Carbon number is 2～10 acyl group, for example acetyl group, propiono, ゼ Application ゾ イ Le, capryl etc.; Deng substituting group.
R 1Be the hydrocarbon residue of n valency (n is 1,2 or 3), R when perhaps needing only n=2 1It can be Direct Bonding.
As the hydrocarbon residue (during n=1) of 1 valency, the first, can enumerate carbon number for example and be 1～10 unsubstituted aliphatic group, carbon number and be 6～12 not substituted aromatic group, carbon number and be 5～12 not replacement alicyclic group.
As carbon number is 1～10 unsubstituted aliphatic group, can enumerate for example methyl, ethyl, propyl group, hexyl, decyl etc.; As carbon number is 6～12 not substituted aromatic group, can enumerate for example phenyl, naphthyl, xenyl etc.; As carbon number is 5～12 not replacement alicyclic group, can enumerate for example cyclopenta, cyclohexyl etc.
In addition, hydrocarbon residue as above-mentioned 1 valency, the second, substituted aliphatic residue or the aromatic residue that can enumerate group with following formula (c) expression, the group of representing with the group of following formula (d) expression, with following formula (e), represent with following formula (f).
Figure A20058004042800141
(in the formula, R 4Be that carbon number is 2～10 alkylidene, phenylene or naphthylene.)
Figure A20058004042800142
(in the formula, R 5Be that carbon number is 1～10 alkyl, phenyl or naphthyl.)
Figure A20058004042800143
(in the formula, R 4And R 5Definition same as described above, R 6Be hydrogen atom or R 5Define in the group any one.)
Figure A20058004042800144
(in the formula, R 4And R 6Definition same as described above, R 7Be hydrogen atom or R 5Define in the group any one.)
In addition, as the hydrocarbon residue of above-mentioned 1 valency, the 3rd, can enumerate the group that above-mentioned unsubstituted aromatic residue replaces with substituting group, this substituting group for for example with as above-mentioned expression X 1The illustrated identical substituting group of substituting group of aromatic residue.Therefore, the example when replacing with described substituting group for example can be enumerated tolyl, methyl naphthyl, nitrobenzophenone, nitro naphthyl, chlorphenyl, benzoyl phenyl, acetylphenyl or acetyl group naphthyl etc.
As the hydrocarbon residue of 1 valency, preferably use above-mentioned formula (c), (d), (e) or (f) group of expression, i.e. substituted aliphatic residue or aromatic residue, particularly wherein substituted aromatic residue.
As the hydrocarbon residue (during n=2) of divalent, first can enumerate divalent, carbon number is that 2～10 do not replace aliphatic residue, carbon number are that 6～12 not substituted aromatic residue, carbon number are 5～12 the alicyclic residue of not replacement.
As the carbon number of divalent is 2～10 not replacement aliphatic residue, can enumerate for example ethylidene, trimethylene, tetramethylene, decamethylene etc.; As the carbon number of divalent is 6～12 not substituted aromatic residue, can enumerate for example phenylene, naphthylene, p, p '-biphenylene etc.; As the carbon number of divalent is 5～12 the alicyclic residue of not replacement, can enumerate for example cyclopentylene, cyclohexylidene etc.
In addition, as the hydrocarbon residue of above-mentioned divalent, second can enumerate with the group of following formula (g) expression or substituted aliphatic residue or the aromatic residue of representing with following formula (h).
(in the formula, R 8Be R 4Define in the group any one.)
(in the formula, R 8Definition same as described above, R 9Be R 4Any one of defined group, R 10Be R 6Define in the group any one.)
In addition, as the hydrocarbon residue of above-mentioned divalent, the 3rd can enumerate above-mentioned unsubstituted divalent aromatic residue, for example uses and the above-mentioned X of expression 1The material that replaces of the illustrated identical substituting group of the substituting group of aromatic group.
N is 2 o'clock, as R 1Wherein, preferred Direct Bonding or above-mentioned first～the 3rd not replacement or substituted divalent aromatic hydrocarbon residue, preferred especially 2 connecting keys come from the first or the 3rd not replacement or substituted aromatic hydrocarbon residue of highest distance position, wherein, preferably to phenylene, p, p '-biphenylene or 2,6-naphthylene.
As the hydrocarbon residue (during n=3) of 3 valencys, for example, the carbon number that can enumerate 3 valencys is 6～12 aromatic residue.
As described aromatic residue, for example, can enumerate following group etc.
Figure A20058004042800161
Described aromatic residue can be used with the illustrated identical substituting group of above-mentioned substituting group as 1 valency aromatic residue and replace.
In above-mentioned formula (II), R 2And R 3Identical or different, be the hydrocarbon residue of 1 valency, X 2It is the aromatic hydrocarbon residue of 4 valencys.
As R 2And R 3, can enumerate in the explanation of above-mentioned formula (I) R during with n=1 1Illustrated identical group is an example.
As the aromatic hydrocarbon residue of 4 valencys, for example, can enumerate with the represented group of following structural formula.
Figure A20058004042800171
(at this, the definition of R is identical with formula (a).)
The aromatic hydrocarbon residue of above-mentioned 4 valencys, in the explanation of above-mentioned formula (I), can be with representing R with conduct 1The illustrated identical substituting group of the substituting group of 1 valency aromatic residue replace.
The employed in the present invention above-mentioned formula (I) and (II) object lesson of represented cyclic imide base ester for example can be enumerated following compound.
The compound of above-mentioned formula (I)
Compound during n=1
2-methyl-3; 1-benzoxazine-4-ketone; 2-butyl-3; 1-benzoxazine-4-ketone; 2-phenyl-3; 1-benzoxazine-4-ketone; 2-(1-or 2-naphthyl)-3; 1-benzoxazine-4-ketone; 2-(4-xenyl)-3; 1-benzoxazine-4-ketone; 2-p-nitrophenyl-3; 1-benzoxazine-4-ketone; 2-m-nitro base-3; 1-benzoxazine-4-ketone; 2-is to benzoyl phenyl-3; 1-benzoxazine-4-ketone; 2-p-methoxyphenyl-3; 1-benzoxazine-4-ketone; 2-o-methoxyphenyl-3; 1-benzoxazine-4-ketone; 2-cyclohexyl-3; 1-benzoxazine-4-ketone; 2-is to (or) phthalimide phenyl-3; 1-benzoxazine-4-ketone; N-phenyl-4-(3,1-benzoxazine-4-ketone-2-yl) phthalimide; N-benzoyl-4-(3,1-benzoxazine-4-ketone-2-yl) aniline; N-benzoyl-N-methyl-4-(3; 1-benzoxazine-4-ketone-2-yl) aniline; 2-(right-(N-methyl carbonyl) phenyl-3,1-benzoxazine-4-ketone.
Compound during n=2
2; 2 '-two (3; 1-benzoxazine-4-ketone); 2; 2 '-ethylenebis (3; 1-benzoxazine-4-ketone); 2; 2 '-tetramethylene two (3; 1-benzoxazine-4-ketone); 2; 2 '-decamethylene two (3; 1-benzoxazine-4-ketone); 2,2 '-TOPOT 2,2 (3,1-benzoxazine-4-ketone); 2; 2 '-metaphenylene two (3; 1-benzoxazine-4-ketone); 2,2 '-(4,4 '-diphenylene) two (3; 1-benzoxazine-4-ketone); 2; 2 '-(2,6-or 1,5-naphthylene) two (3; 1-benzoxazine-4-ketone); 2; 2 '-(the 2-methyl-to phenylene) two (3,1-benzoxazine-4-ketone); 2,2 '-(the 2-nitro-to phenylene) two (3; 1-benzoxazine-4-ketone); 2; 2 '-(the 2-chloro-is to phenylene) two (3,1-benzoxazine-4-ketone); 2,2 '-(1; the 4-cyclohexylidene) two (3; 1-benzoxazine-4-ketone); N-is right-(3,1-benzoxazine-4-ketone-2-yl) phenyl; 4-(3,1-benzoxazine-4-ketone-2-yl) phthalimide; N-right-(3; 1-benzoxazine-4-ketone-2-yl) benzoyl; 4-(3,1-benzoxazine-4-ketone-2-yl) aniline.
Compound during n=3
1,3,5-three (3,1-benzoxazine-4-ketone-2-yl) benzene, 1,3,5-three (3,1-benzoxazine-4-ketone-2-yl) naphthalene, 2,4,6-three (3,1-benzoxazine-4-ketone-2-yl) naphthalene.
The compound of above-mentioned formula (II)
2,8-dimethyl-4H, the 6H-benzo (1,2-d; 5,4-d ') two (1,3)- piperazines-4,6-diketone, 2,7-dimethyl-4H, the 9H-benzo (1,2-d; 4,5-d ') two (1,3)- piperazines-4,9-diketone, 2,8-diphenyl-4H, the 8H-benzo (1,2-d; 5,4-d ') two (1,3)- piperazines-4,6-diketone, 2,7-diphenyl-4H, the 9H-benzo (1,2-d; 4; 5-d ') two (1; 3)- piperazine-4; the 6-diketone; 6; 6 '-two (2-methyl-4H; 3,1-benzoxazine-4-ketone); 6,6 '-two (2-ethyl-4H; 3; 1-benzoxazine-4-ketone); 6,6 '-two (2-phenyl-4H, 3; 1-benzoxazine-4-ketone); 6; 6 '-di-2-ethylhexylphosphine oxide (2-methyl-4H, 3,1-benzoxazine-4-ketone); 6; 6 '-di-2-ethylhexylphosphine oxide (2-phenyl-4H; 3,1-benzoxazine-4-ketone); 6,6 '-ethylenebis (2-methyl-4H; 3; 1-benzoxazine-4-ketone); 6,6 '-ethylenebis (2-phenyl-4H, 3; 1-benzoxazine-4-ketone); 6; 6 '-butylidene two (2-methyl-4H, 3,1-benzoxazine-4-ketone); 6; two (2-phenyl-the 4H of 6 '-butylidene; 3,1-benzoxazine-4-ketone); 6, the two (2-methyl-4H of 6 '-oxo; 3; 1-benzoxazine-4-ketone); 6,6 '-bis oxide (2-phenyl-4H, 3; 1-benzoxazine-4-ketone); 6; 6 '-sulfonyl two (2-methyl-4H, 3,1-benzoxazine-4-ketone); 6; two (2-phenyl-the 4H of 6 '-sulfonyl; 3,1-benzoxazine-4-ketone); 6, the two (2-methyl-4H of 6 '-carbonyl; 3; 1-benzoxazine-4-ketone); 6,6 '-carbonyl two (2-phenyl-4H, 3; 1-benzoxazine-4-ketone); 7; 7 '-di-2-ethylhexylphosphine oxide (2-methyl-4H, 3,1-benzoxazine-4-ketone); 7; 7 '-di-2-ethylhexylphosphine oxide (2-phenyl-4H; 3,1-benzoxazine-4-ketone); 7,7 '-two (2-methyl-4H; 3; 1-benzoxazine-4-ketone); 7,7 '-ethylenebis (2-methyl-4H, 3; 1-benzoxazine-4-ketone); 7; 7 '-bis oxide (2-methyl-4H, 3,1-benzoxazine-4-ketone); 7; two (2-methyl-the 4H of 7 '-sulfonyl; 3,1-benzoxazine-4-ketone); 7, the two (2-methyl-4H of 7 '-carbonyl; 3; 1-benzoxazine-4-ketone); 6,7 '-two (2-methyl-4H, 3; 1-benzoxazine-4-ketone); 6; 7 '-two (2-phenyl-4H, 3,1-benzoxazines-4-ketone); 6; 7 '-di-2-ethylhexylphosphine oxide (2-methyl-4H; 3,1-benzoxazine-4-ketone); 6,7 '-di-2-ethylhexylphosphine oxide (2-phenyl-4H; 3,1-benzoxazine-4-ketone).
In above-mentioned illustrative compound, preferably use the compound of above-mentioned formula (I), the compound of above-mentioned (I) when more preferably using n=2, the compound shown in the preferred especially following formula (I)-1.
Figure A20058004042800191
In the formula, R 11It is the aromatic residue of divalent.
As the compound of formula (I)-1, wherein preferred 2,2 '-TOPOT 2,2 (3,1-benzoxazine-4-ketone), 2,2 '-(4,4 '-diphenylene) two (3,1-benzoxazine-4-ketone) and 2,2 '-(2, the 6-naphthylene) two (3,1-benzoxazine-4-ketone).
The ultraviolet radiation absorption characteristic of these cyclic imide base esters has for example been put down in writing the correlation circumstance of its representation compound, so it has been quoted in Japanese kokai publication sho 59-12952 communique.
Above-mentioned cyclic imide base ester has excellent intersolubility for polyester, such as institute's record in above-mentioned Japanese kokai publication sho 59-12952 communique or No. 4291152 specification of United States Patent (USP), has the ability that the terminal hydroxyl with polyester reacts.What therefore, require to note nearly cyclic imide base ester and polyester mixes the feasible cyclic imide base ester that contains basically under unreacted state.Yet, as polyester, when the end group that uses main ratio does not have the polyester of reactive end-capping reagent end-blocking for using with this cyclic imide base ester as the polyester of carbonyl or terminal hydroxyl, need not to pay special attention to for being manufactured on the composition that contains cyclic imide base ester under the unreacted state.The main ratio of using end group is during as the polyester of hydroxyl, and the time of melting mixing preferably finishes at short notice, makes to satisfy following formula.
Logt≤-0.008T+4.8 and Tm＜T＜320
(in the formula, t is melting mixing time (second), T be melt mix temperature (℃), Tm be polyester melt temperature (℃).)
In this case, cyclic imide base ester and polyester might be with the reactions of seldom ratio, but since the molecular weight by this reaction polyester increase, so the molecular weight due to the polyester deterioration that can prevent to cause because of visible light absorber according to this ratio reduces.Need to prove that when cyclic imide base ester and pet reaction, therefore the general trend of moving to low wavelength lateral deviation from the ultraviolet radiation absorption wavelength region may of unreacted state that shows of ultraviolet radiation absorption wave-length coverage have the ultraviolet trend that sees through high wavelength side.
When described cyclic imide base ester adds when an amount of, almost there is not sublimate, therefore in the system film, seldom pollute a mouthful mould periphery, because that near light absorbing from the ultraviolet ray to 380nm thereby film do not have is painted, excellence aspect the characteristic that prevents luminous ray absorbent or film deterioration.
With respect to 100 weight % polyester, the addition of above-mentioned ultra-violet absorber is preferably 0.1～5 weight %, further preferred 0.2～3 weight %.If less than 0.1 weight %, prevent that then the effect of UV degradation is little; If surpass 5 weight %, then the system membrane property of polyester reduces, and is not preferred.
As the method for above-mentioned ultra-violet absorber being added in the polyester, for example, can adopt to be blended in the polymer in the fusion operation before polyester operation or film system film, to contain the method that is dipped in the biaxially oriented film.Viewpoint from preventing that the polyester degree from reducing preferably is blended into the method in the polymer in the fusion operation before film system film.This is sneaked into and can be undertaken by direct addition method, the masterbatch method of for example compound powder.
[back protection film]
The highly adhesive polyester film that back protection film of solar cell of the present invention is used can separately or be fitted more than 2, uses as back protection film of solar cell.
The highly adhesive polyester film of using for back protection film of solar cell of the present invention is in order to give the steam shielding, film or paper tinsel that preferred lamination has the steam shielding.Be provided with the highly adhesive polyester film that the back protection film of solar cell of steam screen is used, preferably the moisture-vapor transmission that records according to JIS Z0208-73 is 5g/ (m 224h).
As described film, can enumerate Vingon film, Vingon coating film, Kynoar coating film, evaporated film of silicon oxide, aluminium oxide evaporated film, aluminium-vapour deposition film with steam shielding.As paper tinsel, can the illustration aluminium foil, Copper Foil.
These films or paper tinsel can use with following form: be laminated to the offside of the EVA adhesive surface of the highly adhesive polyester film that back protection film of solar cell of the present invention uses, the structure of the highly adhesive polyester film double team of perhaps the EVA adhesive side is placed the outside, using with 2 back protection film of solar cell of the present invention.According to the present invention, provide solar cell module equally with back protection film of solar cell of the present invention.
Embodiment
Below, further specify the present invention by embodiment.Need to prove that each characteristic value is measured by following method.
(1) vitrifying point (Tg)
Use the Thermal Analyst 2000 type differential calorimeters of DUPONT system, measure with 20 ℃/minute programming rate.
(2) intrinsic viscosity
Measure the solution viscosity of obtaining the o-chlorphenol solvent down at 35 ℃.
(3) with the adhesiveness of EVA
Prepare respectively 2 with film be cut into 20mm wide * the long and film that obtains of 100mm, 1 with EVA sheet (SOLAR EVA (R) SC4 of HI-SHEET industry (strain) system) be cut into 20mm wide * the long and sheet that obtains of 50mm.Order with film/EVA sheet/film is overlapping, pressurizes with heat-sealing instrument (TESTER industry (strain) system TP-701-B), makes the EVA sheet be positioned at the substantial middle of film, and the face of wanting to estimate the easy viscosity of film is the EVA side.The pressing condition is as follows: pressing was warmed up to 150 ℃ after 5 minutes under 120 ℃, 0.02MPa, and moulding pressure was risen to the 0.1MPa pressing 25 minutes.With hot pressing and sample under 23 ℃, the condition of 50%RH atmosphere gas, according to JIS-Z0237, clamp the not film of bonding part with clip up and down, be that 180 °, draw speed are to measure bonding force under the 100mm/ condition of dividing at peel angle.
◎: more than the 20N/20mm ... adhesiveness is very good
Zero: 10N/20mm is above and less than 20N/20mm ... adhesiveness is good
△: 5N/20mm is above and less than 10N/20mm ... adhesiveness is good slightly
*: less than 5N/20mm ... adhesiveness is bad
(4) with the bonding persistence of EVA
According to JIS-C8917-1998, after the hot pressing sample treatment that under 85 ℃, 85%RH, will make 1000 hours, similarly estimate bonding force with above-mentioned (3) by above-mentioned (3), with handle before bonding force relatively, estimate.
◎: the adhesiveness conservation rate is more than 75% ... bonding persistence is very good
Zero: the adhesiveness conservation rate is more than 50% and less than 75% ... bonding persistence is good
△: the adhesiveness conservation rate is more than 25% and less than 50% ... adhesiveness is good slightly
*: the adhesiveness conservation rate is less than 25% ... adhesiveness is bad
(5) weatherability
Use Exposure to Sunlight weather color fastness instrument (SUGA testing machine (strain) system, WEL-SUN-HCL type),, 1000 hours (being equivalent to outdoor exposure 1 year) of sample irradiation that will make by above-mentioned (3), promote to test thereby carry out outdoor exposure according to JIS-K-6783b.Similarly estimate adhesiveness with above-mentioned (3), compare, estimate with promoting the adhesiveness before the test.
◎: the adhesiveness conservation rate is more than 75% ... weatherability is very good
Zero: the adhesiveness conservation rate is more than 50% and less than 75% ... weatherability is good
△: the adhesiveness conservation rate is more than 25% and less than 50% ... weatherability is good slightly
*: the adhesiveness conservation rate is less than 25% ... weatherability is bad
Embodiment 1～7 and comparative example 1
With PETG (intrinsic viscosity: 0.62) melt extrude, make non-stretched film to maintaining on 20 ℃ the rotation chilling roll.Then, be stretched to after 3.3 times in 100 ℃ at longitudinal direction, the concentration that is coated with following coating composition (table 1) equably with roll coater on its two sides is the water-based masking liquid of 8 weight %.Then, this coated thin film is continued to stretch, under 95 ℃, carry out drying, be stretched to 3.6 times in 110 ℃, under 220 ℃, make it shrink 3%, carry out heat fixation, obtain the polyester film that thickness is 50 μ m at Width at transverse direction.Need to prove that the thickness of filming is 0.05 μ m.These evaluation results are shown in Table 2.
Table 1
Figure A20058004042800221
Crosslinking agent A-1: with the polymer with  azoles quinoline base (Tg=50 ℃) that 30 moles of % of methyl methacrylate/2-isopropenyl-30 moles of % of 10 moles of %/acrylamides of 2- azoles 30 moles of %/poly(ethylene oxide) of quinoline (n=10) methacrylate constitute.
Crosslinking agent A-2: epoxy resin; N, N, N ', N '-four glycidyl group m-xylene diamine.
Crosslinking agent A-3: melmac; The trimethoxy methyl melamine (with methyl alcohol with the trimethylol melamine etherificate and material).
Crosslinking agent A-4: dihydroxymethyl ethylene urea.
Other resinous principle B-1: by sour composition is 2,30 moles of % of 65 moles of %/M-phthalic acids of 6-naphthalenedicarboxylic acid/5 moles of % of 5-5-sodium sulfo isophthalate, glycol component is the copolyester (Tg=80 ℃) that 10 moles of % of 90 moles of %/diethylene glycols of ethylene glycol constitute.
Other resinous principle B-2: by sour composition is 15 moles of % of 80 moles of %/M-phthalic acids of terephthalic acid (TPA)/5 moles of % of 5-5-sodium sulfo isophthalate, and glycol component is the copolyester (Tg=43 ℃) that 40 moles of % of 60 moles of %/diethylene glycols of ethylene glycol constitute.
Other resinous principle B-3: with the acrylic resin (Tg=27 ℃) of 2 moles of % formations of 3 moles of %/2-hydroxyethyl methacrylates of 40 moles of %/N-n-methylolacrylamide of 55 moles of %/ethyl acrylates of methyl methacrylate.
Filler: silica filler (average grain diameter is 60nm)
Additive: Brazil wax
Wetting agent: polyethylene glycol oxide (n=7) lauryl ether
Table 2
Adhesiveness with EVA Bonding persistence with EVA Weatherability Overall merit
Embodiment 1 ◎ ◎ ○ ◎
Embodiment 2 ◎ ◎ ○ ◎
Embodiment 3 ◎ ○ ○ ◎
Embodiment 4 ○ ○ △ ○
Embodiment 5 ○ ◎ ○ ◎
Embodiment 6 ○ ○ △ ○
Embodiment 7 ○ ○ △ ○
Comparative example 1 △ × - ×
Embodiment 8 ◎ ◎ ◎ ◎
Comparative example 2 × - - ×
Embodiment 9 ◎ ◎ ◎ ◎
(in the table ,-mark is represented not judge.)
Embodiment 8
PETG (the intrinsic viscosity: 0.62) melt extrude, make non-stretched film that will contain the ultra-violet absorber that the following formula of 1 weight % represents to maintaining on 20 ℃ the rotation chilling roll.
Figure A20058004042800241
Below, operation obtains film similarly to Example 3.The evaluation result of this polyester film is shown in Table 2.
Comparative example 2
Except not being coated with the waterborne liquid, operation obtains polyester film similarly to Example 1.The characteristic of gained polyester film is shown in Table 2.
Embodiment 9
To gather 2,6-(ethylene naphthalate) (intrinsic viscosity: 0.58) melt extrude, make non-stretched film to maintaining on 60 ℃ the rotation chilling roll.Then, be stretched to after 3.3 times in 140 ℃, be coated on employed water-based masking liquid among the embodiment 3 equably with roll coater in its one side at longitudinal direction.Then, this coated thin film is continued to stretch, under 130 ℃, carry out drying, be stretched to 3.6 times in 150 ℃, under 240 ℃, on Width, make it shrink 3%, carry out heat fixation, obtain the polyester film that thickness is 50 μ m at transverse direction.Need to prove that the thickness of filming is 0.05 μ m.These evaluation results are shown in Table 2.
Embodiment 10～13 and comparative example 3
To contain the porous SiO that the 120ppm particle diameter is 1.7 μ m 2PETG (intrinsic viscosity: 0.62) melt extrude, make non-stretched film to maintaining on 20 ℃ the rotation chilling roll.Then, be stretched to after 3.2 times in 100 ℃ at longitudinal direction, the concentration that is coated with following coating composition (table 3) equably with roll coater on its two sides is 8% water-based masking liquid.
Table 3
Figure A20058004042800251
Polyvinyl alcohol A-1: saponification degree is the polyvinyl alcohol of 86～89mol%.
Polyvinyl alcohol A-2: saponification degree is the polyvinyl alcohol of 74～78mol%.
Particulate B-1: average grain diameter is the spherical silicon dioxide particle of 100nm.
Particulate B-2: average grain diameter is the crosslink propylene acid particles of 100nm.
Crosslinking agent C-1: the compound shown in the following formula.
Figure A20058004042800252
N, N, N, N '-four glycidyl group m-xylene diamine.
Compound C-2: the compound shown in the following formula
Figure A20058004042800253
N, N, N, N '-four glycidyl group-1, the two amino methyl cyclohexanes of 3-.
Adhesive D-1: by sour composition is 2,30 moles of % of 65 moles of %/M-phthalic acids of 6-naphthalenedicarboxylic acid/5 moles of % of M-phthalic acid 5-sodium sulfonate, and glycol component is the copolyester (Tg=80 ℃) that 10 moles of % of 90 moles of %/diethylene glycols of ethylene glycol constitute.
Adhesive D-2: by sour composition is 15 moles of % of 80 moles of %/M-phthalic acids of terephthalic acid (TPA)/5 moles of % of 5-5-sodium sulfo isophthalate, and glycol component is the copolyester (Tg=43 ℃) that 40 moles of % of 60 moles of %/diethylene glycols of ethylene glycol constitute.
Wetting agent: polyethylene glycol oxide (n=7) lauryl ether
Then, this coated thin film is continued to stretch, under 95 ℃, carry out drying, be stretched to 3.4 times in 110 ℃, under 225 ℃, make it shrink 3%, carry out heat fixation, obtain the polyester film that thickness is 50 μ m at Width at transverse direction.Need to prove that the thickness of filming is 0.08 μ m.These evaluation results are shown in Table 4.
Embodiment 14
To contain the porous SiO that the 80ppm particle diameter is 1.7 μ m 2With the PETG of the ultra-violet absorber shown in the following formula of 1 weight % (intrinsic viscosity: 0.62) melt extrude, make non-stretched film to maintaining on 20 ℃ the rotation chilling roll.
Figure A20058004042800261
Below, operation obtains film similarly to Example 10, and the evaluation result of this polyester film is shown in Table 4.
Comparative example 4
Except not being coated with the waterborne liquid, operation obtains film similarly to Example 10.The characteristic of gained polyester film is shown in Table 4.
Embodiment 15
To gather 2,6-(ethylene naphthalate) (intrinsic viscosity: 0.58) melt extrude, make non-stretched film to maintaining on 60 ℃ the rotation chilling roll.Then, be stretched to after 3.2 times in 140 ℃, be coated on employed water-based masking liquid among the embodiment 10 equably with roll coater in its one side at longitudinal direction.
Then, this coated thin film is continued to stretch, under 130 ℃, carry out drying, be stretched to 3.4 times in 150 ℃, under 240 ℃, make it shrink 3%, carry out heat fixation, obtain the polyester film that thickness is 50 μ m at Width at transverse direction.Need to prove that the thickness of filming is 0.05 μ m.
These evaluation results are shown in Table 4.
Table 4
Adhesiveness with EVA Bonding persistence with EVA Weatherability Overall merit
Embodiment 10 ◎ ◎ ○ ◎
Embodiment 11 ◎ ○ ○ ◎
Embodiment 12 ○ ◎ ○ ◎
Embodiment 13 ○ ○ △ ○
Comparative example 3 △ × - ×
Embodiment 14 ◎ ◎ ◎ ◎
Comparative example 4 × - - ×
Embodiment 15 ◎ ◎ ◎ ◎
(in the table ,-mark is represented not judge.)
By the result shown in table 2 and 4 as can be known, the adhesiveness excellence of Biaxially oriented polyester film of the present invention and EVA can be used as the polyester film that back protection film of solar cell is used.

Claims (11)

1. a highly adhesive polyester film is characterized in that, contains polyester film and the resin coating on this polyester film one side,
This resin coating contains following resin and crosslinking agent; described resin is selected from that one of any and saponification degree are the combination of the polyvinyl alcohol of 70～90 moles of % in combination that vitrifying point is 20～100 ℃ mylar, acrylic resin that vitrifying point is 20～100 ℃, these resins and these resins; and, can be used in the protection rear surface of solar cell.
2. highly adhesive polyester film as claimed in claim 1, wherein, crosslinking agent is to be selected from least a in polymer, urea resin, melmac and the epoxy resin that contains  azoles quinoline base.
3. highly adhesive polyester film as claimed in claim 1, wherein, this resin coating contains the resin of 20～95 weight % and the crosslinking agent of 5～80 weight %.
4. highly adhesive polyester film as claimed in claim 1, wherein, this resin coating contains the particulate that average grain diameter is 20～200nm with the ratio of 1～20 weight %.
5. highly adhesive polyester film as claimed in claim 1, wherein, polyester film is 2,6-naphthalenedicarboxylic acid ester film.
6. highly adhesive polyester film as claimed in claim 1, wherein, polyester film contains the ultra-violet absorber of 0.1～5 weight %.
7. highly adhesive polyester film as claimed in claim 1, wherein, ultra-violet absorber is at least a kind of compound selecting from the cyclic imide base ester shown in cyclic imide base ester shown in the following formula (I) and the following formula (II);
Figure A2005800404280002C1
At this, X 1Be to come from X shown in the following formula 12 connecting keys be positioned at 1, the divalent aromatic residue of 2 bit positions relations; N is 1,2 or 3; R 1Be the hydrocarbon residue of n valency, it can further contain hetero-atom, perhaps R during n=2 1It can be Direct Bonding;
At this, A is the group shown in the group shown in following formula (II)-a or following formula (the II)-b; R 2And R 3Identical or different, be the hydrocarbon residue of 1 valency; X 2Be the aromatic residue of 4 valencys, it can also contain hetero-atom.
Figure A2005800404280003C2
8. highly adhesive polyester film as claimed in claim 1, this polyester film is biaxial stretch-formed polyester film, resin coating smear following carrying out: before the crystalline orientation of polyester film finishes, on polyester film, be coated with masking liquid, carry out drying, stretching, heat treatment.
9. back protection film of solar cell, it contains each described highly adhesive polyester film in the claim 1～7.
10. each described highly adhesive polyester film in the claim 1～7 is used for the application of rear surface of solar cell protection.
11. a solar cell module, it has the described back protection film of solar cell of claim 9.
CNA2005800404288A 2004-11-25 2005-11-24 Easily adhesive polyester film for solar cell back surface-protecting film and solar cell back surface-protecting film obtained using the same Pending CN101065849A (en)

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