CN104812810A - Fluorinated resin film, method for producing same, and solar cell module - Google Patents
Fluorinated resin film, method for producing same, and solar cell module Download PDFInfo
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- CN104812810A CN104812810A CN201380059896.4A CN201380059896A CN104812810A CN 104812810 A CN104812810 A CN 104812810A CN 201380059896 A CN201380059896 A CN 201380059896A CN 104812810 A CN104812810 A CN 104812810A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
Disclosed is a fluorinated resin film which is formed by carrying out the extrusion molding of a fluorinated resin containing a polyvinylidene fluoride resin as the main component and then cooling the resultant molded product at a cooling temperature that is set at a temperature falling within the range from 85 to 120 DEG C, and which has an endothermic peak (an inherent peak) inherent in the polyvinylidene fluoride resin which falls within the range from 150 to 190 DEG C and at least one endothermic peak on the lower temperature side relative to the inherent peak in a DSC curve (first run) produced by a heat-flux differential scanning calorimetry method in which the heating is carried out from room temperature to 200 DEG C at a temperature-rising rate of 10 DEG C/min.
Description
Technical field
The present invention relates to a kind of novel fluorine resin film and its manufacture method, and the rear surface of solar cell screening glass using this fluorine resin film and formed, and possess the solar module of this rear surface of solar cell screening glass.
Background technology
Fluorine resin film, because of the feature such as weathering resistance, thermotolerance, stain resistance, chemical proofing, solvent resistance of its excellence, is widely used in the field requiring long durability.The film being particularly principal constituent with vinylidene fluoride resin plays the cost advantage obtained by filming effectively; as various surface protecting material, be widely used in interior exterior component of buildings etc. all the time, require the vessel surface material of chemical-resistant resistance, organic solvent resistance, the table backing material, fuel cell member etc. of solar cell.And then, in recent years, along with solar module demand significantly increases, start to be widely used as rear surface of solar cell screening glass (patent documentation 1 ~ 2).
The requirement of the long durability for the purposes as such rear surface of solar cell screening glass is become more and more stricter, requires the use under severe cruel condition, its long lifetime.Therefore, the applicant, by controlling the crystal habit of vinylidene fluoride resin for specific crystal habit, develops thermotolerance, the manufacturing technology (patent documentation 3) of the vinylidene resin film of xanthochromia when particularly inhibit heating.Namely, after forming film by extrusion moulding, temperature more than 100 DEG C reheats, the ratio that the II N-type waferN obtained by the absorbancy utilizing infrared absorption spectrum to obtain thus in controlling diaphragm becomes to divide is 90 ~ 100%, wherein with the summation of I type crystal structure (β brilliant) and II type crystal structure (α crystalline substance) for 100, thus obtain the little fluorine resin film of xanthochromia degree.But, along with the long lifetime of goods, the fluorine resin film of long durability of iting is desirable to be further improved.
Patent documentation 1: Japanese Unexamined Patent Publication 2011-129672 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2008-28294 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2006-273980 publication
Summary of the invention
The present invention implements in view of the foregoing, and object is to provide the fluorine resin film further improving long durability, particularly yellowing resistance compared with existing film.
In addition, the present invention also aims to provide a kind of manufacture above-mentioned fluorine resin film method, use the rear surface of solar cell screening glass of above-mentioned fluorine resin film and possess the solar module of this rear surface of solar cell screening glass.
In patent documentation 3, control in the mode making the ratio of the α crystalline substance obtained by the absorption intensity utilizing infrared absorption spectrum to obtain in film raise, but for the ratio of the α crystalline substance of being tried to achieve by the method, if its numerical value known is increased to a certain degree, then sometimes fully do not reflect the difference of crystalline structure.So, the further index to the crystalline structure of resin such as the present inventor is studied, found that, the absorption intensity obtained by utilizing infrared absorption spectrum cannot judge that the crystalline structure difference of significant difference is carried out DSC Curve Resolution by heat flux dsc and identified clearly.And, the present inventor conducts in-depth research to obtain the brilliant ratio of the α fluorine resin film higher than currently available products to use the method, result is also surprised to find that, if the cooling temperature in extrusion moulding to be set as the scope of 85 ~ 120 DEG C, then the fluorine resin film of can be further improved long durability, particularly yellowing resistance.
Namely, according to a mode of the present invention, a kind of fluorine resin film is provided, it is characterized in that, it is that the fluorine resin composition being principal constituent containing polyvinylidene difluoride (PVDF) system resin is extruded shaping, be set as 85 ~ 120 DEG C scope cooling temperature under cooled and to be formed, and by heat flux dsc, the DSC curve (first run) of the first round heating obtained when room temperature is heated to 200 DEG C with the heat-up rate of 10 DEG C/min, there is the endotherm(ic)peak (intrinsic peak) that the polyvinylidene difluoride (PVDF) system resin of the scope being in 150 ~ 190 DEG C is intrinsic, and be in more than 1 endotherm(ic)peak of low temperature side at this intrinsic peak.
In aforesaid way, as long as the crystallization of the cooling conditions after the method for extrusion moulding is resin extruded on resin produces the forming method of significant impact, be not limited to specific method, but the method that the present inventor etc. inquire into especially is in detail T mold forming method, therefore preferred T mold forming method.In T mold forming method, one or more cooling roller that is cooled through of the resin be extruded is implemented, and the temperature in the first cooling roller cooled by the resin be extruded at first is the cooling temperature in the present invention, remains on the certain temperature in the scope of 85 ~ 120 DEG C.
Like this cooling temperature during extrusion moulding is set as 85 ~ 120 DEG C, using comprise polyvinylidene difluoride (PVDF) system resin form film as the fluorine resin composition extrusion moulding of principal constituent time, in the DSC curve (first run) that the first round that can obtain being obtained by heat flux dsc under above-mentioned specified conditions is heated, in the endotherm(ic)peak (intrinsic peak) that the scopes of 150 ~ 190 DEG C have polyvinylidene difluoride (PVDF) system resin intrinsic, observe the new membrane of more than 1 endotherm(ic)peak at the low temperature side at this intrinsic peak.
This film is also the film of the brilliant ratio of α more than 80% defined by following formula (1).
In addition, in above-mentioned fluorine resin film, as long as above-mentioned fluorine resin composition is the resin combination of principal constituent containing polyvinylidene difluoride (PVDF) system resin, any resin, additive etc. that usually contain in fluorine resin can be comprised.Herein, " be principal constituent containing polyvinylidene difluoride (PVDF) system resin " refers to the polyvinylidene difluoride (PVDF) system resin containing more than 50 quality %, preferably more than 60 quality % in resin combination as resinous principle, and situation, i.e. polyvinylidene difluoride (PVDF) system resin that also comprising only has polyvinylidene difluoride (PVDF) system resin are the situation of 100 quality %.Therefore, in an embodiment of the invention, fluorine resin composition only contains polyvinylidene difluoride (PVDF) system resin as resinous principle.On the other hand, in other embodiments of the present invention, compounding have the plexiglass with the excellent compatibility of polyvinylidene difluoride (PVDF) system resin, carries out mixing and extrusion moulding.Such as, the resin combination of extrusion moulding contains 50 ~ 95 quality %, the polyvinylidene difluoride (PVDF) system resin being preferably 60 ~ 95 quality % and 5 ~ 50 quality %, is preferably the plexiglass of 5 ~ 40 quality %.
And then in above-mentioned fluorine resin film, fluorine resin composition, except resinous principle, can contain various additive, particularly in order to cover ultraviolet, preferably containing titanium oxide or UV light absorber., add the titanium oxide of 5 ~ 40 mass parts relative to resin combination 100 mass parts herein, add 0.1 ~ 5 mass parts relative to resin combination 100 mass parts, be preferably the UV light absorber of 0.3 ~ 5 mass parts.
In addition, the preferred thickness of above-mentioned fluorine resin film is the film in the scope of 10 ~ 50 μm.
According to other modes of the present invention, a kind of method manufacturing fluorine resin film is provided, described fluorine resin film is passing through heat flux dsc, the DSC curve (first run) of the first round heating obtained when room temperature is heated to 200 DEG C with the heat-up rate of 10 DEG C/min, there is the endotherm(ic)peak (intrinsic peak) that the polyvinylidene difluoride (PVDF) system resin of the scope being in 150 ~ 190 DEG C is intrinsic, and be in more than 1 endotherm(ic)peak of low temperature side at this intrinsic peak, described method possesses: using containing comprise the molten resin of polyvinylidene difluoride (PVDF) system resin as the fluorine resin composition of principal constituent be extruded into membranaceous operation and by the film resin that is extruded under the cooling temperature of the scope of 85 ~ 120 DEG C, preferably by being set as that the cooling roller of such cooling temperature carries out the operation cooled.
In this manufacture method, the brilliant ratio of the α that manufactured fluorine resin film is defined by formula (1) is also more than 80%.In addition, above-mentioned fluorine resin composition in a preferred embodiment, containing 50 ~ 95 quality %, the plexiglass that is preferably the polyvinylidene difluoride (PVDF) system resin of 60 ~ 95 quality % and 5 ~ 50 quality %, is preferably 5 ~ 40 quality %.And then, in fluorine resin composition, preferably amount to 100 mass parts relative to resinous principle, containing 5 ~ 40 mass parts titanium oxide or 0.1 ~ 5 mass parts UV light absorber.In addition, the preferred thickness of above-mentioned fluorine resin film is in the scope of 10 ~ 50 μm.
According to other modes of the present invention, provide the rear surface of solar cell screening glass formed by above-mentioned fluorine resin film and the solar module using this rear surface of solar cell screening glass to be formed.
Fluorine resin film involved in the present invention is formed by containing the fluorine resin of pvdf resin as principal constituent, so have excellent weathering resistance, thermotolerance, stain resistance, chemical proofing, solvent resistance, mechanical properties and secondary workability, in addition owing to being the resin molding in heat flux dsc with specific peak pattern, so long durability, particularly yellowing resistance are excellent.In addition, the rear surface of solar cell screening glass using fluorine resin film involved in the present invention to be formed and solar module also have excellent long durability, particularly yellowing resistance.
Accompanying drawing explanation
Fig. 1 is the graphic representation representing the DSC curve that the heat flux dsc by carrying out the fluorine resin film formed in embodiment 1 (chill-roll temperature: 85 DEG C), embodiment 2 (chill-roll temperature: 100 DEG C) and embodiment 3 (chill-roll temperature: 120 DEG C) obtains.
Fig. 2 is the cooling temperature relative to cooling roller in T mold forming, and the curve brilliant for the α obtained by infrared absorption spectrum analysis ratio and the Δ b value mapping obtained by hot resistance test obtained, expression cooling temperature is on the impact of the Yellowing of film.Cooling temperature is changed between 45 ~ 75 DEG C and the film made is comparative example 3 ~ 6, cooling temperature is changed between 85 ~ 120 DEG C and the film made is embodiment 11 ~ 14.
Fig. 3 is the spectrogram representing the result that the infrared absorption spectrum carried out the film made by the fluorine resin containing plexiglass with various content is analyzed.The ratio of the plexiglass in resin combination is changed between 0 ~ 50 quality % and the film that makes is embodiment 15 ~ 19, the film that this ratio is made in 60 ~ 70 quality % changes is comparative example 7 ~ 8.
Fig. 4 represents that the film to embodiment 15 ~ 19 and comparative example 7 ~ 8 implements the graphic representation of the result of X-ray diffraction.
Fig. 5 represents that the film to embodiment 15 ~ 19 and comparative example 7 ~ 8 implements the graphic representation of the result of dsc analysis.
Embodiment
Below embodiments of the present invention are described in detail.
The fluorine resin film of an embodiment of the invention is formed by extrusion moulding by the fluorine resin composition being principal constituent containing polyvinylidene difluoride (PVDF) system resin.
< fluorine resin composition >
As long as fluorine resin composition is the resin combination of principal constituent containing polyvinylidene difluoride (PVDF) system resin, any resin, additive etc. that usually contain in fluorine resin can be comprised.Herein, " be principal constituent containing polyvinylidene difluoride (PVDF) system resin " to refer in resin combination containing more than 50 quality %, is preferably the polyvinylidene difluoride (PVDF) system resin of more than 60 quality % as resinous principle, and situation, i.e. polyvinylidene difluoride (PVDF) system resin that also comprising only has polyvinylidene difluoride (PVDF) system resin are the situation of 100 quality %.
In addition, " polyvinylidene difluoride (PVDF) system resin " refers to and is principal constituent with vinylidene fluoride monomers and the crystalline resin showing the various crystalline structure such as α type, β type, γ type, refers to the homopolymer of vinylidene or vinylidene and can the multipolymer of monomer of copolymerization.As multipolymer, such as, there is vinylidene-hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) based copolymer, biasfluoroethylene-hexafluoropropylene based copolymer etc.The homopolymer of preferred use vinylidene.
In fluorine resin composition, can containing the resinous principle beyond polyvinylidene difluoride (PVDF) system resin, as such resinous principle, in order to play with the excellent compatibility of vinylidene fluoride resin, reduced by extrusion temperature when making film extruding forming and improve processibility, in addition improves and other materials stackedization time the effect such as cementability, preferred methacrylate system resin.Herein, methacrylate ester resin is except imperplex (polymethylmethacrylate), the methyl methacrylate monomer that contains specified amount such as more than 50 % by mole as Component units and specified amount can be enumerated such as lower than the multipolymer of the acrylate of 50 % by mole, the methacrylic ester beyond methyl methacrylate, and then the mixture of more than two kinds etc. of these polymkeric substance can be enumerated.As aforesaid propylene acid esters, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate etc. can be enumerated, in addition, as the methacrylic ester beyond methyl methacrylate, can β-dimethyl-aminoethylmethacrylate, propyl methacrylate etc. be enumerated.Should illustrate, multipolymer is not limited to random copolymers, such as, also can use graft copolymer etc., is also preferably used in monomer based on methyl methacrylate of graft polymerization on the saturated cross-linked rubber of acrylic acid series and the multipolymer obtained.Particularly preferred methacrylate ester resin is plexiglass.
Therefore, in one example in which, fluorine resin composition only contains polyvinylidene difluoride (PVDF) system resin as resinous principle.In addition, in other examples, fluorine resin composition contains polyvinylidene difluoride (PVDF) system resin and plexiglass as resinous principle.When the latter, as long as polyvinylidene difluoride (PVDF) system resin is principal constituent, the content of plexiglass can be arbitrary, in a preferred embodiment, fluorine resin composition contains 50 ~ 95 quality %, the polyvinylidene difluoride (PVDF) system resin being preferably 60 ~ 95 quality % and 5 ~ 50 quality %, is preferably the plexiglass of 5 ~ 40 quality %.
And then, in fluorine resin composition, in order to give ultraviolet screening effect, preferably containing at least one in pigment and UV light absorber.Such as, film, when to protect for the purpose of base substrate, sometimes can not add pigment, but also add UV light absorber in this case.This is because although the weathering resistance of film itself is good, but when not adding pigment and just using, ultraviolet arrives various base materials etc., even if there is not deterioration in vinylidene resin film, various base material, in order to stacked with base material and deterioration also can occur tackiness agent etc. that is that use, may to occur and the problem that polyvinylidene difluoride (PVDF) resin film is peeled off.
Used pigment is not particularly limited, has the pigment arbitrarily such as mineral dye, pigment dyestuff, pearly pigment, from the viewpoint of weathering resistance, preferably use the mineral dye of oxide compound, combined oxidation system, particularly preferably titanium oxide.The addition of pigment, particularly titanium oxide is 5 ~ 40 mass parts relative to 100 mass parts resins, is preferably 10 ~ 30 mass parts.When addition is lower than 5 mass parts, cannot be evenly dispersed in film, sometimes occur part color spot.On the other hand, when adding more than 40 mass parts, the dispersiveness of fluorine resin is significantly reduced, sometimes causes bad order.
As long as UV light absorber has consistency person with vinylidene fluoride resin, such as, can use benzotriazole system, oxalic acid system, benzophenone series, hindered amine system and other multiple UV light absorber.Preferably, in order to volatilization when making manufacturing process and use as film is inferior limit, preferably use molecular weight is the UV light absorber of the high molecular type of more than 300.The addition of UV light absorber, relative to 100 mass parts resins, is 0.1 ~ 5 mass parts, is preferably 0.3 ~ 5 mass parts.
In film of the present invention, except pigment or UV light absorber, according to use, the various additives such as stabilization agent, dispersion agent, antioxidant, matting agent, tensio-active agent, static inhibitor, silicon-dioxide, aluminum oxide and so on packing material, fluorine system surface-modifying agent and processing aid can be added in the scope of dispersiveness that can't harm them.
As the method being mixed into pigment, UV light absorber, other various additives in film of the present invention, can adopt and resin and additive be pre-mixed and use normally used single axle extruding machine to carry out the method for melting mixing.In addition, carried out the method for melting mixing after using the biaxial extruder of high mixed milling type, the at high temperature pre-mixing in advance of use high-speed rotation type mixing machine by employing by single axle extruding machine, the film that dispersion state is good, exterior quality is excellent of additive can be obtained.
The thickness of fluorine resin film of the present invention is preferably less than 50 μm, more preferably 10 ~ 30 μm.During lower than 10 μm, operability significantly reduces, and in addition, sometimes cannot obtain sufficient endurance quality.On the other hand, if more than 50 μm, then raw material cost increase etc. are unfavorable to cost.In addition, also can be with film of the present invention for upper layer, as back layer, the blend of stacked acrylic resin layer, vinylidene fluoride resin and acrylic resin, makes the film of more than 2 layers.
The manufacture > of < fluorine resin film
The method that fluorine resin film can be filmed by the T-shaped mould of use usually, the method using blow mold to be filmed implement extrusion moulding, in the present invention, preferably use the method that T-shaped mould is filmed.Extrusion condition is not particularly limited, the conventional condition for the formation of vinylidene resin film can be used, but the scope that in the present invention, the cooling temperature after extruding must be set as 85 ~ 120 DEG C, be preferably 90 ~ 120 DEG C, be more preferably 100 ~ 120 DEG C.Namely, when using T die forming machine to be filmed, the high-temperature resin extruded from T-shaped mould is film forming by the metal cooling roller cooling curing be configured in T-shaped mould, the scope that the temperature of this metal cooling roller is set as 85 ~ 120 DEG C, is preferably 90 ~ 120 DEG C, is more preferably 100 ~ 120 DEG C.Should illustrate, when being equipped with multiple cooling roller in extrusion shaping machine, the temperature of initial cooling roller (the first cooling roller) is set to 85 ~ 120 DEG C, preferably 90 ~ 120 DEG C, is more preferably the scope of 100 ~ 120 DEG C.In addition, whether under T-shaped mould, arranging metal cooling roller and rubber rollers are conventions in pairs, but use the design temperature of rubber rollers and rubber rollers to be optional.When above-mentioned cooling temperature is set as lower than 85 DEG C, the film with desired long durability, particularly yellowing resistance cannot be obtained.On the other hand, when above-mentioned cooling temperature is set as higher than 120 DEG C, peeling off the bad film that causes with roller cannot good filming.
Should illustrate, the supply of raw material can use each raw material melting mixing and resin combination made in advance, can also various raw material be directly supplied in the forcing machine of single shaft or twin shaft, usually at the temperature of 150 ~ 260 DEG C, carry out melting, undertaken extruding by film T mould and implement masking.
< fluorine resin film >
Above-mentioned fluorine resin composition is carried out extrusion moulding under these conditions and the fluorine resin film that obtains be the brilliant ratio of α defined according to above-mentioned formula (1) is the film of more than 80%, but according to formula (1) if the brilliant ratio of the α defined exceedes certain numerical value, then can become state of saturation, the changes in crystal structure of film cannot be reflected.But this change of state can be held by using the analysis of heat flux dsc.Namely, for fluorine resin film, no matter whether cooling temperature is set in the scope of 85 ~ 120 DEG C, the DSC curve (first run) of the first round heating obtained when to be heated to 200 DEG C from room temperature with the heat-up rate of 10 DEG C/min by heat flux dsc, near 170 DEG C, all observe the intrinsic endotherm(ic)peak of polyvinylidene difluoride (PVDF) system resin.But, cooling temperature is set as 85 ~ 120 DEG C of scopes and in the fluorine resin film of the present invention that masking obtains, can be observed more than 1 endotherm peak temperature from α crystalline substance at the low temperature side of the intrinsic endotherm(ic)peak of above-mentioned polyvinylidene difluoride (PVDF) system resin.Further, the endotherm(ic)peak of this low temperature side is more remarkable, and the ratio of α crystalline substance more increases, and the long durability of film, particularly yellowing resistance more improve.Such as, in fluorine resin film of the present invention, film just make after form and aspect b value be about-2.5 ~-0.5, also do not have significant xanthochromia in after humidity resistance described later test, the Δ b value before and after test is suppressed in less than 2.
Should illustrate, in the fluorine resin film formed in the conditions of the invention, the endotherm(ic)peak observed at the low temperature side of the intrinsic endotherm(ic)peak of polyvinylidene difluoride (PVDF) system resin is usually brilliant from α, but when forming film under the condition beyond the conditions of the present invention such as the temperature range beyond cooling temperature scope of the present invention, observe endotherm(ic)peak at the low temperature side of the intrinsic endotherm(ic)peak of polyvinylidene difluoride (PVDF) system resin sometimes.But this endotherm(ic)peak is not the endotherm(ic)peak from α crystalline substance, but from the endotherm(ic)peak of β crystalline substance, confirmed by such as X-ray diffraction method.Therefore, the fluorine resin film of the DSC curve desired by the display formed under condition within the scope of the invention, compared with the fluorine resin film formed under extraneous condition of the present invention, has excellent weathering resistance, particularly yellowing resistance.
Embodiment
Further illustrate the present invention by the following examples, but the present invention is not limited to this.Should illustrate, the raw material used in embodiment is as described below with the evaluating characteristics of each sample of the film made.
< uses raw material >
Pvdf resin: Kynar K720 (Arkema Corporation system), for the polyvinylidene difluoride (PVDF) system resin of crystalline polymer, Oil repellent about 59%, fusing point about 170 DEG C, MFR (condition: 230 DEG C, 3.8kg loading) 5 ~ 29 (g/10min)
Methacrylate ester resin: Acrypet IR-S404 (Mitsubishi Rayon Co., Ltd's system), comprise the methacrylate ester resin of the rubber constituent of butyl acrylate (n-BA) and butyl methacrylate (BMA), MFR (condition: 230 DEG C, 37.3N) 7.8 (g/10min)
Titanium oxide: Ti-Pure R960 (E.I.Du Pont Company's system), (particle diameter: about 0.35 μm, pure titanium composition: about 89%)
< evaluation method >
(1) the brilliant ratio of α
The mensuration of infrared absorption spectrum is carried out by NICOLET380FT-IR (Thermo Fisher Scientific Corporation system).The characteristic absorption of the β N-type waferN of the polyvinylidene difluoride (PVDF) system resin in infrared absorption spectrum is at wave number 840cm
-1, the characteristic absorption of alpha type crystal is present in wave number 765cm
-1so for the brilliant ratio of α, use following formula (1) by each peak intensity of the spectrum obtained and calculate the brilliant ratio of α (see flower Tian Pengmei, the peace rattan stalks of rice, wheat, etc., " Port リ Off ッization PVC ニ リ デ Application と Port リ jealous woman acid PVC ニ Le and び Port リ エ チ Le メ タ Network リ レ ー ト Block レ Application De system To お け Ru Port リ Off ッization PVC ニ リ デ ン Knot crystallization (crystallization of the polyvinylidene difluoride (PVDF) in polyvinylidene difluoride (PVDF) and polyvinyl acetate and polyethyl methacrylate co-mixing system) ", Tokyo university of housekeeping institute summary, in July, 1992, No.32,5-12 page).
(2) form and aspect after humidity resistance test
Humidity resistance test uses Pressure Cooker SPY-4016 (ALP Corporation system) to implement as trier.For the membrane sample of fitting with EVA, use the colour examining colour-difference-metre ZE-2000 of Japanese electricity Se Industrial Co., Ltd carry out with the color difference measurement of the binding face of this EVA after, drop in trier, implement long duration test under the following conditions.
Temperature: 125 DEG C
Humidity: 100%
Pressure: 2.3atm
Time: 50hr
After test, that again carry out film with color difference measurement that the is binding face of EVA, calculate the Δ b value before and after test.Metewand by Δ b value below 2 time be judged as that xanthochromia is few.
(3) UV transmitance
Hitachi spectrophotometer U-3310 (Hitachi-Hightech Fielding Co.Ltd. system) is used to measure the UV transmitance of film at wavelength 340nm place.
(4) heat flux dsc
Means of differential scanning calorimetry device DSC3100SA (BrukerAXS Corporation system) is used to measure under the following conditions.
Temperature: room temperature → 200 DEG C
Heat-up rate: 10 DEG C/min
Sample quality: 1.5mg
(5) X-ray diffraction
X-ray diffraction device Ultima IV (company of science) is used to measure under the following conditions.
X-ray source: Cu sealed tube
Apply voltage/current: 40kV/40mA
Detector: high-speed detector D/teX Ultra
< embodiment 1 ~ 10 and comparative example 1 ~ 2 >
By vinylidene fluoride resin, plexiglass, titanium oxide presses PMMA ratio shown in table 1 (relative to the total 100 quality % of vinylidene fluoride resin and plexiglass, the quality % of plexiglass) and titanium oxide amount (relative to resin 100 mass parts, the mass parts of titanium oxide) be prepared, drop into carry out in φ 65mm single axle extruding machine mixing after, extruded by T-shaped mould under extrusion temperature 240 DEG C from this forcing machine, by being set as the first cooling roller of the cooling temperature shown in table 1, make its cooling curing and to carry out film shaping, obtain the embodiment 1 ~ 10 of the thickness shown in table 1 and the film of comparative example 1 ~ 2.
For the film made, according to aforesaid evaluation method, evaluate form and aspect, UV transmitance, the heat flux means of differential scanning calorimetry after the brilliant ratio of α, humidity resistance test.The results are shown in table 1.In addition, for the film of representational embodiment 1 ~ 3, the DSC curve obtained by heat flux dsc is shown in Fig. 1.Should illustrate, in comparative example 2, film is successfully peeled off from cooling roller, fails to make the film that can supply evaluating characteristics.
As shown in Table 1, the film of embodiment 1 ~ 10 is except the brilliant ratio of high α, and also have endotherm(ic)peak at the low temperature side at intrinsic peak, the aberration Δ b after humidity resistance test is enough little value, and yellowing resistance is excellent.In contrast, in known comparative example 1, the brilliant ratio of α is low, and yellowing resistance is deteriorated.Should illustrate, although comparative example 1 also been observed endotherm(ic)peak, this peak is known by X-ray diffraction is peak from β crystalline substance.In addition, from the result of Fig. 1, in the fluorine resin film of embodiment 1 ~ 3, observe endotherm(ic)peak at the low temperature side at the intrinsic peak of polyvinylidene difluoride (PVDF) system resin, along with chill-roll temperature raises further, this endotherm(ic)peak becomes remarkable.
[table 1]
* film has just manufactured the value of rear mensuration
< embodiment 11 ~ 14, comparative example 3 ~ 6 >
In order to study the design temperature of metal cooling roller to the impact of the Yellowing of film, make that PMMA ratio is 25%, titanium oxide amount is 22 mass parts, the setting cooling temperature of metal cooling roller is become 45 DEG C, 55 DEG C, 65 DEG C, 75 DEG C, 85 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, the fluorine resin film of comparison example 3 ~ 6 and embodiment 11 ~ 14.For the film obtained, obtain the brilliant ratio of α and measure Δ b value.Result is shown in Fig. 2.
As shown in Figure 2, if cooling temperature is low, then the brilliant ratio of α is low, result, and Yellowing becomes remarkable, if cooling temperature raises until cooling temperature reaches 80 DEG C, then the brilliant ratio of α also increases, although Yellowing does not fully reduce, but in slow reduction.But if cooling temperature reaches about 85 DEG C, then the brilliant ratio of α reaches capacity state, do not continue to increase, but Yellowing still slowly reduces.That is, be appreciated that to be limited according to the reduction method resolving to the Yellowing on basis of the brilliant ratio of α based on infrared absorption spectrum analysis by this experimental result.
< embodiment 15 ~ 19, comparative example 7 ~ 8 >
In order to study the impact of PMMA ratio on the crystalline structure of fluorine resin film, make that the design temperature of metal cooling roller is 85 DEG C, titanium oxide amount is 22 mass parts, PMMA ratio is increased to 10 quality %, 20 quality %, 30 quality %, 40 quality %, 50 quality %, 60 quality %, 70 quality % from 0 quality %, makes the fluorine resin film of embodiment 15 ~ 19 and comparative example 7 ~ 8.Analyzed by ultra-red absorption spectrometry, X-ray diffraction method, the crystalline structure of heat flux dsc to the fluorine resin film obtained.Result is shown in Fig. 3 ~ 5.From the analytical results utilizing ultra-red absorption spectrometry to obtain of Fig. 3, along with PMMA ratio increases, brilliant from α, that β is brilliant peak diminishes.In addition, from the analytical results utilizing X-ray diffraction method to obtain of Fig. 4, if PMMA ratio is more than 50 quality %, then the crystallization of PVDF is suppressed.And then from the result utilizing the analysis of heat flux dsc of Fig. 5, along with PMMA ratio increases, fusing point Tm gradually reduces from about 170 DEG C (PMMA ratios: 0 quality %).In addition, if PMMA ratio is more than 50 quality %, then intrinsic endotherm(ic)peak weakened, PVDF and PMMA is compatible.
Claims (8)
1. a fluorine resin film, it is characterized in that, it is that the fluorine resin composition being principal constituent containing polyvinylidene difluoride (PVDF) system resin is extruded shaping, be set as 85 ~ 120 DEG C scope cooling temperature under cooling and formed, and by heat flux dsc, the DSC curve of first round heating that obtains when room temperature is heated to 200 DEG C with the heat-up rate of 10 DEG C/min, there is the intrinsic endotherm(ic)peak of the polyvinylidene difluoride (PVDF) system resin of the scope being in 150 ~ 190 DEG C and intrinsic peak and be in more than 1 endotherm(ic)peak of low temperature side at this intrinsic peak.
2. fluorine resin film according to claim 1, wherein, the brilliant ratio of the α that formula 1 defines is more than 80%,
3. fluorine resin film according to claim 1 and 2, wherein, the plexiglass of polyvinylidene difluoride (PVDF) system resin and 5 ~ 50 quality % that fluorine resin composition contains 50 ~ 95 quality % is as resinous principle.
4. fluorine resin film according to claim 3, wherein, amounts to 100 mass parts relative to resinous principle, and fluorine resin composition contains the titanium oxide of 5 ~ 40 mass parts or the UV light absorber of 0.1 ~ 5 mass parts.
5. the fluorine resin film according to any one in Claims 1-4, wherein, thickness is in the scope of 10 ~ 50 μm.
6. one kind manufactures the method for fluorine resin film, described fluorine resin film is by heat flux dsc, the DSC curve of the first round heating obtained when room temperature is heated to 200 DEG C with the heat-up rate of 10 DEG C/min, there is the intrinsic endotherm(ic)peak of the polyvinylidene difluoride (PVDF) system resin of the scope being in 150 ~ 190 DEG C and intrinsic peak, and be in more than 1 endotherm(ic)peak of low temperature side at this intrinsic peak, described method possesses: using containing the operation comprising the molten resin of polyvinylidene difluoride (PVDF) system resin as the fluorine resin composition of principal constituent and be extruded into membranaceous operation and cooled under the cooling temperature of the scope of 85 ~ 120 DEG C by the film resin be extruded.
7. a rear surface of solar cell screening glass, it is formed by the fluorine resin film described in any one in claim 1 to 5.
8. a solar module, it uses the rear surface of solar cell screening glass described in claim 7 to be formed.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2012251620 | 2012-11-15 | ||
| JP2012-251620 | 2012-11-15 | ||
| PCT/JP2013/079440 WO2014077133A1 (en) | 2012-11-15 | 2013-10-30 | Fluorinated resin film, method for producing same, and solar cell module |
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| CN104812810A true CN104812810A (en) | 2015-07-29 |
| CN104812810B CN104812810B (en) | 2018-07-10 |
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| KR (1) | KR102181433B1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108051136A (en) * | 2017-12-08 | 2018-05-18 | 马鞍山合力仪表有限责任公司 | A kind of preparation method of diaphragm pressure gage isolation diaphragm |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015166427A (en) * | 2014-03-04 | 2015-09-24 | 株式会社クレハ | Fluororesin film, production method of the same, laminate, and back sheet for solar cell module |
| JP6407918B2 (en) * | 2016-05-30 | 2018-10-17 | 住友化学株式会社 | Resin laminate, display device and polarizing plate |
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| JP2006273980A (en) * | 2005-03-29 | 2006-10-12 | Denki Kagaku Kogyo Kk | Vinylidene fluoride resin film and method for producing it |
| CN101661962A (en) * | 2008-08-29 | 2010-03-03 | 苏州中来太阳能材料技术有限公司 | Solar battery back film with high cohesiveness and processing process |
| CN102167836A (en) * | 2011-03-01 | 2011-08-31 | 宜兴市高拓高分子材料有限公司 | Preparation method of polyvinylidene fluoride thin film |
| JP2012149152A (en) * | 2011-01-18 | 2012-08-09 | Kureha Corp | Polyvinylidene fluoride resin composition, colored resin film, and backsheet for solar cell module |
| CN102666715A (en) * | 2009-11-30 | 2012-09-12 | 电气化学工业株式会社 | Polyvinylidene fluoride resin composition, film, back sheet, and solar cell module |
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| US4808352A (en) * | 1985-10-03 | 1989-02-28 | Minnesota Mining And Manufacturing Company | Crystalline vinylidene fluoride |
| JP5125012B2 (en) | 2006-07-25 | 2013-01-23 | 凸版印刷株式会社 | Solar cell backside sealing sheet |
| JP5415247B2 (en) | 2009-12-17 | 2014-02-12 | 電気化学工業株式会社 | Surface protection sheet for solar cells |
| WO2012172876A1 (en) * | 2011-06-15 | 2012-12-20 | 株式会社クレハ | Polyvinylidene fluoride resin film, multilayer film, backsheet for solar cell module, and film manufacturing process |
-
2013
- 2013-10-30 WO PCT/JP2013/079440 patent/WO2014077133A1/en active Application Filing
- 2013-10-30 CN CN201380059896.4A patent/CN104812810B/en not_active Expired - Fee Related
- 2013-10-30 JP JP2014546934A patent/JP6310858B2/en active Active
- 2013-10-30 KR KR1020157015701A patent/KR102181433B1/en active IP Right Grant
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| JP2006273980A (en) * | 2005-03-29 | 2006-10-12 | Denki Kagaku Kogyo Kk | Vinylidene fluoride resin film and method for producing it |
| CN101661962A (en) * | 2008-08-29 | 2010-03-03 | 苏州中来太阳能材料技术有限公司 | Solar battery back film with high cohesiveness and processing process |
| CN102666715A (en) * | 2009-11-30 | 2012-09-12 | 电气化学工业株式会社 | Polyvinylidene fluoride resin composition, film, back sheet, and solar cell module |
| JP2012149152A (en) * | 2011-01-18 | 2012-08-09 | Kureha Corp | Polyvinylidene fluoride resin composition, colored resin film, and backsheet for solar cell module |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108051136A (en) * | 2017-12-08 | 2018-05-18 | 马鞍山合力仪表有限责任公司 | A kind of preparation method of diaphragm pressure gage isolation diaphragm |
Also Published As
| Publication number | Publication date |
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| KR102181433B1 (en) | 2020-11-23 |
| WO2014077133A1 (en) | 2014-05-22 |
| JPWO2014077133A1 (en) | 2017-01-05 |
| CN104812810B (en) | 2018-07-10 |
| KR20150085024A (en) | 2015-07-22 |
| JP6310858B2 (en) | 2018-04-11 |
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