TW201223995A - Polyester film and method for producing same - Google Patents

Abstract

The purpose of the present invention is to provide a polyester film having sufficiently superior thermal dimensional stability, resistance to thermal deformation and improved thermal strength stability and a method for producing the same. The present invention relates to a biaxially oriented polyester film containing a polyester resin formed by polycondensation of an alcohol component that contains a diol compound represented by general formula (I) (wherein, ring A is either a cyclohexane ring or a benzene ring; n1 is an integer of 0 - 4; and R1 is a hydrogen atom or alkyl group) and a carboxylic acid component containing a dicarboxylic acid compound represented by general formula (II) (wherein, ring type B is the other of the cyclohexane ring or benzene ring; n2 is an integer of 0 - 4; R2 is a hydrogen atom or an alkyl group; and R3 is a hydrogen atom or an alkyl group), wherein the coefficient of thermal expansion of the polyester film when the temperature is raised from 50 DEG C to 100 DEG C is 50 ppm/ DEG C or less, and the absolute value for the rate of contraction at 150 DEG C is less than 2.0%. The present invention further relates to a method for producing the polyester film wherein a precursor film containing the polyester resin is produced, and thereafter, a heat treatment step that contains at least a biaxial drawing process is carried out on this precursor film.

Description

201223995 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a polys(R) film (particularly to a thermal polyester film) and a method of producing the same. C Before ^: is good;}| Background technology In recent years, in the fields of electronic equipment, semiconductors, solar cells, etc., it is called the lamination technology of plastic film and metal foil, the vapor deposition technology of plastic film or sputtering technology, The lamination technology of plastic film and ceramics, the coating technology of various resins to plastic film or the composite technology of laminated technology are very prosperous and complicated. In the case where the composite system such as the laminated product is used as a product, the plastic film (so-called process film (release film)) is peeled off and removed from the composite, and the product is used as a product. . As such, the use of plastic film involves a variety of aspects. At the time of compositing, there are generally many cases where heat is imparted to the plastic film, and the case of giving higher temperatures is gradually increased. In addition, with the demand for performance in the south in recent years, the heat resistance of the plastic film is required to be strict, for example, not only the heat deformation resistance of the plastic film, but also the behavioral characteristics of the dimensional change due to heat. (heat-resistant dimensional stability) is also an important factor * It is generally known that a polyimide film is used as a heat-resistant base film. However, the 'Poly 醯 赖 麟 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 201223995 Although it is known that a polyethylene terephthalate film is used as a polyester film, it has various problems because it does not have a degree of richness that can sufficiently correspond to a composite technique such as a laminate technique in recent years. Specifically, since the molten layer is deformed on the base film due to heat when the metal layer is laminated, it is required to have good heat deformation resistance to the base film. Even if it has good heat deformation resistance, warpage occurs in the entire laminate due to dimensional changes (thermal expansion and/or heat shrinkage) in the substrate film due to heat. Therefore, it is required to have good heat resistance to the substrate film. Dimensional stability. Further, since heat is required to lower the strength of the substrate film, it is required to have good heat resistance stability. Other polyester film materials are known to be obtained by polycondensing a diol component composed of 1 > 4_cyclohexanedimethanol with a dicarboxylic acid component composed of terephthalic acid and isophthalic acid. Polyester (so-called pCTA) (for example, Patent Document 1). However, as with the PET film, sufficient heat resistance could not be obtained by using the pcTA film alone. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The object of the present invention is to provide a heat-resistant dimensional stability and heat deformation resistance which are excellent, and A polyester film having improved heat resistance stability and a method for producing the same. 201223995 means for solving the problem at least the present invention relates to a biaxial alignment polyester crucible, a bacon " having a mixture of a diol component and a diminishing component; wherein the diol component comprises a formula (1) The diol compound. [Chemical 1]. '

(I) (wherein, the ring is a cyclohexene ring or a benzene ring; an integer of nU〇~4; and Ri is selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, and "When it is an integer of 2 to 4, the 2 to 4 groups are each independently selected from the group consisting of the dicarboxylic acid component represented by the formula (II): [Chemical 2]

(Π) (In the formula, when the ring is a cyclohexane ring, the ring is a benzene ring; when the ring is a benzene ring, the ring is a ring of a ring; η2 is an integer of 〇~4; R2 is selected From the group consisting of a hydrogen atom and an alkyl group having a carbon number of 3, and when !! 2 is an integer of 2 to 4, the 2 to 4 R2 systems are each independently selected from the group; The Han 3 series are each independently a hydrogen atom or a carbon atom having a carbon number of 1 to 3); 5 f is obtained under conditions of a tensile weight of 5 gf and a temperature rising rate of 1 〇 ° c /min.绝对 The absolute value of the coefficient of thermal expansion after heating to 100 ° C is 50 ppm / ° C or less; the absolute value of the heat shrinkage at 150 ° C is less than 2.0%. 201223995 The present invention also relates to a method for producing a polyester film which comprises a heat treatment step comprising a biaxial stretching treatment after the precursor film containing the polyester resin is produced. EFFECT OF THE INVENTION The polyester film of the present invention is excellent in heat-resistant dimensional stability and heat-resistant deformability and has good heat-resistant strength stability. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a solar cell module-level back surface protective sheet according to an embodiment of the invention of the present invention (Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Fig. 2] A schematic cross-sectional view of a solar battery module according to an embodiment of the invention of the basic application of the present invention. [Fig. 3] shows an embodiment of the basic application regarding the case! And the film of Comparative Examples 1 to 3 was subjected to a graph showing the change in tensile strength in the pressure cooker test over time. [Fig. 4] Fig. 4 is a graph showing changes with time in the tensile elongation retention rate in the pressure cooker test of the films of Examples 1 and 2 and Comparative Examples 1 to 3 of the basic application of the present application. Fig. 5 is a view showing the results of X-ray diffraction of the films of Examples 丨, 2 and Comparative Example 2 of the basic application of the present application. [Embodiment: J is a mode for carrying out the invention. The polyester film of the present invention contains a biaxial alignment film of a specific polyester resin", and a biaxial alignment means a polymer which constitutes the film in the in-plane direction of the crucible The 201223995 compound molecule is mainly oriented in two different directions (preferably two directions at a slightly right angle), and can be achieved by, for example, biaxial stretching as described later. In the present invention, by forming a film containing a specific polyester resin as a biaxial alignment film, it is possible to exhibit very excellent thermal dimensional stability and heat deformation resistance, and heat resistance strength, compared to a film which is not subjected to biaxial alignment. Increased stability. In the present specification, the thermal dimensional stability means the film property which can sufficiently prevent the expansion and contraction of the film even if the film is heated. The thermal deformability means that the film characteristics of the film can be sufficiently prevented from being melted and deformed even if the film is heated. The heat-resistant strength stability means a film property which can sufficiently prevent a decrease in film strength even if the film is heated. <Polyester Resin> The specific polyester resin (hereinafter simply referred to as "polyester resin A") contained in the polyester film of the present invention is obtained by at least condensing a diol component and a dicarboxylic acid component. The polyester resin, and the diol component contains a diol compound represented by the following formula (I), and the dicarboxylic acid component contains a dicarboxylic acid compound represented by the following formula (II). (diol component) [Chemical 3]

The two methylol groups on ring A may be 1,2-substituted, 1,3-substituted or 1,4-substituted, 201223995, and preferably have a relationship of 1,3-substituted or 1,4-substituted. And the relationship with 1,4- substitution is the best. Nl is an integer of 0 to 4, and preferably 0 or 1, and more preferably 0. R1 is selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 3 carbon atoms. Specific examples of the alkyl group include a mercapto group, an ethyl group, an isopropyl group and a n-propyl group. R1 is preferably a hydrogen atom or a sulfhydryl group, and more preferably a hydrogen atom. When n1 is an integer of 2 to 4, the 2 to 4 R1 systems are each independently selected from the above group, and the preferred one is a hydrogen atom at the same time. Specific examples of the diol compound represented by the formula (1) include a cyclohexane-based diol compound represented by the formula (la) and a benzene-based diol compound represented by the formula (lb). A cyclohexane diol compound is preferred. 【化4】

[化5] hoch2

(la) (lb) In the formulas (la) and (lb), nl and R1 are the same as in the formula (I). The cyclohexane-based diol compound represented by the formula (1) is a diol compound in which the ring A in the formula (I) is a cyclohexane ring. Specific examples thereof include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and 1,2-bis(hydroxymethyl)-3. ,4,5,6-tetradecyl-cyclohexane, 1,3-bis(hydroxymethyl)-2,4,5,6-201223995 tetramethyl-cyclohexane, 1,4-bis(hydroxyl Methyl)-2,3,5,6-tetradecyl-cyclohexane, and the like. It is preferably 1,3-cyclohexanedimethanol or 1,4-cyclohexanedodecanol, more preferably 1,4-cyclohexanedimethanol. The benzene-based diol compound represented by the formula (lb) is a diol compound in which the ring A in the formula (I) is a benzene ring. Specific examples thereof include 1,2-bis(hydroxyindenyl)benzene, 1,3-1,3-bis(hydroxyindenyl)benzene, 1,4-bis(hydroxyindenyl)benzene, and 1,2-double ( Hydroxymethyl)-3,4,5,6-tetramethyl-benzene, 1,3-bis(hydroxymethyl)-2,4,5,6-tetradecyl-benzene 1,4-bis(hydroxyl) Mercapto)-2,3,5,6-tetradecyl-benzene) and the like. Preferably, 1,3-bis(hydroxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene is preferred, and 1,4-bis(hydroxyindenyl)benzene is more preferred. The diol component may contain other diol compounds in addition to the diol compound represented by the above formula (I). As the other diol compound, a diol compound used as a raw material of the polyester film can be used, and examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, neopentyl glycol, and 1,2-butylene. Alcohol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol An aliphatic diol compound such as an alcohol or a polyalkylene glycol; and a diphenyl diol compound such as 2,2-bis(4·-/3··hydroxyethoxyphenyl)propane. From the viewpoints of heat resistance dimensional stability, heat deformation resistance, cost, extrusion moldability, and crystallinity (extensibility), among the diol compounds represented by the above formula (I), the polyester resin A The alcohol component is preferably a 1,4-diol compound having a 1,4 -substituted relationship in which two methylol groups on the ring A in the above formula (I) are used, and only the 1,4-diol compound is used. (especially 1,4-cyclohexanedimethanol) is more preferred. The ratio of the diol compound represented by the above formula (i) to the total diol component is from the viewpoints of heat resistance dimensional stability, heat deformation resistance, cost, extrusion moldability 201223995, and crystallinity (extensibility). It is preferably 50 mol% or more, more preferably 80 mol% or more, and most preferably 95 mol% or more. The diol component may contain two or more kinds of the diol compounds represented by the above formula (I). In this case, the total content of the diols may be within the above range. In addition to the diol component, the polyester resin A may contain, for example, a trifunctional or higher functional group such as trishydroxymethane, trimethylolethane, trihydroxymethylpropane, neopentyl alcohol, glycerin or hexanetriol. The polyol component is used as a constituent monomer. The content of the trifunctional or higher polyhydric alcohol component relative to the total alcohol component is usually 50 mol% or less, and preferably 20 mol% or less. (dicarboxylic acid component)

In the formula (II), when the ring A is a cyclohexane ring, the ring B is a benzene ring; and when the ring A is a benzene ring, the ring B is a cyclohexane ring. The two -COOR3 groups on ring B are 1,2-substituted, 1,3-substituted or 1,4-substituted, and preferably have a relationship of 1,3-substituted or 1,4-substituted. The relationship of 1,4-substitution is better. An integer of n2S〇~4, preferably 0 or 1, and more preferably 0. R2 is selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 3 carbon atoms. Specific examples of the alkyl group include the same alkyl groups as those exemplified in the description of R1. R2 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. And when n2 is an integer of 2 to 4, the 2 to 4 R2 systems are each independently selected from the group of 10 201223995, and it is preferably a hydrogen atom at the same time. Each of the two R3 groups is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Specific examples of the alkyl group include the same alkyl groups as those exemplified in the description of R1. R3 is preferably each independently a hydrogen atom or a ruthenium group, and more preferably a hydrogen atom at the same time. Specific examples of the dicarboxylic acid compound represented by the formula (II) include a benzene-based dicarboxylic acid compound represented by the formula (Ila) and a cyclohexane-based dicarboxylic acid compound represented by the formula (lib). . A benzene-based dicarboxylic acid compound is preferred. [7] r3ooc

(Ila) [化8] r3ooc

(Hb) In the formulae (Ila) and (lib), n2, R2 and R3 are the same as in the formula (II). The benzene-based dicarboxylic acid compound represented by the formula (Ila) is a dicarboxylic acid compound in which the ring B in the formula (II) is a benzene ring. Specific examples thereof include terephthalic acid, isophthalic acid, phthalic acid, 5-tert-butylisophthalic acid, phthalic acid, and 4,4-biphenyldicarboxylic acid. , 4,4-biphenylpyrene dicarboxylic acid, methyl terephthalate, methyl isophthalate, decyl phthalate, 1,2-dicarboxy-3:, 4:, 5, 6-tetramethyl-benzene, 1,3-dicarboxy-2,4,5,6-tetradecyl-benzene, 1,4-dicarboxy-2,3,5,6-tetramethyl-benzene, etc. . Preferred are terephthalic acid, p-benzoquinone 201223995 methyl ester, isophthalic acid, isophthalic acid vinegar. The cyclohexane-based dicarboxylic acid compound represented by the formula (iib) is a diwei compound in which the ring B in the formula (ι) is a cyclohexane ring. Specific examples thereof include, for example, 1,2-3⁄4 of burnt dibutyl acid, 1,3-cyclohexanal acid, ι, 4_学己尸^ 丨, 2-二县-3,4,5 , 6-tetradecyl-cyclohexane, U-dimercapto 2: 6: methylcyclohexene, 1,4-disulfo-2,3,5'6-tetramethyl, cyclohexene, etc. . Preferred is 1,4-cyclohexanaldicarboxylic acid. In addition to the dicarboxylic acid compound represented by the above formula (H), the Λ component may contain other dicarboxylic acid compounds. As the other dicarboxylic acid compound, a dicarboxylic acid compound used as a raw material of the polyester film can be used, and examples thereof include a naphthalene system such as a 1*carboxylic acid, a 1'5-naphthalenedicarboxylic acid, or a 2,6-naphthalenedicarboxylic acid. Carboxylation 4-inclusion: Diphenyl-based dicarboxylic acid compounds such as Μ'-diphenyldicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4,-diphenyliso-monocarboxylic acid An adipic acid compound such as adipic acid or earth oxalic acid. From the viewpoint of heat dimensional stability, heat deformation resistance, cost, extrusion moldability, and crystallinity (extensibility), among the monocarboxylic acid compounds represented by the above formula (11), the polyacetate resin The second component is composed of two _C00R3 groups on the ring B in the formula m, which are M. in the substitution relationship of 14·2 oxo acid ^, and includes the compound and the above-mentioned general formula I: The R3 group is 1,3_substitution relationship, the 仏2 化 3 堇 认 认 认 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( From the viewpoint of daily extensibility, the second formula represented by the above formula (II)

12 201223995 The content ratio of the acid compound to the total dicarboxylic acid component is preferably 50 mol% or more, more preferably 80 mol% or more, and most preferably 95 mol% or more. When the dicarboxylic acid component contains two or more kinds of the dicarboxylic acid compound represented by the above formula (II), the total content of the catalyst (10) is in the above range, that is, the above-mentioned dicarboxylic acid component is removed, and the polyester resin is eight. A monocarboxylic acid component and/or a trifunctional or higher polycarboxylic acid component may be contained as a constituent monomer. Further, the polyester resin A has a thickness of 40 to 250. (: (especially the transfer temperature of the 〜~ fine 艽沁 glass is preferred. The glass transition temperature of the raw resin can be measured based on jISK7121. The polyester resin A has a temperature of 180 to 350 ° C (especially 2 〇〇 to 300). The melting point of ruthenium is preferably measured. The melting point can be measured based on JIS K7121. The polyester resin A can be produced by polycondensation of the above monomer component by a well-known method, or can be obtained from a commercially available product. Commercially available products are, for example, copolyester 13319 (manufactured by Eastman Co., Ltd.), etc. Copolyester 13319 (manufactured by Eastman Co., Ltd.) is 1, 4-cyclohexanedimethanol and terephthalic acid and A polycondensate of a stearic acid. In the 5^1 曰 film, the resin A may contain two or more kinds of monomer compositions, glass transition temperatures, melting points, and/or carboxyl terminal concentrations in the above range. Ester Resin A. Although the polyester film of the present invention may contain other polymers in addition to the aforementioned polyester resin A, it is in the film from the viewpoint of further improving heat-resistant dimensional stability and heat-resistant deformation 13 201223995. Polymer component to be only from the aforementioned poly-lipid A is preferable. From the viewpoint of further improving the size of the 19-size material, it is preferable that the ratio of the polyester resin A to the polymer of the polyester film is 80% by weight or more, and It is best to use 8% by weight, and it is best to use 1% by weight. In the range that does not adversely affect the properties such as heat-resistant dimensional stability and heat distortion, or film forming properties, The poly-feeding chess contains, for example, poly(ethylene bromide), polybutylene terephthalate (four), polyethylene natriate (PEN), poly-terephthalic acid = fat; Amine, polystyrene, polychlorite, =Aku, etc. «Trees. Other polymerizations such as polyethers<Additives> In addition to the aforementioned polymers, the polyester film may also be an external absorbent, a colorant, or a light. Stabilizers, moisturizing agents: oxidizing agents, purple flame retardants and other additives 1 resistance to fine ± _, crystal nucleating agent, with antioxidants. From the point of view of weather resistance; the film is preferably containing external absorbents It is preferred to use a purple antioxidant to use a polyester, for example, a phenolic antioxidant, and an antimony The user's agent, the sulfur-based antioxidant, the phenol-based antioxidant is an organic compound containing a truss in the field of poly-films, and an organic compound can be used. The phenol ", phenol-based anti-gasification agent is used. The phenol skeleton has a "gasification agent" which is commercially available.

14 201223995 Commercial products of various antioxidants include, for example, Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Adeka Stab AO-60, Adeka Stab AO-330 (all manufactured by ADEKA), and irgan〇x 245 (Basf Corporation) System), Cyanox 1790 (manufactured by CYTEC), etc. The structure antioxidant is an organic compound containing a phosphorus atom, and a phosphorus atom-containing organic compound which has been used as a phosphorus-based antioxidant in the field of a polyacetate film can be used. Phosphorus-based antioxidants are commercially available. Commercial products of the phosphorus-based antioxidants include, for example, SumiHzer Gp (manufactured by Sumitomo Chemical Co., Ltd.), Adeka Stab PEP-36 (manufactured by Adeka Co., Ltd.), Irgafos 38, and Irgafosl 68 (all manufactured by BASF Corporation). The sulfur-based antioxidant is an organic compound containing a sulfur atom, and it is possible to use (4) a sulfur atom-containing organic compound as a sulfur-based antioxidant. The sulfur-based antioxidant is commercially available. The commercial product of the sulfur-based antioxidant may, for example, be S-MB (manufactured by Sumitomo Ryokan Co., Ltd.), 八三〇, ^8136 八0-4128 (eight-eight-feet 1 <: manufactured by the company). From a dominant point of view, the antioxidant content is preferably in the form of ~5 5% by weight (particularly g. 〇 2 to 3 〇% by weight) based on the polymer component in the poly sulfonium film. When two or more kinds of antioxidants are contained, the total amount of the antioxidants may be within the above range. From the viewpoint of further improving heat resistance, it is preferred that the antioxidant, the breaking antioxidant, and the (10) antioxidant are contained in the respective relative polymer components in an amount of from 0.05 to 2.0% by weight, particularly preferably from 0.1 to 1.0. The ultraviolet absorber can be used as a user of the ultraviolet absorber in the field of the polyacetate film, and examples thereof include a UV absorber, a urethane absorber, a benzotri(4) feed absorber, and the like. The benzo-deuterated ultraviolet absorber is an organic compound containing a benzo- skeletal structure and can be used as a benzo-containing (tetra) organic compound which has hitherto been used as a benzoic ultraviolet absorber in the field of poly- lys. Benzophenone UV absorbers are commercially available. A commercially available product of the benzotriazine (IV) ultraviolet absorber is exemplified by cy_b UV-3638 (manufactured by CYTEC Co., Ltd.). The triterpenoid ultraviolet absorber is an organic compound containing a triterpene skeleton, and a two-dimensional well skeleton organic compound which has hitherto been used as a three-till ultraviolet absorber in the field of polyester film can be used. The third lecture is that the ultraviolet absorber can be obtained from commercially available products. Commercial products of the three-pigmented ultraviolet absorber include, for example, Tinuvin 1577ED and Tinuvin 479 (all manufactured by BASF Corporation). The benzotriazole-based ultraviolet absorber is an organic compound containing a benzotriazole skeleton, and a benzotriazole-containing skeleton organic compound which has hitherto been used as a benzotriazole-based ultraviolet absorber in the field of polyester film can be used. The benzotriazole-based ultraviolet absorber can be obtained from a commercially available product. Commercial products of the benzotriazole-based ultraviolet absorber include, for example, Sumisorb 250 (manufactured by Sumitomo Chemical Co., Ltd.), Adeka Stab LA-31 (manufactured by Adeka Co., Ltd.), and Tinuvin 234 (manufactured by BASF Corporation). The content of the ultraviolet absorber is 0.1 to 2.0% by weight, and particularly preferably 0.15 to 1.5% by weight based on the polymer component in the polyester film. When two or more types of ultraviolet absorbers are contained, the total amount of the ultraviolet absorbers may be within the above range.

16 201223995 Colorants can use any pigments and dyes that can be used in the field of polycrystalline films. The coloring_content ratio is not particularly limited as long as it can reach the cost of the invention, and is preferably, for example, relative to the weight % of the polymer component. <Method for Producing Polyester Film> The polyester film of the present invention can be produced by the following method. For example, after the precursor film is produced by mixing and kneading the above-mentioned poly-S resin A and other polymers and additives which are desirably contained in a predetermined ratio, at least a two-axis is applied to the obtained precursor film. The heat treatment step of the extension treatment. The method for producing the precursor film can be carried out by a well-known method. For example, a mixture composed of a desired component can be melted and kneaded by a biaxial extruder, and the kneaded product can be extruded by a T-die and then cooled. The thickness of the precursor film is not particularly limited, and is, for example, 100 to 2000 " m ' and preferably 120 to 1 〇〇0//m. The heat treatment step is a step of performing at least a biaxial stretching treatment, usually a heat setting treatment after the shaft stretching treatment. The absolute value of the thermal expansion coefficient and the thermal shrinkage rate of the film can be reduced by the heat treatment step. The two-axis extension processing may perform simultaneous biaxial stretching for extending the MD direction and the TD direction simultaneously, or may perform a two-axis extension extending in the other direction after extending in one of the MD direction or the TD direction. Preferably, simultaneous biaxial stretching is performed. This is because the film which has undergone simultaneous biaxial stretching can improve the heat-resistant dimensional stability more than the film which has been subjected to the secondary biaxial stretching. On the other hand, even if the one-axis extension is substituted for the two-axis extension, the desired heat-resistant dimensional stability cannot be obtained. In the present specification, the MD direction 17 201223995 refers to the so-called flow direction 'in the direction in which the precursor film is drawn from the extruder (longitudinal direction). The TD direction means the so-called width direction ' and the vertical direction with respect to the md direction. In the case of performing the biaxial stretching, the stretching ratio and the stretching temperature are not particularly limited as long as they are cost-effective, but it is preferably set in the following range. This is because the heat-resistant dimensional stability can be further improved. The stretching ratio is in the range of 2.〇 times or more and does not cause breakage in the MD direction and the TD direction, and particularly preferably 2 〇 5 5 ,, and more preferably 2 3 〜 〇 倍 times. The stretching ratio in the MD direction and the TD direction is preferably approximated. Specifically, when the stretching magnification in the MD direction is PMD and the stretching ratio in the td direction is PTD, "Ptd_Pmd" is preferably _〇5 to + 〇5, and -〇·3~+ 0.3 is better. Further, the stretching magnification in the MD direction is based on the magnification of the length in the MD direction immediately before the extension. The extension in the TD direction is based on the magnification of the length in the TD direction immediately before the extension. The thermal expansion rate can be controlled by adjusting the stretching ratio within the aforementioned range. For example, if the stretching ratio in the predetermined direction is made large, the value of the coefficient of thermal expansion in this direction becomes small. When the glass transition temperature of the polymer component constituting the film is 讣 讣 (the 延伸 ' 'extension temperature is Tgp or more, Tgp + 3 〇 t or less, and from the viewpoint of further improving the heat-resistant dimensional stability, It is preferably Tgp°c or more and Tgp+25t or less. Further, the extension temperature is the ambient gas temperature of Weishen. When the polymer component is composed of two or more kinds of polymers, the polymer component is TgP-based polymer. The sum of the values obtained by multiplying the glass transition temperature by the content ratio of the polymer. 201223995 4a, by adjusting the extension temperature within the above range, the reduction in the coefficient of thermal expansion can be controlled. For example, if the elongation temperature is lowered, the thermal expansion is performed. The value of the rate is reduced. The heat setting treatment fixes the alignment of the polymer molecules by maintaining the stretching film at a temperature above the extension temperature. The heat setting temperature is the glass transition temperature of the polymer component constituting the film. It is TgP(t), the melting point is 11 or more in the range of the foot, and the Mpp is below, and from the viewpoint of further improving the dimensional stability and heat deformation resistance,

Up, MPp-2〇t^T. Furthermore, the heat setting temperature is the U ambient gas temperature. The sum of the values obtained by multiplying the melting point of each polymer of the polymer component held by the polymer cover by two or more polymer caps by the polymerization example. The ratio of the object 3 is reduced by the absolute value of the rate by adjusting the heat setting temperature within the aforementioned range. For example, if the _^ heat shrinkage shrinkage heat shrinkage rate is reduced, the absolute value will decrease. ~Fixed temperature' then the treatment system can be implemented in the maintenance of the two-extension of the lower part of the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The same can be implemented to maintain the tension to perform heat fixation (the first) heat fixation or to loosen the heat (the second heat fixation) of the composite type to make the sheet loosely set. __ caution &quot;1. It is preferred that the 'hot material temperature is set within the above range / ~ heat fixation treatment with the above-mentioned slack type "combined type of processing rate, the absolute value of the reduction, stability and heat The deformability = 201223995 θ liter and the flatness of the film, etc., the relaxation magnification is preferably ο 〇〇 〇〇 MD in the MD direction and the TD direction, and is preferably ο υ ( (8) times and 〇. 90 〜 95.95 times optimal. The relaxation ratio in the MD direction and the TD direction is approximately = preferably. Specifically, when the relaxation magnification in the MD direction is qmd, and • the relaxation ratio in the D direction is pQtd, QTD-QMD is preferably -0.1 to +0.1, and is preferably -0.05 to +0.05, and is preferably _〇〇2 to +0.02. Further, MD side The relaxation magnification is based on the magnification of the length in the MD direction immediately after stretching. The relaxation magnification in the TD direction is based on the magnification of the length in the TD direction just after stretching. The thermal shrinkage rate can be controlled by adjusting the relaxation ratio within the above range. For example, if the relaxation ratio in the predetermined direction is reduced, the decrease in the absolute value of the thermal shrinkage ratio in the direction becomes large. <Polyester 犋> Thickness of the polyester film of the present invention It is not particularly limited, and may be, for example, 10 to 15 Å/m' and preferably 12 to 125 #m. The polyester film of the present invention can exhibit remarkably excellent heat-resistant dimensional stability and heat deformation resistance. The poly(4) of the present invention is used as a laminated (four) hot film to sufficiently prevent warpage, melt deformation, and the like even when laminated on the forehead under high temperature conditions. Regarding the dimensional stability of the heat, in detail, The polyester film of the present invention has a thermal expansion coefficient and a heat shrinkage ratio, respectively, in a specific range, for example, when the temperature is raised from 5 〇t to HKTC under the conditions of a tensile load of 5 gf and a temperature increase rate of 1 (rc/min). Thermal expansion rate Based at 45ppm / t in 5〇ppm / t following, and: less' and more preferably at 4〇ppm / t or less account thermal expansion.

20 201223995 The value of the rate is within the above range in either the MD direction or the TD direction. If the value of the coefficient of thermal expansion is too large, the dimensional stability of heat resistance is lowered, and warpage cannot be sufficiently prevented. The polyester film of the present invention has a thermal expansion coefficient of usually + $ to + 50 ppmrc' and is preferably + 10 to + 45 ppm/t, more preferably + 1 〇 to + 4 〇 ρ _ °C. With respect to the coefficient of thermal expansion, from the viewpoint of more sufficiently preventing warpage, the value of the difference between the MD direction and the TD direction of the coefficient of thermal expansion is preferably 30 ppm/t or less, and 2 〇 ppm/r. The following is more preferable, and is preferably 1 〇卯 ^ C or less and preferably 5 ppm / ° C or less. In the present specification, the coefficient of thermal expansion is such that the test piece (2 mm x 25 mm) is suspended so that the longitudinal direction is perpendicular, and a tensile load of 5 g / 2 mm width is applied to the lower end of the test piece, and the temperature rise rate is 1 〇 1 / min. The rate of thermal expansion when the ambient gas temperature is raised from 5 G ° C. The coefficient of thermal expansion is measured in the case where the stretching direction is in the MD direction and the stretching direction is in the TD direction, and is specifically measured by the method described later. The absolute value of the heat shrinkage at 150 ° C is less than 2 %, and preferably less than 0.9%, and more preferably less than 〇.5%. The absolute value of the heat shrinkage rate is within the aforementioned range in the md direction and the TD direction in any direction. If the absolute value of the reduction ratio is too large, the heat-resistant property will be lowered, and the surface curvature will not be sufficiently prevented. Regarding the heat shrinkage rate, the absolute value of the difference between the _ direction and the TD direction from the viewpoint of more adequate prevention of the koji is preferably 1.5 W, more preferably 1% or less, and (4) The following is better, and the best is below 0.2%. 21 201223995 In this specification, the heat shrinkage rate is based on the ambient heat temperature 15 (the test piece (200mm×200mm) is placed in the 1^1) direction and the TD direction in the direction of the TD direction, specifically The method is measured as described later. The positive value of the value of the heat shrinkage rate means the contraction, and the negative value means the meaning of the expansion. Furthermore, the absolute value of the heat shrinkage ratio of less than 2.0% means that the value of the pure shrinkage ratio is greater than _2〇% and less than +2.0%. Regarding the deformability, specifically, the glass transition temperature of the polyester film of the present invention is above the thief, especially at t or more, and preferably at 22 ° C or higher, and at 23 Torr. (The above is more preferable. In the manufacturing process of the polyester film of the present invention, particularly before and after the heat treatment step including the aforementioned -axial stretching treatment and heat treatment), the glass transition temperature of the film rises above the thief, The special increase is above _, and is increased by 100. . The above is better than the increase of 13〇t or more. ▲ In addition, the glass transition temperature of the concentrating film used as a laminate is usually about 300 C, but is not particularly limited thereto. Further, although the glass transition temperature rises and the degree of the dish is about 250 C, it is not particularly limited thereto. Further, the polyester film of the present invention has good heat strength stability. For example, the heat-resistant strength stability may be improved compared to the precursor film before the biaxial stretching. When the polyester film contains an antioxidant, it exhibits remarkable excellent heat strength and stability. Specifically, in the polythene film of the present invention, the tensile strength retention rate after the drying phase test at 20 〇C is 5% 乂 and preferably 5% or more, and is achieved. More than 8〇% is better. Further, in the present invention, the knife behavior of the above-mentioned polystyrene resin crucible in the biaxial alignment film is more than %%, and it is also

22 201223995 About 150% of the situation. The Pu oven test was conducted to evaluate the heat resistance durability of the film, and was carried out by the method described later.

The tensile strength retention rate is based on the 20th generation ambient gas oven (10). (4) The test film is placed after the hour of the test. The retention of the tensile strength before the test. The tensile strength retention rate is based on JIS K7127, 1999. In the measurement, the average value in the case where the stretching direction is the md direction and the td direction is specifically performed by the method described later. The polyester film of the present invention is very useful as a heat resistant film system. It is used under the south temperature condition of 50 ° C or higher (especially at ιοοχ: above) and is required to have heat resistance such as heat resistance dimensional stability, heat deformation resistance and heat strength stability even under such high temperature conditions ( The heat-resistant film is, for example, a heat-resistant film for laminate, a heat-resistant film for mold release, a heat-resistant film for adhesion, etc. The heat-resistant film for laminate is used to laminate a layer on its own surface. A film used for the other layer, and a film having heat resistance is required because it is exposed to high temperature conditions during lamination. Examples of the other layer include a metal layer, a ceramic layer, a resin layer, and the like. The film is useful as, for example, a substrate film used in the production of a flexible printed circuit board such as an electronic device, a substrate film used in the production of a flexible solar cell, etc. Specifically, for example, the present invention is When the polyester film is used as a base film of a printed substrate, a wiring metal 23 is formed on the film by a dry buildup method, a vapor deposition method, a sputtering method, or the like, for example, at a high temperature of 70 to 200 °C. 201223995 Layers Even in such applications, the polyester film of the present invention can sufficiently prevent dimensional changes, strength reduction, and deformation, so that the film can be sufficiently prevented from being detached from the metal layer. The heat-resistant film for mold release is easily referred to as a film of a so-called process film. The heat-resistant film for mold release means that it is used as a support layer or a protective layer of the other layer by forming another layer on the film. The film which will be peeled off and removed at the end. There is also a case where a release layer of a ruthenium layer is provided between the film and other layers. Since it is heated in the formation step of the other layer or the subsequent steps, in order to prevent dimensional change The heat-resistant film for mold release is required to have heat resistance. The heat-resistant film for mold release is useful as, for example, a process film for forming a resin film, a process film for forming a ceramic film, and a process film for forming a metal film. The heat-resistant film for adhesion is very useful as a base film of an adhesive tape used for, for example, 70 to 200. (In particular, the polyester film of the present invention is used as a base for heat-resistant adhesive tape. When the film is used, the polyester film of the present invention can prevent the dimensional change, the strength from being lowered, and the deformation, so that the warpage of the bonded product, the peeling of the adhesive tape, and the like can be sufficiently prevented. Embodiment Examples/Comparative Examples by the two axes The extruder was at a resin temperature of 31 Torr. (: A mixture of the components described in Table 1 was melted, kneaded, and the kneaded product was separately extruded in a T mold, and then cooled to obtain a precursor film. The precursor film was stretched and heat-set by the extension conditions described in Table 1. Thermal fixing at a specified temperature

24 201223995 and relaxation rate for loose heat setting. At the same time, the two-axis extension is simultaneously extended in the MD direction and the TD direction. The successive two-axis extensions are extended in the MD direction and then extended in the TD direction. The one-axis extension extends only in the MD direction. PCTA is a copolymerized vinegar i3319 (manufactured by Eastman Co., Ltd., i, 4-cyclohexanol didecyl alcohol and terephthalic acid and isophthalic acid with a polycondensate, Tg92 ° C, melting point 285. 〇. PET The use of polyethylene terephthalate (Mni5000, Tg75 ° C, refining point 265 ° C, terminal carboxyl concentration 30 equivalent / ton). Thermal expansion rate thermal expansion rate using a thermomechanical measuring device (Q400EM; TA INSTRUMENTS), The test piece (film; 2 mm x 25 mm) was suspended in such a manner that the longitudinal direction of the test piece was perpendicular, and a tensile load of 5 gf / 2 mm width was applied to the lower end of the test piece. Thereafter, it was heated at a rate of 1 〇 / min. The ambient gas temperature is raised, and the dimensional change from 50 ° C to 100 ° C is changed to the amount of change per 1 ° C, and the thermal expansion coefficient is measured in the direction of the MD direction and the TD direction. Measured ◎ ; R^.OppmA: (best); 〇; 40ppm/°C &lt;RiS45ppm/°C (good); △; 45ppm/°C &lt;ΙΚ50ρριη/°(:( practically no problem); X; 50ppm/°C &lt;Ri (practical problem). The heat shrinkage rate is first 'in parallel with the MD direction and Two straight lines of 150 mm in length were drawn on the test piece (film; 200 mm x 200 mm) in the TD direction and at the midpoint phase 25 201223995. The test piece was placed in a standard state (temperature 23 ° C x humidity 50%) for 2 hours. Then, the length of the straight line before the test was measured. Then, in a hot air circulating oven set to an ambient gas of 150 ° C, the suspension was placed in a suspended state for 30 minutes, and then taken out and placed in a standard state for cooling 2 Thereafter, the length of the straight line in each direction is measured, and the amount of change in length before the test is obtained, and the ratio of the heat shrinkage ratio R2 as a change amount with respect to the length before the test is obtained. Regarding the heat shrinkage ratio R2, Positive value refers to the meaning of shrinkage. ◎ ; R2 &lt; 7) absolute value &lt; 0.5 ° / (best); 〇; 0_5% SR2 (?) absolute value &lt; 0.9% (good); △ ; 0.9% SR2 (7) absolute value &lt; 2.0% (practical no problem); X; 2_0 ° / 〇 SR2C7) absolute value (practical problem). The enchantment after lamination is used to evaluate the warpage after bonding the film to the aluminum foil. In detail, laminated aluminum foil (thickness 20 // m) / amine phthalate-based adhesive (solid part is 3g / m2) / each film, and hot pressing at 70 ° C and l 〇 kgf / cm 2 Minutes and samples were obtained (size: 50mm x 50mm). After standing to cool, visually judge the warp produced on the sample. ◎: no facial curvature was observed at all; △: although slight warpage was observed, there was no problem in practical use; and X: warpage was clearly observed. Film glass transition temperature (TMA)

The glass transition temperature was measured in accordance with JIS C6481: 1996 "5.17.1 TMA Method". In particular, the test piece (film; 2mm x 25mm) was heated by a thermomechanical measuring device (Q400EM; TA 26 201223995 INSTRUMENTS) under tensile load (5 gf / 2 mm width) and heating rate io ° c / min. And measure Tg. The Tg is measured in the case where the stretching direction is the MD direction and the TD direction, and is expressed by the average value of the same. The measurement of Tg is performed on the finally obtained film and the film immediately before the elongation, and the degree of increase is obtained (.〇. • Tg of the finally obtained film ◎: 230 ° C STg (best); 〇: 220 $ Tg &lt; 230 ° C (good); △ : 200 $ Tg &lt; 220 ° C (no problem in practical use); and X : Tg &lt; 200 〇 C. • Increase in amplitude ◎ : 130 ° CS increase (best); 100$ increase rate &lt;13〇.〇(good); △ : 5〇$ increase rate &lt;l〇〇t (practical problem); and X: increase range &lt;50°C. The film (100 mm x 100 mm) was placed in a hot air circulating oven set to an ambient gas of 2 〇〇t: for 1 minute, at which time the deformation generated on the film was visually judged. ◎: no deformation was observed at all; △: Although slight deformation was observed, there was no problem in practical use; and X: deformation was clearly observed. Heat-resistance stability The test piece (100 mm x 100 mm) was placed in a hot air circulating oven set to 200 ° C in an environment of 27 201223995 gas for 100 hours. The film was taken out from the oven, and the tensile strength was measured, and the tensile strength before the test was determined. The retention rate is obtained in the case where the stretching direction is the MD direction and the TD direction, and the average value 等 of the etc. is evaluated. The tensile strength is measured in accordance with JIS Κ7127; 1999. ◎ ; 80SMS 100 %(best); 〇;50SM&lt;80%(b);△;10SM&lt;50%(practical no problem); X; M&lt;10°/〇(practical problem) 28 201223995 [Table 1 ss CVj d Supervisor® Buried Cutting

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ό 患 患 08 08 08 l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l Ovqss !pv 1山d VIOd ΛΛ5 Ml W31 inch 丨ovcss^^pv i αι i αι -οοΐΝίδ (αιχα5) (alx§ (30/—) ss (υο) 29 201223995 Industrial availability of the month of the month The film-based heat-resistant film is useful as, for example, a thermal film for laminating, a heat-resistant film for mold release, and a heat-resistant film for bonding. The entire contents of the present application (Japanese Patent Application No. 20ΠΜ92520) are hereby incorporated by reference. The description of the specification is as follows: The contents of the manual [Invention name] terephthalic acid cyclohexyl diimide vinegar and m-benzene gt; formic acid cyclohexyl dimethylene 0 copolymer film, solar cell module BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copolymer film of a terephthalic acid, a cyclohexyl dimethylene phthalocyanine, a cyclohexylene diazide®, and a solar cell. A protective film and a solar cell module are used in the mold group. [Background Art] A solar cell power generation system has been expected As a substitute for the clean energy of fossil fuels, the solar cell module is protected by a package to protect the wires in an in-line or in parallel with dozens of solar cells. The component group of the component. The solar cell module is generally made of white (four) chemical glass, and the surface directly irradiated by sunlight is disposed under the solar cell component group, and is transparent ethylene vinyl acetate acetate. The resin or the like is filled with a gap, and the back surface thereof is configured to be protected by a sheet such as a weather resistant plastic material (for example, Patent Documents 1 and 2). Since the solar battery module is used outdoors, it is configured as a material structure. Requires sufficient durability and weather resistance. In particular,

30 201223995 The protective sheet for solar cell modules (especially the back protective sheet) is more weather resistant (especially hydrolysis resistance). This is because, during a long period of use outside the house, the protective sheet is decomposed and peeled off by moisture such as rain. Therefore, the exposed wiring may be corroded and the output power of the module may be affected. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-243999 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2008-235603 (Summary of the Invention) [Problems to be Solved by the Invention] Various film materials have been studied as substrates for back protective sheets for solar cell modules, but film materials having good hydrolysis resistance have not been provided. For example, polyethylene terephthalate (1&gt; is called membrane or polychlorinated diacetate (P EN) is difficult to be rich and miscellaneous, but in order to be able to withstand ± as a percentage of battery modules The substrate of the back protective sheet is used. Thus, the object of the present invention is to provide a film excellent in hydrolysis resistance, a solar cell mold using the mold, a protective sheet, and a solar cell module. After intensive research by the present inventors, it was found that a copolymer film of a specific terephthalic acid n-cyclohexyl-methylene ester and isophthalic acid i, 4-cyclohexyldimethacene is excellent in hydrolysis resistance. It is suitable as a substrate for a protective sheet for a solar cell module, and thus considers the present invention. It is not poorly known for the supply of terephthalic acid, cyclohexylenediphenyl, 1 benzophenone, 11, 4, cyclohexyl The copolymer medium of the present invention has a glass transition temperature of 13 (^c or more) as measured by the method of 31 201223995. Further, the present invention provides a bismuth subsynthesis and an isophthalic acid. Copolymer film of bismuth dicarboxylate, 4_cyclohexylene dimethylene methyl ester, the glass transition temperature measured by TMA method is 2 Further, the present invention provides a copolymer film of bismuth terephthalate, 4_cyclohexylene dimethylene methyl ester and bismuth metasilicate, 4-cyclohexylene diazide, It has the largest peak in the X-ray diffraction range of 22. $20 $ 24. The terephthalic acid terephthalate, 4-cyclohexylene dipyridinium ester and isophthalic acid 1,4-cyclohexylene The copolymer film of dimethylene ester is excellent in hydrolysis resistance. The present invention provides a protective sheet for a solar cell module, which comprises at least one layer of any of the above-mentioned terephthalic acid M_cyclohexylene dimethylene ester and isophthalic acid. The copolymer of the dicarboxylic acid 1,4·cyclohexylene di?? 8 is excellent in hydrolysis resistance of the solar cell module, and can be used for a long period of use of the solar cell module. The protective sheet is particularly preferably used as a back protective sheet for a solar cell module. The present invention provides a solar cell module having a filling layer including a solar cell element and surface protection disposed on a surface of the filling layer. a sheet, and a back protective sheet disposed on the back surface of the filling layer, At least one of the middle surface protection sheet and the back surface protection sheet has a copolymer film of any of the above-mentioned terephthalic acid 1, 'cyclohexylene dimethylene methyl ester and bismuth isophthalate, 4_cyclohexylene dimethylene methyl ester [Effect of the Invention] According to the present invention, it is possible to provide a film excellent in hydrolysis resistance, a protective sheet for a solar cell module, and a module for a solar cell.

32 201223995 [Brief Description of the Drawings] [Fig. 1] A cross-sectional view of a back surface protective sheet for a solar cell module according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing a solar battery module according to an embodiment of the present invention. [Fig. 3] A graph showing the change with time in the tensile strength retention ratio in the pressure cooker test of the films of Examples 1 and 2 and Comparative Examples 1 to 3. [Fig. 4] A graph showing changes with time in the tensile elongation retention rate in the pressure cooker test of the films of Examples 1 and 2 and Comparative Examples 1 to 3. [Fig. 5] A graph showing the results of X-ray diffraction of the films of Examples 1, 2 and Comparative Example 2. [Embodiment for Carrying Out the Invention] Hereinafter, preferred embodiments of the present invention will be described in detail. The copolymer film of bismuth subteronium phthalate, 4_cyclohexylene di decylene ester and 1,4-cyclohexylene di decylene phthalate of the present embodiment is composed of p-benzoquinone A resin composition of a copolymer of 1,4-cyclohexylidene dimethylene methyl ester and stilbene stilbene hydride and 4 cyclohexylene di decylene ester (hereinafter referred to as r copolymer A). Although the molar ratio of terephthalic acid ester to isophthalate is not particularly limited, but the hanging is 99.9: 0.1~5〇: 50, and 99: 1~7〇: 3〇 or better. . Further, the intrinsic viscosity (IV value) of the copolymer A is preferably 〇 〇 di / g, and more preferably 0 - 75 to 1.0 dl / g. The IV value was obtained as follows. Namely, the copolymer was dissolved in a mixed solvent of 60% by mass of phenol and 40% by mass of iota, 2,2-tetraethylene, in a concentration of 0-5 g/100 ml. Using a thin tube adhesive 33 201223995 ulometer, measure the drop time of the solution at 25 ° C in the thin tube viscometer, let it be ts. Also, measure the drop time of the solvent alone in the thin tube viscometer, and let it be to. The IV value is obtained by a calculation formula of IV value = [ln(ts/to)]/0.5. Furthermore, "In" represents the base of the natural logarithm. From the viewpoint of further improving hydrolysis resistance, the copolymer A content in the resin composition containing the copolymer A is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and further preferably 70 to 100% by mass is better. The resin composition containing the copolymer A may suitably contain an organic substance, an inorganic substance, and various additives other than the copolymer A. Examples of the organic substance other than the copolymer A include a cyclic or linear copolymer A oligomer, a monomer constituting the acid component of the copolymer A or a diol component, and a low molecular weight reactant derived therefrom, and a copolymer A. Other resins and various additives. Examples of the resin other than the copolymer A include thermoplastic polyester such as PET, PBT, PEN, propylene naphthalate, and polybutylene naphthalate, thermosetting polyester, nylon 6, and nylon. 66, nylon 11, nylon 12 and other thermoplastic polyamide, polycarbonate, polyacetal, polystyrene, ABS resin, polyamino phthalate, fluororesin, enamel resin, polyphenylene sulfide resin, A copolymerized resin such as cellulose, a polyphenylene ether resin or the like. Examples of the inorganic material include inorganic fillers such as glass fibers, carbon fibers, talc, mica, ashstone, kaolin, layered silicate, calcium carbonate, titanium oxide, and cerium oxide, inorganic lubricants, and polymerization catalyst residues. Further, the additive may be exemplified by an organic or inorganic dye or pigment, a matting agent, a heat stabilizer, a flame retardant, an antistatic agent, an antifoaming agent, a toner, an antioxidant, an ultraviolet absorber, a crystallization nucleating agent, and an increase White agent, lubricant, 34 201223995 Impurity trapping agent, tackifier, surface conditioner, etc. Among them, a trapping agent containing a heat stabilizer and a low molecular weight volatile impurity is preferred. The heat stabilizer is preferably a pentavalent and/or trivalent phosphorus compound or a hindered phenol compound, and the low molecular weight volatile impurity trapping agent is a polymer or oligomer of polyamine or polyesteramine. A low molecular weight compound having a guanamine or amine group or the like. The glass transition temperature of the copolymer A film of the present embodiment measured by the D Μ A method is 130 ° C or higher. The glass transition temperature measured by the DMA method is preferably 140 ° C or more, more preferably 150 ° C or more. Although the glass transition temperature measured by the DMA method is not particularly limited, it is usually below 200 ° C, preferably below 180 ° C, and preferably below 170 ° C, and at 160 ° C. The following is better. The DMA method refers to the following method. That is, the test piece was heated from room temperature at a rate of 5 ° C / minute, and the dynamic viscoelasticity and loss tangent of the test piece were measured using a viscoelasticity measuring device, and the glass transition temperature was obtained from the peak temperature of the loss tangent. Furthermore, the measurement frequency is 1 Hz. Further, the glass transition temperature of the copolymer A film of the present embodiment measured by the TMA method is 200 ° C or higher. The glass transition temperature measured by the Τ Μ A method is preferably above 210 ° C, and more preferably above 220 ° C, and more preferably above 230 ° C, and above 235 ° C. . Although the glass transition temperature measured by the TMA method is not particularly limited, it is usually below 260 ° C, and preferably below 255, and preferably below 250 ° C, and below 245 ° C. Better. The TMA method refers to the following method. That is, the test piece was heated from room temperature at a rate of 10 ° C /min, and the thermal expansion in the thickness direction was measured using a thermal analyzer. A graph showing the relationship between the temperature and the amount of thermal expansion was made. Then, pull out the wire on the curve before and after the glass transfer point, and the glass transition temperature can be obtained from the intersection of the wires. Further, the copolymer A film of the present embodiment was 22 in the X-ray diffraction. The maximum peak is in the range of $2 0 $24°. The copolymer A film of the present embodiment is excellent in hydrolyzability. Although it is not clear that the copolymer A film of the present embodiment has such a property, one of the reasons may be mentioned. The characteristics of the glass transition temperature and the maximum peak are related to the crystallization of the copolymer A in the copolymer A film of the present embodiment to some extent or more. Further, it is considered that the hydrolysis resistance is improved by the crystallization of the copolymer A to a certain extent or more (the crystallinity is preferably 20% or more and more preferably 30% or more). In the measurement based on JIS-K7127, the breaking strength of the copolymer a film of the present embodiment is preferably 80 MPa or more in the MD direction and the TD direction, and more preferably 90 MPa or more, and i MPa. The above is even better. In the measurement based on JIS-K7127, the elongation at break of the copolymer a film of the present embodiment is preferably 150 MPa or less in the MD direction and the TD direction, and more preferably 120 MPa or less, and 8 MPa. The following is even better. In the measurement based on ASTM D-149, the dielectric breakdown voltage of the present embodiment is preferably 90 kV/mm or more, and more preferably, for example, more than a claw, and more preferably 130 kV/mm or more. In the measurement by the TMA method (50 to 1 Torr.), the thermal expansion coefficient (CTE) of the present embodiment is 80 ppm/° C. or less in both the MD direction and the TD direction.

36 201223995 is better and is better at 6〇pPm/°C, and is better at 40ΡΡπιΛ: below. The thickness of the copolymer ruthenium film of the present embodiment can be appropriately selected depending on the thickness of the back surface protective sheet for a solar cell module and the required performance, but it is preferably 10 Å to 500 ζ πι, and is 2 〇. #m~3〇〇"m is better and is better at 30&quot;m~200&quot; m. By setting it in such a range, the manufacture of the film will be inferior to the valley, and will provide two strengths and rigidity. The operability or the post-processability are made easy. The thickness unevenness is preferably within ±1〇0/〇, and is preferably within 7〇/〇 of the soil, and more preferably within ±5%. The copolymer A film according to the present embodiment can be produced by the following method. First, 'preparation of a copolymer A resin (for example, agglomerates) to be used as a raw material. Copolymer A resin can be obtained by using ruthenium, 4_ ring Hexane dimethanol, terephthalic acid, and isophthalic acid are produced by polycondensation by a well-known method. Further, for example, &amp; 'combined A pellets are also commercially available from Eastman Corporation, for example. The name "Eastman Copolyester 13319" is sold in the market. Then, the copolymer A resin is melted by heating, and if necessary, an additive is added to obtain a resin composition containing the copolymer A. Further, this resin composition was formed into a film. The method of forming a film includes a melt molding method in which a resin composition containing the copolymer A is extruded by a die in a molten state, and a solution obtained by dissolving a resin composition in a solvent is applied to the support. A solution casting method or the like which is followed by drying the solvent. Among them, the melt forming method which is excellent in productivity and environmental suitability and which can obtain a film in a single step is preferable. The melt forming method is preferably a T-die or a 丨-type mold 37 201223995, a water-cooled and air-cooled aeration method (4) ati〇n). The above copolymer A film of the present embodiment can be obtained by stretching the formed unstretched copolymer eight film. The stretching condition, the stretching method, and the like are not particularly limited as long as they are appropriately adjusted within a range in which the glass transition temperature can be obtained and a range in which the maximum peak value can be obtained in the angle range defined by the calender diffraction. For example, s, the extending direction may be - the axis may be two axes, but the two axes are preferred. The stretching method is not particularly limited, and various methods such as roll stretching and tenter stretching can be used singly or in any combination. The stretching ratio is also not particularly limited. For example, it can be set to 2 times to 5 times in the MD (machine direction) direction and 2 times to 5 times in the TD (transverse direction) direction. Fig. 1 shows an embodiment of the configuration of the back protective sheet for a solar cell module of the present invention (hereinafter, simply referred to as "back protective sheet"). The back surface protective sheet 11 has a structure in which heat-sensitive film base materials 30 and 32 are laminated on both surfaces of the gas barrier film 2A. The gas barrier film 20 is provided with a vaporized layer 12 composed of an inorganic compound on one surface of the substrate 10. As the substrate 10, the above copolymer A film can be used. The heat-resistant film substrates 3A and 32 used in the present embodiment may be any heat-resistant one, and may be a fluorine-based substrate selected from the group consisting of polyethylene terephthalate (PET). Film or vinyl fluoride resin (pVF) film, polyvinylidene fluoride resin (PVDF) film, trifluorochemical vaporized vinyl resin (pCTFE) film, ethylene tetrafluoroethylene copolymer (ETFE) film, polytetrafluoroethylene (PTFE) 38 201223995 Membrane, tetrafluoroethylene-dibenzopyrene-based copolymer (pfa). Further, the copolymer A crucible may be suitably used as the heat-resistant film substrates 30 and 32. The thickness of the film base materials 30 and 32 is not particularly limited, and is preferably, for example, 3 to 2 Å A m and more preferably 6 to 3 〇 y m . The material of the vapor-deposited layer 12 is not particularly limited, and examples thereof include a mixture of two or more kinds of alumina, oxidized oxide, tin oxide, oxidized town, oxidized product, and material. The thickness of the vapor-bonding layer is not particularly limited, and is preferably 5 to fine, and more preferably 10 to 150 nm. The method of laminating the gas barrier film 2 of the present embodiment and the heat-resistant film substrates 30 and 32 may be, for example, a dry laminate layer method. The dry laminating agent will produce a material that is degraded by the use of the outside of the house for a long period of time, and the binder does not change, and it is desirable to respond to high heat resistance, moist heat resistance, etc. A resin or the like which is a main component of a carrier constituting an adhesive, such as a crosslinked structure in which a three-dimensional mesh shape can be formed by crosslinking or even hardening. Specifically, the adhesive constituting the above-mentioned interlayer adhesive layer is preferably formed by a reaction energy composed of heat, light or the like in the presence of a curing agent or a crosslinking agent to form a crosslinked structure. For example, 5, an isocyanate i-based hardener or cross-linking such as an aliphatic or alicyclic isocyanide-based aromatic isocyanic acid, such as a two-component-curing polyamino phthalic acid m-clay In the presence of the agent, the back surface protective sheet for a solar cell module excellent in heat, properties, moisture resistance, and the like is produced by using the reaction energy composed of heat or light to cause lamination. 39 201223995 In the above-mentioned adhesive, an aliphatic isocyanurate may be, for example, anthracene, 6-hexamethylene diisocyanate (HDI); an alicyclic isocyanate may be, for example, isophorone diisocyanate (IPDI); an aromatic system As the isocyanate, for example, methylphenyl diisocyanate (TDI), diphenylmethane diisocyanate (1), n-naphthyl diisocyanate (NDI), benzalidine-isophthalic acid (T) can be used. 〇Di), benzodimethyl diisocyanate (XDI), and the like. Further, in the above-mentioned adhesive, an ultraviolet absorber or a light stabilizer may be added in order to prevent ultraviolet rays or the like. Although the amount of use varies depending on the particle shape, density, etc., it is preferably about 10% by weight. The above-mentioned adhesive can be applied by, for example, a roll coating method, a gravure coating method, an anastomosis coating method, or the like, a coating method, a printing method, or the like, and the coating amount thereof is about 2 to 20 g/m 2 (dry state), and Good hope is in the range of 3~i〇g/m2 (dry state). The back surface protective sheet for a solar cell module of the present invention thus obtained has the above-mentioned copolymer A film, and is therefore particularly excellent in hydrolysis resistance. Therefore, such a back protective sheet for a solar cell can protect a solar cell for a long period of time and is inexpensive. Further, the configuration of the back protective sheet for a solar cell module is not limited to the above configuration. For example, a transparent undercoat layer for improving the adhesion therebetween may be provided between the vapor deposition layer 12 and the substrate 1A. The resin of the transparent undercoat layer may be exemplified by a decane coupling agent or a hydrolyzate thereof, and a complex of a polyalcohol and an isocyanate compound. As the decane coupling agent, for example, ethyl trimethoxy decane or vinyl three can be used.

40 201223995 methoxy decane, propyl propyl decyl dimethoxy decane, τ-chloropropyl trioxoxane, glycidoxypropyl trioxane, r-methyl propylene oxypropyl trioxane One to two or more kinds of decane coupling such as decane or methacryloxypropyl decyl decyl oxane or a hydrolyzate thereof. Further, there are also, for example, r-isocyanate propyl triethoxy decane, 7-isocyanate propyl trimethoxy decane, including isocyanate groups; 7-mercaptopropyl triethoxy oxane-containing sulfhydryl groups or τ-aminopropyl groups Triethoxylate, Τ-aminopropyltrioxoxalate, N-/3-(aminoethyl)-7-aminopropyltriethoxylate, oxime-phenyl Aminopropyl trioxoxanes generally contain an amine group. Further, it may be an epoxy group such as r-glycidoxypropyltrimethoxysilane or s-(3,4-epoxycyclohexyl)ethyltrioxane or a vinyltrioxane. The decane or the vinyl (/3-methoxyethoxy) decane is equivalent to the addition of a hydrazine coupling agent, an alcohol or the like, and the like, and one or more of them may be used. The polyalcohol can be suitably used, for example, by polymerizing an acrylic acid derivative monomer such as ethyl methacrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate or hydroxybutyl methacrylate, or adding styrene. An acrylic polyol or the like obtained by copolymerizing other monomers or the like. As the isocyanate compound, for example, an aromatic phenyl diisocyanate (TDI) or diphenylmethane diisocyanate (MDI), an aliphatic xylene diisocyanate (XDI) or hexamethylene diisocyanate (HMDI) can be used. And a monomer, a polymer, a derivative, etc., etc., and one type or two or more types can be used. The thickness of the transparent undercoat layer is not particularly limited, but is preferably 0.001 to 2/m, and more preferably 0.03 to 0.5 #m. 41

Further, a protective film layer having a gas P and having a property of X can be further disposed between the vapor-deposited layer 12 and the film substrate 32. The protective film layer can be applied to the vapor-deposited layer 12 by, for example, applying a coating liquid containing a water-soluble cerium molecule, a metal alkoxide or a hydrolyzate thereof, and water or water as a solvent. Come up to form. Examples of the water-containing polymer include polyvinyl alcohol, polyvinyl pyrrolidine, powder, sulfhydryl cellulose, carboxymethyl cellulose, and sodium alginate. Examples of the metal alkoxide include tetraethoxysilane, aluminum triisopropoxide, and the like. , the vapor deposition layer 12 may be formed on both surfaces of the substrate 10. At this time, the transparent undercoat layer or the protective film layer may be formed on the plating surface of the square. Further, the back surface protective sheet 11 for a solar cell module may not have the film substrate 3〇, 32#_' or both, or may be composed only of the substrate 10. Next, a back-side protection sheet solar battery module using the solar cell of the present invention will be described. Fig. 2 is a schematic cross-sectional view showing a layer configuration of an embodiment of a solar cell module 1 having a back Φ' and a vine of a solar cell of the present invention. The solar cell module of the present embodiment is configured as a solar cell module 4 surface protection sheet 6G, a front side filler layer 51, and a solar cell element 5G and a back side of the photovoltaic device in which the wiring 52 is disposed. The filler layer 53 has a configuration in which the front side correction-removing property of the substrate 11 is arranged on the substrate 3, and the back side of the anode and the tilting group is filled (four). These two materials can be integrated by, for example, vacuum suction or the like, and the above-mentioned respective layers of the wire-body formed body can be thermally s formed by the press-fitting method. The group 1 (10) can also be provided with, for example, a frame (not shown). 201223995 The surface protection sheet 60 for a solar cell module constituting the solar cell module described above has the transparency of sunlight, insulation, and the like, and has the characteristics of finance, finance, finance, water, and defense. Excellent properties such as wetness, antifouling properties, and other physical and chemical strength, toughness, etc., and extremely high durability. In addition, due to the protection of solar cell components as photovoltaic elements, scratch resistance Sex, shock absorption, etc. must be excellent. Specifically, a well-known glass plate or the like can be used, and for example, a polyamine resin (various nylon), a polyester resin, a cyclic polyolefin resin, or a polystyrene resin can be used. Various resin films or sheets such as a methyl methacrylate resin, a polycarbonate resin, an acetal resin, and the like may be used, and the copolymer A may be suitably used. As the film or even the sheet of the above resin, a stretched film or a sheet which is biaxially stretched can be used. Further, the thickness of the resin film or the sheet may be a minimum thickness required for holding strength, rigidity, stiffness, etc., and if it is too thick, there is a disadvantage that the cost is increased, and if it is too thin, strength, rigidity, and strength are obtained. Stiffness and so on will be lower and less. In the present embodiment, the thickness of the resin film or the sheet is preferably 12 to 200 / / m, and more preferably 25 / _ to 150 / zm. The filler layer 51 laminated under the surface protection sheet 60 for a solar cell module constituting the solar cell module is required to have transparency because it is incident on the surface protection sheet 60 and is absorbed by the sunlight. It is also necessary to have the adhesion of the surface protection sheet and the back surface protection sheet. Further, in order to exhibit the function of maintaining the smoothness of the surface of the solar cell element as a photovoltaic element, it is necessary to have thermoplasticity, and further, from the viewpoint of protecting the solar cell element as a photovoltaic element, scratch resistance and impact absorption Sex and so on must be excellent. 43 201223995 Specifically, the aforementioned filler layer may be, for example, an ethylene-vinyl acetate copolymer, an ionic polymer resin, an ethylene acrylic acid, or an acid-modified poly-saturated resin, a polyvinyl butyral resin, an anthrone. Resin, epoxy resin,

(A) type of (meth)acrylic resin and other resins, to two or more kinds of Kun A products. In the present embodiment, in order to improve the heat resistance, the light resistance, the water resistance, the weather resistance, and the like, the resin constituting the filler layer can be arbitrarily added and mixed in a range that does not impair the transparency thereof, for example, cross-linking. Agents, thermal anti-deuteration agents, light stabilizers, UV absorbers, photo-oxidants and other additives. In addition, in the present embodiment, in consideration of the weather resistance performance surface and the price surface such as water resistance, heat resistance, and water resistance, the ethylene-vinyl acetate-based resin is preferable as a filler for the sunlight incident side. . Further, the thickness of the filler layer is preferably 2 〇〇 to 1 〇〇〇 &quot; m, and more preferably 35 〇 to 6 〇〇 Vm. The solar cell element 5〇' which is a photovoltaic cell component constituting a solar cell module can be used as far as is known, for example, a single junction (four) type solar cell element, a crystallization, a 5th solar cell element, etc. A solar electronic component, an amorphous tantalum solar cell element composed of a single junction type or a tandem structure type, a ΙΙΙ-ν compound semiconductor such as gallium germanium (GaAs) or indium phosphorus (InP), and a known electronic component. Group II-VI compound semi-solar electronic components such as hoof (CdTe) or copper indium citrate (cuinse2), organic solar cell elements, and the like. Further, a film polycrystalline solar cell element, a thin film microcrystalline solar cell element, a mixed material of a thin film crystal sand solar cell element and an amorphous sand solar cell element, or the like can be used. The back side 44 201223995 surface side filler layer 53 underlying the photovoltaic element of the solar cell module is laminated, and the surface side of the surface protection sheet is laminated on the surface of the solar cell module and the back surface protection sheet. &amp; s 51 the same material. It is also necessary to have a solar cell to turn "^ ^ 保持 keep as a photovoltaic elemental 'in addition' from the protection as a photovoltaic month, the work must have thermal plasticity, to trace resistance, (four) π, hit the sun The viewpoint of the battery component is as good as the above-mentioned present invention: it must be excellent. At least one battery pack of the moon protection and surface protection sheet, due to the above-mentioned back protection

Membrane, so the back protective sheet or surface: the use of the copolymer A is higher than the use of the conventional poly-p-benzophenone, '7. Therefore, the phase of the bismuth ethylene glycol (PET) film or the polyphthalic acid dicarboxylic acid:::: the case of a holding - the electric two is not limited to the above-mentioned composition, but can be various components: for example In other words, the 'back protection sheet Η can be used as various constituents as described above. If necessary, it may be a filling layer having a solar cell element%, a surface protective sheet 6 disposed on the surface of the filling layer, a back protective sheet 11 disposed on the back surface of the filling layer, and a surface protective sheet 6 and a back surface protection. At least one of the sheets u contains the above copolymer A film. [Examples] Hereinafter, the contents of the present invention will be more specifically described by way of examples and comparative examples. Further, the present invention is not limited by the following examples. The raw materials of the film were thickened using the following resin groups. Furthermore, 'PEN is polyethylene naphthalate. (1) Copolymer A (manufactured by Eastman Co., Ltd., trade name: Eastman 45 201223995

Copolyester 13319) (2) PEN (manufactured by Teijin DuPont Film Co., Ltd., trade name: Teonex Q51) (3) 1,4-cyclohexanedimethanol · 2,2,4,4-tetradecyl-1,3- Cyclobutanediol • The monocarboxylic acid polycondensate (Eastman, trade name: Eastman)

Tritan Copolyester FX200) (hereinafter referred to as "copolymer b") [Example 1] Copolymerization of copolymer A (agglomerate) by melt extrusion, and further by biaxial stretching to obtain a thickness of 50 / / m The copolymer A film was stretched. [Example 2] A thickness of 100 ((/111 copolymer A film) was obtained in the same manner as in Example j except that the stretching ratio was changed to 1 Å in m. [Comparative Example 1] The PEN (agglomerate) was film-molded by melt extrusion, and an extended pen film having a thickness of 25/zm was obtained by biaxial stretching. [Comparative Example 2] Copolymerization of a copolymer A by a melt extrusion (agglomerate) Thus, an unstretched copolymer eight film having a thickness of 110#m was obtained. [Comparative Example 3] The copolymer B (agglomerate) was deuterated by melt extrusion to obtain an unstretched copolymer B film having a thickness of 100/m. &lt;Various physical properties&gt; The films of Examples 1 and 2 and Comparative Example 3 were measured for breaking strength, elongation at break, glass transition temperature, charm, dielectric breakdown voltage, specific gravity, and thermal expansion coefficient. Measurement methods and measurements of each measurement The value is shown in Table 2.

46 201223995 [Table 2] Elongation at break (%) Glass transition temperature (.〇 Melting point (°〇) Insulation breaking (kV/mm) Specific gravity Thermal expansion coefficient [50~10QoC](ppm/°C)

Item Breaking Strength (MPa) &lt;Hydrolysis Test&gt; The films of Examples 1 and 2 and Comparative Examples 1 to 3 were subjected to a pressure steel test (120 ° C, 100% RH (relative humidity), 2 atm). The tensile strength retention and the tensile elongation retention ratio after 5 hours, 100 hours, 150 hours, and 200 hours were measured for each film. The results are shown in Figures 3 and 4. The film of Examples 1 and 2 had a slower decrease in the tensile strength retention ratio and the tensile elongation retention ratio as compared with the films of Comparative Examples 1 to 3. &lt;Measurement of crystallinity&gt; The films of Example 1, Example 2, and Comparative Example 2 were subjected to powder X-ray diffraction by CuKa ray, and the diffraction pattern was confirmed and the crystallinity was calculated 47 201223995. The measurement method and measurement conditions are as follows. Target ^ Cu, x light reward Current: 40mA, X-ray tube voltage: 45kV, scanning range: 2 θ = 4~65, step size: 2 0 = 0.01671. Average time/step size: l〇.160s, fixed divergence Slot: 1/2. Rotation speed: 60 rotations per minute, crystallinity analysis: Hermans method, pre-treatment: none. The relationship between the angle 2 Θ and the diffraction intensity by the incident direction and the reflection direction of the X-ray is shown in Fig. 3. In the film of Example 2, although a clear and sharp maximum peak was observed in the range of 22 ° S 2 6 &gt; $ 24 °, the film of Comparative Example 2 did not confirm a sharp peak at any position, and It was found to be amorphous. Further, the crystallinity of the films of Example 1 and Example 2 was determined based on Fig. 3, which were 42.8% and 39.7%, respectively. Further, in Examples 1 and 2, the peak of the second intensity appears at 2 (9 = 16 to 17°, and the peak of the third intensity appears at 20 = 19 to 2 〇. The peak intensity ratio is the second intensity. The peak value/maximum peak value. [Symbol description] 11...Solar battery module back protection sheet, 10...substrate, 12...steam key layer, 20...gas barrier film, 3〇, 32.·. Film substrate, 5 〇...solar cell element '51...surface side filler layer, 52...wiring, 53...back side filler layer, 6G·..solor frequency_surface protection sheet , just... solar battery module. [Contents of patent request] [Request item 1] Kind of p-Benzene-formic acid i, 4. Stretched cyclohexyl dimethylene acetonate and isophthalic acid, Shen * Jiji _ The copolymer film of the melon is 'glassy measured by the method

48 201223995 The glass transfer temperature is above 130 °C. [Request 2] The copolymer film of M-cyclohexylene dimethylene terephthalate and 1,4-cyclohexylene dimethylene methyl isophthalate as in Item 1 of the claim The glass transition temperature measured by the TMA method is above 200 °C. [item 3 of the request] Copolymerization of 1,4-cyclohexylene dipyridinium terephthalate with 1,4-cyclohexylene dipyridinium isophthalate as claimed in item 1 or 2 of the claim The film, in X-ray diffraction, has the largest peak in the range of 22° $2 0 $24°. [Requirement Item 4] A copolymer film of 1,4-cyclohexylene dimethylene terephthalate and 1,4-cyclohexyl dipyridinium isophthalate, which is measured by TMA method The resulting glass transition temperature is above 200 °C. [item 5 of the request] Copolymer of 1,4-cyclohexylene dipyridinium terephthalate and 1,4-cyclohexylene dimethylene ester of isophthalic acid as in item 4 of the claim The membrane, in X-ray diffraction, has a maximum peak in the range of 22° $2 0 $24°. [Claim Item 6] A copolymer film of 1,4-cyclohexylene dipyridinium terephthalate and 1,4-cyclohexylene dipyridinium isophthalate, which is wrapped in X-rays. Shot with a maximum peak in the range of 22 ° $ 2 0 $ 24 °. [item 7 of the request] 1,4-benzoic acid 1,4 -cyclohexylidene dimethylene phthalate and isophthalic acid 1,4-cyclohexyldiyl as described in any one of claims 1 to 6. Methylene ester copolymer 49 201223995 film, which is used for surface or back protection of solar cell modules. [Claim Item 8] A protective sheet for a solar cell module comprising at least one layer of terephthalic acid 1 &gt; 4_cyclohexylene dimethylene ester according to any one of claims 1 to 6 A copolymer film of 1,4-dicyclohexyl dimethylene phthalate. [Claim Item 9] A back protective sheet for a solar cell module, comprising at least one layer of terephthalic acid M_cyclohexylene dimethylene phthalate or the like according to any one of claims 1 to 6. The present phthalic acid 1,4-stretched copolymer film of hexyl dithylene vinegar. [Claim Item 10] A solar cell module comprising a filling layer including a solar cell element, a surface protection sheet disposed on a surface of the filling layer, and a back surface protective sheet disposed on a surface of the filling layer, and the foregoing At least one of the surface protective sheet and the foregoing back protective sheet has 1,4-cyclohexyl dimethylene phthalate and bismuth isophthalate, as in any one of claims 6 to 4, 4- A copolymer film of cyclohexyldipyridinium ester is stretched. [Brief Description of the Drawings] [Fig. 1] A cross-sectional view of a back protective sheet for a solar cell module according to an embodiment of the invention of the present invention (Japanese Patent Application No. 2010-192520). [Fig. 2] A schematic cross-sectional view of a solar battery module according to an embodiment of the present invention. [Fig. 3] is a graph showing the change of the tensile strength retention rate in the dynamic steel test of the film of Example 2 and the comparative example of the basic application of the present application. [Fig. 4] is a graph showing changes with time in the tensile elongation retention rate in the pressure cooker test of the films of Examples i and 2 and Comparative Examples 1 to 3 of the basic application of the present application. Fig. 5 is a view showing the results of X-ray diffraction of the films of Examples 1, 2 and Comparative Example 2 of the basic application of the present application. [Description of main component symbols] 11... Back surface protective sheet 51 for solar cell module... Surface side filler layer 10... Substrate 12: Steamed layer 20: Gas barrier film 30, 32 · Film substrate 50. .. solar battery element 52... wiring 53... back side filler layer 60... solar cell module surface protection sheet 100... solar battery module 51

Claims (1)

201223995 VII. Patent Application Range: 1. A polyester film comprising a biaxially oriented polyester film comprising a polyester resin obtained by at least condensing a diol component and a dicarboxylic acid component, wherein the diol component comprises a general formula (1) represented by a diol compound: [Chemical 1] ch2oh (wherein, ring A is a cyclohexane ring or a benzene ring; n1 is an integer of 0 to 4; and R1 is selected from the group consisting of an argon atom and an alkyl group having 1 to 3 carbon atoms, and when nl is When the integer is 2 to 4, the 2 to 4 R1 groups are each independently selected from the group); wherein the dicarboxylic acid component comprises the dicarboxylic acid compound represented by the general formula (II): (wherein, when ring A is a cyclohexane ring, ring B is a benzene ring; when ring A is a benzene ring, ring B is a cyclohexane ring; n2 is an integer of 0 to 4; R2 is selected from a group consisting of a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, and when n2 is an integer of 2 to 4, the 2 to 4 R2 systems are each independently selected from the group; the two R3 systems are each independently Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; wherein the polyester film is heated from 50 ° C to 1 〇〇 ° C under a tensile load of 5 gf and a temperature increase rate of 10 ° C / min 52 201223995 The subsequent thermal expansion coefficient is 50 ppm/° C. or less, and the absolute value of the thermal shrinkage of the polyester film at 150° C. is less than 2.0%. 2. The polyester film of claim 1, wherein the ring A is a cyclohexane ring and the ring B is a benzene ring. 3. For the polyester film of claim 1 or 2, wherein the two hydroxyindoles on ring A are in the form of 1,3-substituted or 1,4-substituted, and the two in the ring B are -COOR3 The relationship between the 1,3-substituted or 1,4-substituted groups. 4. The polyester film according to any one of claims 1 to 3, wherein the diol component comprises a 1,4-substituted relationship of two hydroxyindole groups on the ring A in the above formula (I). a 4-diol compound; and the dicarboxylic acid component comprises: a 1,4-dicarboxylic acid compound in which two 2-COOR3 groups on the ring B in the above formula (II) are in a 1,4-substituted relationship; The two -COOR3 groups on the ring B are 1,3-dicarboxylic acid compounds in a 1,3-substituted relationship. 5. The polyester film of claim 4, wherein the diol component is composed of the 1,4-diol compound, and the dicarboxylic acid component is a 1,4-dicarboxylic acid compound and The 1,3-dicarboxylic acid compound is composed of the above. 6. The polyester film of claim 4, wherein the 1,4-diol compound is 1,4-cyclohexanedimethanol and the 1,4-dicarboxylic acid compound is terephthalene An acid, and the aforementioned 1,3-dicarboxylic acid compound is isophthalic acid. 7. A polyester film comprising a biaxially oriented polyester film of a polyester resin obtained by polycondensing 1,4-cyclohexanedimethanol with p-benzoquinone 53 201223995 acid and isophthalic acid The polyester film has a thermal expansion coefficient of 50 ppm/°c or less after heating from 5 〇t:100° C. under a tensile load of 5 gf and a temperature increase rate of 10 〇C/min. The polyester film according to any one of claims 1 to 7 wherein the biaxially oriented polyester film system contains the film of the aforementioned polyester resin. At least two-axis extension processing is performed. 9. The polyester film of claim 8 wherein the biaxial extension is simultaneously-axially extended. The polyester film according to any one of claims 1 to 9 has a thermal expansion coefficient of 45 ppm/°c or less and an absolute value of the heat shrinkage ratio of less than 9%9%. The polyester film according to any one of claims 1 to 10, wherein a difference between the MD direction and the TD direction of the coefficient of thermal expansion is 3 〇ppm/〇c or less, and the MD direction and the td direction of the shrinkage ratio are The absolute value of the difference is below 15 〇 / 0. Such as Shen. The polyester film of any one of the inventions of the present invention, which has a tensile strength retention rate of more than 〇% after an hour of oven test at 2 ° C. 13· For example, in the Shen-Hui patent range from i to 12, it has a glass transition temperature of 2 〇 0 °C or more. The polyester film according to any one of claims 1 to 13, which further contains an antioxidant. 54 201223995 15. The polyester film of claim 14, wherein the antioxidant is selected from the group consisting of a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant. 16. The polyester film of claim 15, wherein the phenolic antioxidant, the phosphorus-based antioxidant, and the sulfur-based antioxidant are each contained in an amount of 0.05 to 2.0% by weight based on the polymer component. The polyester film according to any one of claims 1 to 16, which is used as a heat resistant film. The method for producing a polyester film according to any one of claims 1 to 17, wherein after the precursor film containing the polyester resin is produced, the precursor film is subjected to at least biaxial stretching treatment. Heat treatment step. 55