WO2012077469A1 - Film de résine et son procédé de fabrication - Google Patents

Film de résine et son procédé de fabrication Download PDF

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Publication number
WO2012077469A1
WO2012077469A1 PCT/JP2011/076319 JP2011076319W WO2012077469A1 WO 2012077469 A1 WO2012077469 A1 WO 2012077469A1 JP 2011076319 W JP2011076319 W JP 2011076319W WO 2012077469 A1 WO2012077469 A1 WO 2012077469A1
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Prior art keywords
polymer
mass
layer
resin film
group
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PCT/JP2011/076319
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English (en)
Japanese (ja)
Inventor
畠山　晶
和史 古川
ゆきえ 渡邊
一路 尼崎
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富士フイルム株式会社
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Publication of WO2012077469A1 publication Critical patent/WO2012077469A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/049—Protective back sheets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a resin film and a manufacturing method thereof.
  • inorganic and organic ultraviolet absorbers are known.
  • organic ultraviolet absorbers have a higher degree of design freedom in compound structure than inorganic ultraviolet absorbers, and therefore, various absorption wavelengths can be obtained by devising the molecular structure.
  • various organic ultraviolet absorbers have been proposed, and as one example, a triazole ultraviolet absorber has been disclosed (for example, see JP-T-2002-524452).
  • a triazole ultraviolet absorber has been disclosed (for example, see JP-T-2002-524452).
  • trisaryl-s-triazine having an alkoxy group and a hydroxy group at specific positions see, for example, Japanese Patent No. 3965631).
  • those having a maximum absorption wavelength in the long wave ultraviolet region tend to have poor light resistance, and the ultraviolet shielding effect decreases with time. For this reason, in a usage form that is left for a long time under ultraviolet light exposure, the shielding effect cannot be maintained, so that the long-term durability cannot be greatly improved.
  • a solar cell module is generally a transparent glass substrate disposed on the side on which sunlight is directly incident, and a so-called back sheet for protecting the back surface disposed on the side opposite to the side on which sunlight is incident (back side). Between the two solar cells. The space between the glass and the solar battery cell and the space between the solar battery cell and the back sheet are generally sealed with a sealing agent such as EVA (ethylene-vinyl acetate) resin.
  • EVA ethylene-vinyl acetate
  • the back sheet has a function of preventing moisture from entering from the back surface of the solar cell module, and polyester is used from the viewpoint of cost and the like.
  • a backsheet using polyester for example, a sheet having a polyester support provided with a light-reflective colored layer or a layer that easily adheres to a sealing material is known (for example, Japanese Patent Application Laid-Open No. 2007-2007). 118267).
  • UV-A long wave ultraviolet
  • UV absorbers are generally used by mixing with resin, etc.
  • the thickness is limited to about several tens of ⁇ m.
  • an ultraviolet absorber In order to impart ultraviolet absorbing ability in the long wavelength region, an ultraviolet absorber must be contained at a high concentration. However, if it is simply contained in a high concentration, there is a problem that the ultraviolet absorber is liable to precipitate, causes bleed out during long-term use, and deteriorates odor.
  • benzophenone-based and benzotriazole-based UV absorbers known in the past often have low solubility, so there is a problem that it is actually difficult to form a coating film well by the conventional coating method. .
  • the present invention has been made in view of the above, a method for producing a resin film that forms a coating film having a good coating surface shape and excellent adhesion between adjacent organic materials, and a long-wave ultraviolet light around 400 nm.
  • An object of the present invention is to provide a resin film that has an ultraviolet shielding effect in a wide wavelength region including the (UV-A) region, exhibits excellent light resistance, and has a good surface shape and excellent adhesion of the coating layer. The goal is to achieve this.
  • R 1a , R 1b , R 1c , R 1d , and R 1e each independently represent a monovalent substituent other than a hydroxy group, and at least one of R 1a to R 1e Represents a substituent having a Hammett's rule ⁇ p value of 0.3 or more.
  • the substituents represented by R 1a to R 1e may be bonded to each other to form a ring.
  • R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n , and R 1p each independently represent a hydrogen atom or a monovalent substituent, and the substituents are bonded to each other A ring may be formed.
  • R 1a , R 1c , and R 1e in the general formula (1) represent a hydrogen atom, and at least one of R 1b and R 1d is an alkoxycarbonyl group (COOR n [R n : alkyl group]), ⁇ 1> which is a nitro group (NO 2 ), a cyano group (CN), a fluoroalkyl group (R f ), a sulfonic acid or an alkali metal salt thereof (SO 3 H or SO 3 M [M: alkali metal]) It is a manufacturing method of the resin film of description.
  • the concentration of the compound represented by the general formula (1) in the coating liquid is 3% by mass to 9% by mass with respect to the total mass of the coating liquid, and the coating liquid of the binder polymer It is a manufacturing method of the resin film as described in said ⁇ 1> or ⁇ 2> whose density in the inside is 6 mass% or more and 25 mass% or less with respect to the total mass of a coating liquid.
  • the method includes a step of preparing a dispersion by dispersing the compound represented by the general formula (1) in a solvent, In the polymer layer forming step, any one of the above ⁇ 1> to ⁇ 3>, wherein the coating liquid containing the compound represented by the general formula (1) in a dispersed state is applied using the dispersion liquid. It is a manufacturing method of the resin film as described in one.
  • ⁇ 5> The method for producing a resin film according to any one of ⁇ 1> to ⁇ 4>, wherein a polymer selected from a fluorine-based polymer and a silicone-based polymer is contained as at least one of the binder polymers.
  • ⁇ 6> The method for producing a resin film according to any one of ⁇ 1> to ⁇ 5>, wherein the coating liquid further contains a crosslinking agent that crosslinks the binder.
  • ⁇ 7> It is a manufacturing method of the resin film as described in said ⁇ 6> whose said crosslinking agent is a carbodiimide type crosslinking agent and / or an oxazoline type crosslinking agent.
  • ⁇ 8> The resin film according to ⁇ 6> or ⁇ 7>, wherein the content of the crosslinking agent in the polymer layer is 0.5% by mass or more and 40% by mass or less with respect to the binder polymer. It is a manufacturing method.
  • ⁇ 9> The method for producing a resin film according to any one of ⁇ 1> to ⁇ 8>, wherein the coating liquid further contains a solvent, and 50% by mass or more of the solvent is water.
  • the support is a polyester base material.
  • ⁇ 12> In any one of the above items ⁇ 1> to ⁇ 11>, including a protective layer forming step of forming a protective layer by applying a coating solution for a protective layer containing at least the binder polymer on the polymer layer It is a manufacturing method of the resin film of description.
  • ⁇ 13> Any one of the above ⁇ 1> to ⁇ 12>, which is used as a solar cell backsheet provided on a side opposite to a side on which solar light is incident on a battery side substrate in which a solar cell element is sealed with a sealing material It is a manufacturing method of the resin film as described in any one.
  • the manufacturing method of the resin film which forms the coating film excellent in the adhesiveness between the organic materials with favorable coating surface shape and adjacent can be provided.
  • a film can be provided.
  • the method for producing a resin film of the present invention comprises a step of forming a polymer layer by applying a coating liquid containing at least a compound represented by the general formula (1) shown below and a binder polymer on a support (hereinafter referred to as a polymer layer). It may also be referred to as a “polymer layer forming step.”), And if necessary, further provided with other steps such as a drying step for heating and drying the coated film after coating. May be.
  • the triazole-based compound has low solubility and has been conventionally considered to be difficult to apply uniformly.
  • a compound having a specific structure as an ultraviolet absorber hereinafter sometimes abbreviated as UV agent
  • UV agent an ultraviolet absorber
  • Using the compound in a support instead of kneading it into the support, it is formed by coating a mixed solution containing the compound together with a binder polymer, so that a good coated surface can be obtained and the coating amount is small (thin film). Since the UV agent is unevenly distributed in the vicinity of the support surface, excellent light resistance is maintained over a long period of time. In particular, the ultraviolet shielding effect is excellent in a wide range including a long wave ultraviolet (UV-A) region around 400 nm. Moreover, since the coating amount of the compound having a specific structure can be reduced, it is possible to form a coating film having excellent adhesion with an adjacent organic material (a support when applied to the support surface).
  • UV-A long wave ultraviolet
  • the polymer layer in the present invention is not particularly limited and may be any layer provided on the support depending on the application.
  • the resin film of the present invention is applied to the use of a solar cell and used as a so-called back sheet for protecting the back surface disposed on the side opposite to the side on which sunlight directly enters (back side)
  • Easy adhesion to improve the adhesion of the polymer layer to (1) a colored layer containing a colorant such as a pigment and a battery-side substrate (especially a sealing material such as EVA for sealing the solar cell element) provided with the solar cell element.
  • a back surface protective layer provided on the side not facing the battery side substrate.
  • the colored layer includes, for example, a white pigment, a reflective layer that reflects light that has passed through the solar cells and reaches the back sheet and returns to the solar cells, and a design layer that enhances the decorativeness of the appearance. It is.
  • a coating solution is applied on a support to form a polymer layer.
  • a coating solution is applied on a support to form a polymer layer.
  • the dry thickness of the polymer layer is preferably 0.5 to 10.0 ⁇ m.
  • the thickness of the polymer layer is 0.5 ⁇ m or more, it exhibits a higher ultraviolet shielding effect with a thinner film, exhibits higher durability performance, and has good adhesion to the polymer support.
  • the thickness of the polymer layer is 10.0 ⁇ m or less, the surface shape becomes better, and the adhesive strength between the adjacent layer and the polymer substrate is excellent. That is, when the thickness of the polymer layer is in the range of 0.5 to 4.0 ⁇ m, the durability and planarity of the polymer layer are compatible, and the adhesion between the polymer substrate and the polymer layer is superior.
  • the thickness of the polymer layer is particularly preferably in the range of 1.0 to 5.0 ⁇ m.
  • the polymer layer may be provided as a single layer or may be provided with two or more layers.
  • the coating solution is a compound represented by the following general formula (1), a binder polymer, a solvent, and a dispersant, a surfactant, a crosslinking agent, a pigment, or a compound represented by the general formula (1) as necessary. And other components such as various additives such as UV absorbers.
  • the coating liquid in the present invention preferably contains at least the compound represented by the general formula (1) in a dispersed state dispersed in the liquid.
  • the compound represented by the general formula (1) may be used after being dissolved in a solvent that dissolves the compound. However, it is preferable that the compound is dispersed in a solvent and is present as dispersed particles in the coating solution.
  • the layer is formed when the polymer layer is exposed to a moist heat environment or the like compared to the case where it is dissolved and contained. The phenomenon of exuding from the inside can be prevented.
  • the method for producing a resin film of the present invention preferably includes a dispersion step of preparing a dispersion by dispersing the compound represented by the general formula (1) in a solvent.
  • the dispersion prepared in the dispersing step, the binder polymer, and other components such as a surfactant and a crosslinking agent as necessary are mixed to form a coating solution for forming the polymer layer.
  • a polymer layer is suitably formed by preparing and apply
  • the dispersed state means a state (emulsion) in which a solution of the compound represented by the general formula (1) is dispersed in a water-insoluble phase (oil phase) in an aqueous medium (aqueous phase), and an aqueous solution. It includes both a dispersed state (suspension) in which a water-insoluble compound is dispersed in a medium in a solid state or a liquid state. By being contained in a dispersed state, it can be retained in the layer after forming the polymer layer, and the occurrence of bleed out is prevented.
  • the compound represented by the general formula (1) is added to a solvent and stirred to prepare an oil phase in which the compound is dissolved.
  • the water-soluble resin include polyvinyl alcohol (PVA), methyl cellulose, and hydroxypropyl cellulose.
  • the organic solvent include tetrahydrofuran, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.
  • the presence of the compound represented by the general formula (1) in a dispersed state means that after preparing an emulsion (emulsion) or suspension shown below, after removing an organic solvent from the emulsion or suspension, A state in which the dispersion state can be visually confirmed to exist stably at 25 ° C. for at least one week. Specifically, it can be confirmed by measuring and comparing the average particle diameter of the dispersed particles immediately after the preparation of the emulsion and after at least one week has passed at 25 ° C.
  • the emulsion is prepared by adding 20 g of the compound represented by the general formula (1) to 100 g of an organic solvent (for example, tetrahydrofuran) and heating and stirring to prepare an oil phase in which the compound is dissolved.
  • an organic solvent for example, tetrahydrofuran
  • the average particle diameter is a value obtained as a median diameter by a laser analysis / scattering particle size distribution measuring apparatus LA950 (manufactured by Horiba, Ltd.).
  • the coating liquid in the present invention is preferably an emulsion (or suspension) in which the compound represented by the general formula (1) is dispersed and contained, a binder polymer, and other surfactants and crosslinkers as necessary. It can be prepared by mixing the ingredients.
  • a disperser for dispersing the compound represented by the general formula (1) a known stirrer or the like can be used.
  • a disperser, a bead mill, a ball mill, an ultrasonic disperser or the like is preferably used. Can do.
  • the coating solution may be an aqueous system using water as a coating solvent or a solvent system using an organic solvent such as toluene or methyl ethyl ketone.
  • a mixed solvent of water and an organic solvent miscible with water is used.
  • the form which used water as the solvent for the said coating liquid from a viewpoint of environmental impact is preferable, and the form whose 50 mass% or more is water with respect to all the solvents contained in a coating liquid is more preferable.
  • the proportion of water in the total solvent is preferably 60% by mass or more, and more preferably 80% by mass or more.
  • a coating solvent may be used individually by 1 type, and may mix and use 2 or more types.
  • a conventionally known coating method can be appropriately selected.
  • a known coating method such as a gravure coater or a bar coater can be used.
  • the coating solution for forming a polymer layer in the present invention contains at least one compound represented by the following general formula (1) as an ultraviolet absorber.
  • This ultraviolet absorber absorbs longer-wave ultraviolet rays than conventional ultraviolet absorbers, and provides an ultraviolet shielding effect in a wide range including a long-wave ultraviolet (UV-A) region around 400 nm. Thereby, in the long-term use, superior light resistance performance can be maintained as compared with the conventional case.
  • UV-A long-wave ultraviolet
  • the content concentration of the ultraviolet absorber represented by the general formula (1) in the coating liquid for forming the polymer layer is preferably 3% by mass or more and 9% by mass or less with respect to the total mass of the coating liquid. 5 mass% or more and 8.5 mass% or less are more preferable.
  • the content concentration is 3% by mass or more, a good coated surface shape is obtained, and excellent light resistance is maintained over a long period of time. In particular, in a wide range including a long wave ultraviolet (UV-A) region around 400 nm. Excellent ultraviolet shielding effect.
  • UV-A long wave ultraviolet
  • Excellent ultraviolet shielding effect when the content concentration is 10% by mass or less, a good coated surface shape can be obtained, and excellent light resistance can be maintained over a long period of time, and the occurrence of bleed out when a polymer layer is formed can be prevented. it can.
  • R 1a , R 1b , R 1c , R 1d , and R 1e each independently represent a monovalent substituent other than a hydroxy group (OH group).
  • the substituents represented by R 1a to R 1e may be bonded to each other to form a ring.
  • At least one of the substituents represented by R 1a to R 1e is a group having a Hammett's Hammett's Hammett's substituent constant ⁇ p value of 0.3 or more.
  • the substituent represented by R 1a , R 1b , R 1c , R 1d , and R 1e is not particularly limited as long as at least one of R 1a to R 1e has a Hammett's ⁇ p value of 0.3 or more.
  • Preferred examples of the substituent having a Hammett's rule ⁇ p value of 0.3 or more include an alkoxycarbonyl group (COOR n ), a nitro group (NO 2 ), a cyano group (CN), a halogenated alkyl group (fluoroalkyl group (Rf)). ), Sulfonic acid or an alkali metal salt thereof (SO 3 H or SO 3 M).
  • R n represents an alkyl moiety.
  • the number of carbon atoms of the alkyl moiety represented by R n of the alkoxycarbonyl group is preferably in the range of 1-20.
  • the alkyl moiety may be linear or branched, and may further contain a double bond or a triple bond. Among these, the carbon number of the alkyl moiety is more preferably in the range of 1 to 10, and further preferably in the range of 1 to 5.
  • Specific examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group and the like.
  • the halogenated alkyl group is not particularly limited in the number of halogen substitutions, and may be arbitrarily selected.
  • the kind of halogen is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, among which a fluorine atom is particularly preferred.
  • a fluoroalkyl group is preferable, a fluoroalkyl group having 1 to 5 carbon atoms is more preferable, and a perfluoroalkyl group having 1 to 5 carbon atoms is particularly preferable.
  • the fluoroalkyl group may be either a straight chain or a branched chain, and may further contain a double bond or a triple bond. Specific examples of the fluoroalkyl group include a fluoromethyl group, a difluoroethyl group, a perfluoromethyl group, and a hexafluoropropyl group.
  • M in the SO 3 M represents an alkali metal.
  • an alkali metal represented by M lithium, sodium, or potassium is mentioned suitably, Especially sodium or potassium is more preferable.
  • the substituent represented by R 1a to R 1e in the general formula (1) represents a monovalent group other than the above-described groups
  • the monovalent substituent (hereinafter referred to as “substituent A”).
  • the substituent A includes, for example, the following groups. That is, Specific examples of the substituent A include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group having 1 to 20 carbon atoms (including a halogenated alkyl group.
  • methyl, ethyl, perfluoromethyl Fluoroethyl aryl groups having 6 to 20 carbon atoms (eg phenyl, naphthyl), cyano groups, carboxyl groups, alkoxycarbonyl groups (eg methoxycarbonyl), aryloxycarbonyl groups (eg phenoxycarbonyl), carbamoyl groups (eg carbamoyl) , N-phenylcarbamoyl, N, N-dimethylcarbamoyl), alkylcarbonyl group (eg acetyl), arylcarbonyl group (eg benzoyl), nitro group, amino group (eg amino, dimethylamino, anilino, substituted sulfoamino group), acyl Amino group (e.g.
  • acetamido, ethoxycarbonylamino a sulfonamido group (e.g., methanesulfonamido), an imido group (e.g. succinimido, phthalimido), an imino group (e.g., benzylideneamino), a hydroxy group (R 1a, R 1b, R 1c, Not included in the monovalent substituent represented by R 1d and R 1e ), an alkoxy group having 1 to 20 carbon atoms (for example, methoxy), an aryloxy group (for example, phenoxy), an acyloxy group (for example, acetoxy), Alkylsulfonyloxy group (for example, methanesulfonyloxy), arylsulfonyloxy group (for example, benzenesulfonyloxy), sulfo group, sulfamoyl group (for example, sulfamoyl
  • the monovalent substituent may be unsubstituted, may be further substituted with a substituent, and when having a plurality of substituents, the plurality of substituents may be the same or different. Examples of the substituent in the case of being substituted with a substituent include the groups listed as examples of the “monovalent substituent A”. Moreover, substituents may couple
  • Examples of the ring formed by bonding substituents include benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyridazine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, oxadi Examples thereof include an azole ring, a thiazole ring, a thiadiazole ring, a furan ring, a thiophene ring, a selenophene ring, a silole ring, a gelmol ring, and a phosphole ring.
  • a halogen atom a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (including a halogenated alkyl group), a cyano group, a carboxyl group, substituted or unsubstituted
  • alkoxy group a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, a substituted or unsubstituted sulfamoyl group, a thiocyanate group, or a substituted or unsubstituted alkyl moiety having 1 carbon atom Preferred alkylsulfonyl groups of 20.
  • a hydroxy group (not included in the monovalent substituent represented by R 1a , R 1b , R 1c , R 1d , and R 1e ), an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 6 are more preferably an aryloxy group having ⁇ 20, an alkyl group having 1 to 20 carbon atoms, and an amide group, and the monovalent substituent represented by a hydroxy group (R 1a , R 1b , R 1c , R 1d , R 1e is Not more preferred), an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms are more preferred.
  • the alkyl moiety of the alkoxy group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 6 carbon atoms.
  • Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i -Pentyl, t-pentyl, n-hexyl, i-hexyl, t-hexyl, n-octyl, t-octyl, i-octyl can be mentioned, methyl or ethyl is preferred, and methyl is particularly preferred.
  • R 1a , R 1b , R 1c , R 1d and R 1e represents a monovalent substituent
  • at least one of the substituents represents a substituent having a positive Hammett's ⁇ p value.
  • R 1c represents a substituent having a positive Hammett's ⁇ p value
  • R 1a , R 1b , R 1d , and R 1e represent a hydrogen atom.
  • the “substituent in which the Hammett's ⁇ p value is positive” in R 1a , R 1c , and R 1e in the general formula (1) preferably has a ⁇ p value of 0.1 to 1.
  • 2 electron withdrawing groups As specific examples of the electron withdrawing group having a ⁇ p value of 0.1 or more, COOR r (R r represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or an alkyl group, more preferably CONR s 2 (R s represents a hydrogen atom or a monovalent substituent), CN, halogen atom, NO 2 , SO 3 M (M represents a hydrogen atom or an alkali metal).
  • the “substituent having a positive Hammett's ⁇ p value” is more preferably COOR r , CONR s 2 , CN, CF 3 , a halogen atom, NO 2 , from the viewpoint of excellent light resistance and solubility. And SO 3 M.
  • R r and R s each independently represent a hydrogen atom or a monovalent substituent.
  • M represents a hydrogen atom or an alkali metal (the same applies to M hereinafter). ).
  • the “substituent having a positive Hammett's ⁇ p value” is more preferably COOR r or CN, and particularly preferably COOR r for the same reason as above.
  • R r and R s each represent a hydrogen atom or a monovalent substituent, and examples of the monovalent substituent herein include the substituent A.
  • a linear or branched alkyl group having 1 to 20 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable.
  • Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, and n-pentyl.
  • alkali metal represented by M include lithium, sodium, and potassium, and sodium and potassium are particularly preferable (hereinafter the same applies to M).
  • R 1c is any one of COOR r , CONR s 2 , CN, CF 3 , a halogen atom, NO 2 , SO 3 M, and further, COOR
  • the aspect which is r or CN is more preferable, and the aspect which is CN is still more preferable.
  • R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n , and R 1p each independently represent a hydrogen atom or a monovalent substituent, The substituents may be bonded to each other to form a ring.
  • R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p represent a monovalent substituent
  • R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p preferably represent the “substituent having a positive Hammett ⁇ p value”, and at least one of R 1g , R 1h , R 1i and R 1j It is more preferable that the ⁇ p value of the rule is positive (preferably 0.1 to 1.2) ”, and R 1h represents the“ substituent whose ⁇ p value of the Hammett rule is positive ”. More preferably, it represents.
  • R 1n and R 1h represent the above-mentioned “substituents whose Hammett's ⁇ p value is positive (preferably 0.1 to 1.2)” in view of excellent light resistance. preferable.
  • R 1h or R 1n is independently a hydrogen atom, COOR r , CONR s 2 , CN, CF 3 , halogen atom, NO 2 , SO 3 M, or the like, in that it exhibits excellent light resistance.
  • R 1h or R 1n is preferably a hydrogen atom
  • R 1h and R 1n are more preferably a hydrogen atom
  • R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p particularly preferably represent a hydrogen atom.
  • R 1c is “a substituent having a positive Hammett's ⁇ p value (preferably 0.1 to 1.2)” in that it exhibits excellent light resistance.
  • R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p are preferably hydrogen atoms
  • R 1c is COOR r , CONR s 2 , CN, CF 3 , More preferably, it is any one of a halogen atom, NO 2 , and SO 3 M
  • R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n, and R 1p are hydrogen atoms.
  • the compound represented by the general formula (1) preferably has a pKa in the range of ⁇ 5.0 to ⁇ 7.0, more preferably in the range of ⁇ 5.2 to ⁇ 6.5. More preferably, it is in the range of -5.4 to -6.0.
  • R 1a , R 1c and R 1e each represent a hydrogen atom
  • R 1b and R 1d each independently represent a monovalent substituent
  • R 1b and R 1d An embodiment in which at least one is a substituent having a positive Hammett's ⁇ p value can be given.
  • the compound represented by General formula (1) is excellent in solvent solubility. Compatibility with polymer (especially because of excellent compatibility with polyester, when a polyester resin composition containing the compound is used, precipitation or bleeding out of the compound represented by the general formula (1) is difficult to occur. It has the effect.
  • the solvent solubility means solubility in an organic solvent such as ethyl acetate, methyl ethyl ketone, and toluene.
  • compatibility with the polymer particularly compatibility with the polyester, it is preferably 10% by mass or more, more preferably 30% by mass or more, based on the solvent used.
  • the “substituent having a positive Hammett's ⁇ p value” in R 1b and R 1d in the general formula (1) is preferably COOR r , CONR s 2 , CN, CF 3. , A halogen atom, NO 2 , and SO 3 M.
  • R r and R s each independently represent a hydrogen atom or a monovalent substituent.
  • M represents a hydrogen atom or an alkali metal.
  • Examples of the monovalent substituent represented by R r and R s include the substituent A described above. Among these, an alkoxycarbonyl group, a nitro group, a cyano group, a fluoroalkyl group, and a sulfonic acid or an alkali metal salt thereof are preferable.
  • the "substituent ⁇ p value of Hammett's rule is positive” is a point showing the solubility and excellent light resistance, more preferably COOR r or a cyano group, it is preferably further is COOR r.
  • the “substituent having a positive Hammett's ⁇ p value” is a cyano group, it exhibits better light resistance, and when the “substituent having a positive Hammett's ⁇ p value” is COOR r , Better solvent solubility.
  • R r preferably represents a hydrogen atom or an alkyl group, more preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and still more preferably a linear or branched alkyl group having 1 to 15 carbon atoms. . R r is more preferably a branched alkyl group having 5 to 15 carbon atoms from the viewpoint of solubility in a solvent.
  • the branched alkyl group has a secondary carbon atom or a tertiary carbon atom, preferably contains 1 to 5 secondary carbon atoms or tertiary carbon atoms, preferably contains 1 to 3, preferably 1 or It is preferable to include two, and it is more preferable to include one or two secondary carbon atoms and tertiary carbon atoms. Further, it preferably contains 1 to 3 asymmetric carbons.
  • R r is a branched alkyl group having 5 to 15 carbon atoms containing 1 or 2 secondary carbon atoms and tertiary carbon atoms and 1 or 2 asymmetric carbon atoms. It is particularly preferred. This is because the symmetry of the compound structure is lost and the solubility is improved.
  • a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable.
  • the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i -Pentyl, t-pentyl, n-hexyl, i-hexyl, t-hexyl, n-octyl, t-octyl, i-octyl can be mentioned, methyl or ethyl is preferred, and methyl is particularly preferred.
  • R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p represent a monovalent substituent in terms of exhibiting excellent light resistance
  • at least one of 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p represents the above-mentioned “substituent with a positive Hammett ⁇ p value”
  • R 1g More preferably, at least one of R 1h , R 1i and R 1j represents the “substituent whose Hammett's ⁇ p value is positive (preferably 0.1 to 1.2)”, and R 1h represents the “Hammett More preferably, it represents a “substituent whose ⁇ p value of the rule is positive”.
  • R 1b or R 1d and R 1h represent the above-mentioned “substituents whose Hammett's ⁇ p value is positive (preferably 0.1 to 1.2)”.
  • R 1h or R 1n is independently any one of a hydrogen atom, COOR r , CONR s 2 , a cyano group, CF 3 , a halogen atom, a nitro group, and SO 3 M in that excellent light resistance is exhibited.
  • R 1h or R 1n is preferably a hydrogen atom
  • R 1h and R 1n are more preferably a hydrogen atom
  • R 1g , R 1h , R 1i , R 1j , R 1k R 1m , R 1n and R 1p particularly preferably represent a hydrogen atom.
  • R 1b , R 1c or R 1d is “a Hammett's ⁇ p value is positive (preferably 0.1 to 1.2). It is preferable that R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n and R 1p are hydrogen atoms, and R 1b , R 1c or R 1d Is one of COOR r , CONR s 2 , cyano group, CF 3 , halogen atom, nitro group, or SO 3 M, and R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R More preferably, 1n and R 1p are hydrogen atoms.
  • R 1a , R 1b , R 1d , R 1e , R 1g , R 1h , R 1i , R 1j , R 1k , R 1m , R 1n , and R 1p are hydrogen atoms
  • R 1c is COOR r [R r represents a monovalent substituent. ].
  • the compound represented by the general formula (1) can take a tautomer depending on the structure and the environment in which the compound is placed, but the compound represented by the general formula (1) includes a tautomer. .
  • the compound represented by the general formula (1) may contain an isotope (for example, 2 H, 3 H, 13 C, 15 N, 17 O, 18 O, etc.).
  • the compound represented by the general formula (1) can be synthesized by any method.
  • known patent documents and non-patent documents for example, JP-A-7-188190, JP-A-11-315072, JP-A-2001-220385, “Dye and Drug”, Vol. 40, No. 12 (1995) ), Pages 325 to 339) and the like.
  • the exemplified compound (16) can be synthesized by reacting salicylamide, 3,5-bis (trifluoromethyl) benzoyl chloride and 2-hydroxybenzamidine hydrochloride.
  • it can be synthesized by reacting salicylamide, salicylic acid and 3,5-bis (trifluoromethyl) benzamidine hydrochloride.
  • the compound represented by the general formula (1) has a feature of excellent solubility in an organic solvent, and has a “substituent having a positive Hammett's ⁇ p value” at a specific position in the structural formula. Since LUMO is stabilized by the electron withdrawing group, the excitation life is shortened and the light resistance is excellent. Therefore, when used as a UV absorber, conventional UV absorbers such as triazine compounds, when used at a high concentration, have adverse effects such as precipitation, bleeding out due to long-term use, or yellowing due to decomposition.
  • the compound represented by the general formula (1) in the present invention has excellent solubility and light resistance, precipitation and bleed-out do not occur even when it is contained at a high concentration, and it takes a long time. Even when used, yellowing can be prevented without decomposition.
  • the compound represented by the general formula (1) may be used alone or in combination of two or more having different structures.
  • the maximum absorption wavelength of the compound represented by the general formula (1) is not particularly limited, but is preferably 250 to 400 nm, and more preferably 280 to 380 nm.
  • the full width at half maximum is preferably 20 to 100 nm, more preferably 40 to 80 nm.
  • the maximum absorption wavelength and the full width at half maximum are values easily measured by a conventionally known method. The measurement method is described in, for example, “The Fourth Edition Experimental Chemistry Course 7 Spectroscopy II” (Maruzen, 1992), pages 180 to 186, edited by the Chemical Society of Japan. Specifically, the sample is dissolved in an appropriate solvent, and measurement is performed by a spectrophotometer using two cells for sample and control using a cell made of quartz or glass.
  • the solvent is required to have no absorption in the measurement wavelength region, have a small interaction with the solute molecule, and have a very low volatility in accordance with the solubility of the sample.
  • the maximum absorption wavelength and half width in the present invention are values measured by preparing a solution having a concentration of about 5 ⁇ 10 ⁇ 5 mol ⁇ dm ⁇ 3 using ethyl acetate and using a quartz cell having an optical path length of 10 mm.
  • the half width of the spectrum is described in, for example, “Chapter 4 of Experimental Chemistry Lecture 3, Basic Operation III” (Maruzen, 1991), page 154, edited by the Chemical Society of Japan.
  • the half width may be explained with an example in which the horizontal axis is taken on the wave number scale, but the half width in the present invention uses a value obtained on the axis on the wavelength scale.
  • the unit of the half width is [nm]. Specifically, it represents the width of the absorption band that is half the absorbance at the maximum absorption wavelength, and is used as a value that represents the shape of the absorption spectrum.
  • a spectrum with a small half-value width shows a sharp spectrum
  • a spectrum with a large half-value width shows a broad spectrum.
  • UV-absorbing compounds that give a broad spectrum also have absorption in a wide range from the maximum absorption wavelength to the long wave side, so there is no yellowish coloration, and a spectrum with a small half-value width is effective for shielding the long wave ultraviolet region.
  • a UV-absorbing compound having is preferred.
  • the intensity of light absorption is proportional to the integral of the molar extinction coefficient, as described in Sumida Tokita “Chemical Seminar 9 Color Chemistry” (Maruzen, 1982), pages 154 to 155.
  • the oscillator strength is proportional to the product of the absorbance at the maximum absorption wavelength and the full width at half maximum (however, the full width at half maximum is a value centered on the wavelength scale). This means that when the transition moment values are the same, a compound having a spectrum with a small half width has a large absorbance at the maximum absorption wavelength.
  • Such UV-absorbing compounds have the advantage of being able to effectively shield the area around the maximum absorption wavelength with a small amount of use, but since the absorbance decreases sharply when the wavelength is slightly away from the maximum absorption wavelength, a wide range of areas can be used. It cannot be shielded.
  • the compound represented by the general formula (1) preferably has a molar extinction coefficient at the maximum absorption wavelength of 20000 or more, more preferably 30000 or more, and particularly preferably 50000 or more.
  • the molar extinction coefficient is 20000 or more, the absorption efficiency per mass of the compound represented by the general formula (1) is high, and therefore, it is represented by the “general formula (1) required to completely absorb the ultraviolet region.
  • the amount of “compound” can be reduced. This is preferable from the viewpoint of preventing skin irritation and accumulation in a living body and from the point that bleeding out hardly occurs.
  • the molar extinction coefficient is described in, for example, “New Edition Experimental Chemistry Course 9 Analytical Chemistry [II]” (Maruzen, 1977), page 244, edited by the Chemical Society of Japan. It can be obtained together.
  • the content of the ultraviolet absorber represented by the general formula (1) in the formed polymer layer is preferably 0.15 to 5.0 g / m 2 , and preferably 0.3 to 4.0 g / m 2. More preferred.
  • the ultraviolet shielding effect is excellent in a wide range including a long-wave ultraviolet (UV-A) region near 400 nm.
  • production of bleed-out can be prevented because content is 5.0 g / m ⁇ 2 > or less.
  • the coating solution for forming a polymer layer in the present invention may contain two or more compounds represented by the general formula (1) having different structures as an ultraviolet absorber. Moreover, you may use together the compound represented by the said General formula (1), and 1 or more types of other ultraviolet absorbers other than that. When two types (preferably three types) of ultraviolet absorbers having different basic skeleton structures are used in combination, the dispersion state of the ultraviolet absorber is stabilized and ultraviolet rays in a wide wavelength region can be absorbed.
  • Examples of other ultraviolet absorbers other than the general formula (1) include triazine, benzotriazole, benzophenone, merocyanine, cyanine, dibenzoylmethane, cinnamic acid, cyanoacrylate, and benzoate. And the like.
  • Examples of the other ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, salicylic acid compounds, benzoxazinone compounds, cyanoacrylate compounds, benzoxazole compounds, merocyanine compounds, and triazine compounds. More preferred are benzoxazinone compounds, benzotriazole compounds, benzophenone compounds, triazine compounds and the like. Particularly preferred are benzoxazinone compounds.
  • Other ultraviolet absorbers are described in detail in paragraphs [0117] to [0121] of JP-A-2008-273950, and the materials described in the publication can be applied. When other ultraviolet absorbers are used in combination, the content ratio of the other ultraviolet absorbers is based on the amount of the ultraviolet absorber represented by the general formula (1) from the viewpoint of maintaining the effects of the present invention. 20 mass% or less is preferable.
  • the compound represented by the general formula (1) is preferably contained in combination with a benzoxazinone compound. Since the compound represented by the general formula (1) has excellent light resistance in the long wavelength region, it has the effect of preventing the deterioration of benzoxazinone that can be shielded to a longer wavelength region, together with the benzoxazinone-based compound. Use is preferable because the shielding effect can be sustained for a long time up to a longer wavelength region.
  • a high ultraviolet shielding effect can be obtained, and furthermore, a white pigment having a strong hiding power, such as titanium oxide, may be used in combination. Further, a slight amount (0.05% by mass or less) of a colorant may be used in combination depending on the viewpoint of appearance, color tone or preference.
  • a fluorescent brightener may be used in combination. Examples of the fluorescent brightening agent include commercially available products, general formula [1] described in JP-A-2002-53824, and specific compound examples 1 to 35.
  • the coating solution for forming a polymer layer in the present invention contains at least one binder polymer.
  • binder polymer examples include silicone polymers (for example, silicone-acrylic composite polymer, silicone-polyester composite polymer), polyester-based polymers (for example, polyethylene terephthalate (PET), polyethylene-2,6-naphthalate (PEN)).
  • silicone polymers for example, silicone-acrylic composite polymer, silicone-polyester composite polymer
  • polyester-based polymers for example, polyethylene terephthalate (PET), polyethylene-2,6-naphthalate (PEN)
  • polyurethane polymers eg, polymers comprising hexamethylene diisocyanate or toluene diisocyanate and ethylene glycol or propylene glycol
  • acrylic polymers eg, polymers containing polymethyl methacrylate, polyethyl acrylate, etc.
  • Appropriately selected from known polymers such as polyolefin polymers (for example, polymers composed of polyethylene and acrylic acid or methacrylic acid) It can be used Te.
  • adhesion between the support or other layers such as a colored layer and an undercoat layer, and weather resistance (particularly in a high humidity environment with temperature and humidity changes and heat and moisture (humidity))
  • weather resistance particularly in a high humidity environment with temperature and humidity changes and heat and moisture (humidity)
  • the compound represented by the general formula (1) is incorporated to prevent deterioration of itself more effectively, and is resistant to weathering (particularly in a high humidity environment having changes in temperature and humidity, heat and moisture (humidity)).
  • a fluorine-based polymer and a silicone-based polymer are preferable, and a silicone-based polymer is particularly preferable.
  • X 1 , X 2 , and X 3 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or a perfluoroalkyl group having 1 to 3 carbon atoms.
  • fluorine-based polymer examples include polytetrafluoroethylene (hereinafter sometimes referred to as PTFE), polyvinyl fluoride (hereinafter sometimes referred to as PVF), and polyvinylidene fluoride (hereinafter referred to as PVDF). ), Polychlorinated ethylene trifluoride (hereinafter sometimes referred to as PCTFE), polytetrafluoropropylene (hereinafter sometimes referred to as HFP), and the like.
  • PTFE polytetrafluoroethylene
  • PVF polyvinyl fluoride
  • PVDF polyvinylidene fluoride
  • PCTFE Polychlorinated ethylene trifluoride
  • HFP polytetrafluoropropylene
  • the fluoropolymer may be a homopolymer obtained by homopolymerizing one kind of monomer, or may be obtained by copolymerizing two or more kinds of monomers.
  • a copolymer obtained by copolymerizing tetrafluoroethylene and tetrafluoropropylene abbreviated as P (TFE / HFP)
  • P tetrafluoroethylene and vinylidene fluoride
  • a polymer obtained by copolymerizing a fluorine-based monomer having a structural portion of-(CFX 1 -CX 2 X 3 )-and another monomer for example, a copolymer of tetrafluoroethylene and ethylene (abbreviated as P (TFE / E)), a copolymer of tetrafluoroethylene and propylene (abbreviated as P (TFE / P)), Copolymer of tetrafluoroethylene and vinyl ether (abbreviated as P (TFE / VE)), copolymer of tetrafluoroethylene and perfluorovinyl ether (abbreviated as P (TFE / FVE)), chlorotri Copolymers of fluoroethylene and vinyl ether (abbreviated as P (CTFE / VE)), copolymers of chlorotrifluoroethylene and perfluorovinyl ether (abbreviated as P (CTFE /
  • the fluoropolymer may be used by being dissolved in an organic solvent, or may be used by being dispersed in water as polymer particles. The latter is preferable in that the environmental load is small.
  • the aqueous dispersions of fluoropolymers are described in, for example, Japanese Patent Application Laid-Open Nos. 2003-231722, 2002-20409, and 9-194538.
  • silicone-based polymer examples include a composite polymer of silicone and acrylic, a composite polymer of silicone and polyester, and the like.
  • Commercially available products that are marketed may be used as the silicone polymer.
  • a composite polymer of silicone and acrylic Seranate WSA1060 and WSA1070 manufactured by DIC Corporation, Asahi Kasei Chemicals Corporation H7620, H7630, H7650, and the like.
  • the coating liquid for forming the polymer layer may be a combination of a fluorine-based polymer and / or a silicone-based polymer and a polymer other than these polymers.
  • a fluorine-based polymer and / or a silicone-based polymer and a polymer other than these polymers When other polymers are used in combination, it is preferable to use the polymers other than the fluorine-based polymer and the silicone-based polymer in the range of 50% by mass or less of the total mass of the binder. When the amount of the other polymer is 50% by mass or less, good weather resistance as a back sheet can be exhibited.
  • the concentration of the binder polymer in the coating solution for forming the polymer layer is preferably 6% by mass or more and 25% by mass or less, more preferably 8% by mass or more and 20% by mass or less, with respect to the total mass of the coating solution. It is. When the content of the binder polymer is 6% by mass or more, a layer having a good strength is obtained, and when the content is 25% by mass or less, the amount of the ultraviolet absorber is not relatively decreased. This is preferable for maintaining high light resistance.
  • the coating amount of the binder polymer in the formed polymer layer is preferably 1.0 to 8.5 g / m 2 , more preferably 2.0 to 6.0 g / m 2 or less.
  • the content of the polymer is 1.0 g / m 2
  • a layer having good strength can be obtained, and when it is 8.5 g / m 2 or less, the amount of the UV absorber may be relatively too small. In view of maintaining high light resistance, it is preferable.
  • the coating liquid for forming the polymer layer may contain a crosslinking agent for crosslinking the binder polymer contained in the polymer layer.
  • a crosslinking agent for crosslinking the binder polymer contained in the polymer layer.
  • the crosslinking agent include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents.
  • a carbodiimide-based crosslinking agent and an oxazoline-based crosslinking agent are preferable from the viewpoint of securing adhesiveness after wet heat aging.
  • carbodiimide crosslinking agent examples include N, N′-dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N- [3- ( And dimethylamino) propyl] -N′-ethylcarbodiimide, N- [3- (dimethylamino) propyl] -N′-propylcarbodiimide, N-tert-butyl-N′-ethylcarbodiimide, and the like.
  • commercially available products include Carbodilite V-02-L2 (manufactured by Nisshinbo Industries, Inc.).
  • oxazoline-based crosslinking agent examples include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2- Oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2,2'-bis- (2-oxazoline), 2,2'-methylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (2-oxazoline), 2,2′-trimethylene-bis- (2-oxazoline), 2,2′-tetramethylene-bis- (2-oxazoline) ), 2,2′-hexamethylene-bis- (2-oxazoline), 2,2′-octamethylene-bis- (2-oxazoline), 2,2′-ethylene-bis- (4,4 ′) Dimethyl-2-oxazoline), 2,2'-p-pheny
  • the content of the crosslinking agent in the polymer layer is preferably 0.5% by mass or more and 100% by mass or less, more preferably 0.5% by mass or more and 50% by mass or less, and still more preferably 5.0% by mass with respect to the binder.
  • the mass is 30% by mass or more.
  • the coating liquid used for forming the polymer layer in the present invention may contain a pigment, and the polymer layer may be formed as a colored layer.
  • the same pigment as in the colored layer described later can be used, and the preferred embodiment is also the same.
  • a pigment having a desired hue may be included to give design properties, or a white pigment may be included to give the polymer layer a function as a reflective layer.
  • the coating liquid for forming the polymer layer may contain other additives such as a surfactant and a filler as necessary.
  • the surfactant examples include anionic and nonionic (for example, polyoxyalkylene having 2 or 3 carbon atoms and an alkyl group having 1 to 30, preferably 2 to 24, more preferably 6 to 24 carbon atoms).
  • Known surfactants such as alkylene alkyl ethers can be used.
  • the range of the content in the polymer layer is 0.1 mg / m 2 or more, and when the layer is formed, a good layer can be obtained while suppressing the occurrence of repelling. When it is m 2 or less, it is possible to maintain the adhesion between the polymer support and the second polymer layer satisfactorily.
  • the filler a known filler (inorganic fine particles) such as titanium dioxide can be used.
  • the content of the filler in the polymer layer is preferably 200% by mass or less, more preferably 150% by mass or less based on the amount of the binder in the polymer layer.
  • the lower limit of the filler content is preferably 0.5% by mass.
  • the filler content is 200% by mass or less, it is advantageous in that a good surface shape can be obtained.
  • the adhesiveness after wet heat aging is favorable in content of a filler being 0.5 mass% or more.
  • the content of the inorganic fine particles is more preferably in the range of 1% by mass to 15% by mass.
  • two or more polymer layers can be laminated. Specifically, after forming the first polymer layer containing the compound represented by the general formula (1), the binder polymer, and other components as necessary, as the first layer on the support, As the second layer on the first polymer layer, it further contains one or more binder polymers and optionally other components such as a surfactant and a crosslinking agent.
  • An embodiment having a second polymer layer (hereinafter also referred to as “protective polymer layer”) in which the content of the represented compound is 1.0% by mass or less with respect to the total amount of the binder polymer is also preferable.
  • the protective polymer layer preferably further has a total content of the compound represented by the general formula (1) and other ultraviolet absorbers of 1.0% by mass or less based on the total amount of the binder polymer.
  • a polymer layer containing a large amount of an ultraviolet absorber by having a laminated structure in which the polymer layer mainly containing an ultraviolet absorber (including a compound represented by the general formula (1)) is protected by a protective polymer layer.
  • the absorption of ultraviolet rays is more stable, and it is possible to suppress deterioration that appears as cracks or peeling of the support over a long period of time.
  • the protective polymer layer may contain an ultraviolet absorber (including the compound represented by the general formula (1)) to the extent that the effects of the present invention are not impaired, but the compound represented by the general formula (1). It is preferable that the content of the UV absorber, and hence the content of the UV absorber, is 1.0% by mass or less of the total binder mass, and the protective polymer layer does not substantially contain the UV absorber and does not contain the UV absorber (0 (Mass%) is more preferable.
  • the content of the ultraviolet absorber of 1% by mass or less of the total binder mass means that the ultraviolet absorber is not actively contained, although the inclusion of the ultraviolet absorber is not excluded at all.
  • binder polymer contained in the protective polymer layer examples include known polymers such as a fluorine polymer, a silicone polymer, a polyester polymer, a polyurethane polymer, an acrylic polymer, and a polyolefin polymer. Can be used. Details and preferred embodiments of specific examples and the like of the polymer are as described in the polymer layer. Among these, from the viewpoint of further improving the durability performance when exposed to changes in temperature and humidity and high humidity and heat environment, it may contain one or more selected from the group consisting of fluorine-based polymers and silicone-based polymers. preferable.
  • the content of the binder polymer in the protective polymer layer is preferably 50% by mass to 95% by mass, and more preferably 60% by mass to 90% by mass with respect to the total mass of the protective polymer layer.
  • the content of the polymer is 50% by mass or more, good durability is obtained, and when it is 95% by mass or less, the amount of the crosslinking agent and the surfactant can be secured. Is advantageous.
  • the protective polymer layer further contains at least one crosslinking agent for crosslinking the binder polymer.
  • the crosslinking agent include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents.
  • a carbodiimide-based crosslinking agent and an oxazoline-based crosslinking agent are preferable, and a carbodiimide-based crosslinking agent is more preferable from the viewpoint of securing adhesiveness after wet heat aging.
  • the details of the crosslinking agent, particularly the details and preferred embodiments of the carbodiimide-based crosslinking agent and the oxazoline-based crosslinking agent are as described in the polymer layer.
  • the content of the crosslinking agent in the protective polymer layer is preferably 0.5% by mass or more and 40% by mass or less, and more preferably 0.5% by mass or more and 30% by mass or less with respect to the binder polymer constituting the layer.
  • the content of the crosslinking agent is 0.5% by mass or more, a sufficient crosslinking effect is obtained while maintaining the strength and adhesiveness of the polymer layer, and when it is 40% by mass or less, particularly 30% by mass or less, The pot life of the liquid when the coating liquid for forming the polymer layer is adjusted can be kept longer.
  • the protective polymer layer may further contain other additives such as a surfactant and a filler (inorganic fine particles) as necessary. These details are as described above.
  • the thickness of the protective polymer layer is preferably 0.5 to 12 ⁇ m. When the thickness of the protective polymer layer is 0.5 ⁇ m or more, higher durability can be obtained, and when it is 12 ⁇ m or less, the surface shape is good and the adhesiveness to the adjacent layer is excellent.
  • the thickness of the protective polymer layer is more preferably 1.0 to 10 ⁇ m.
  • the protective polymer layer can be formed by preparing a coating solution containing a binder polymer or the like, applying the coating solution on the first polymer layer, and drying the coating solution. After drying, it may be cured by heating.
  • a coating method for example, a gravure coater or a bar coater can be used.
  • the solvent used for the preparation of the coating solution can be selected from one or more of water and organic solvents such as toluene and methyl ethyl ketone.
  • the protective polymer layer is preferably formed by a method in which an aqueous coating solution in which a polymer is dispersed in water is prepared and applied. In this case, the proportion of water in the solvent is preferably 60% by mass or more, and more preferably 80% by mass or more.
  • the resin film of the present invention may have other layers such as a colored layer as necessary.
  • it can be configured as a solar cell backsheet in which a polymer layer is provided on one of the supports and a colored layer (particularly a light reflecting layer) is provided on the other.
  • a colored layer may be provided on one side of the support.
  • it can apply as a back sheet for solar cells as an example of the resin film of this invention.
  • a colored layer is provided on the light-receiving side of the support (the side facing the battery-side substrate provided with the solar cell element), and the back side is protected on the side opposite to the side provided with the colored layer.
  • a mode in which the above-described polymer layer in the present invention is provided as a layer is preferable.
  • the colored layer in the present invention contains at least a pigment and a binder, and may further include other components such as various additives as necessary.
  • the resin film of the present invention When the resin film of the present invention is used as a back sheet for solar cells, as a function of the colored layer, first, the light that has passed through the solar cells and reaches the back sheet without being used for power generation among the incident light. Increasing the power generation efficiency of the solar cell module by reflecting it back to the solar cell, and secondly, the decorativeness of the appearance when the solar cell module is viewed from the side where sunlight enters (front side) And so on. In general, when the solar cell module is viewed from the front side (glass substrate side), the back sheet is visible around the solar cell, and by providing a colored layer on the back sheet, the decorativeness of the back sheet itself is improved. The appearance can be improved.
  • the colored layer can contain at least one pigment.
  • the pigment include inorganic pigments such as titanium dioxide, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin, talc, ultramarine blue, bitumen, and carbon black, and organic pigments such as phthalocyanine blue and phthalocyanine green. It can be appropriately selected and contained.
  • the colored layer is configured as a reflective layer that reflects light that has entered the solar cell and passed through the solar cell and returns it to the solar cell
  • white inorganic particles white pigments such as titanium dioxide, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin and talc are preferable. Of these, titanium dioxide is preferable.
  • the content of the white inorganic particles in the reflective layer is preferably in the range of 30% by mass to 90% by mass with respect to the total mass of the binder polymer and the white inorganic particles, and more preferably white inorganic particles.
  • the range of the content of is 50 to 85% by mass.
  • the content of the pigment in the colored layer is preferably in the range of 2.5 to 12 g / m 2 , and more preferably in the range of 2.5 to 8.5 g / m 2 .
  • the pigment content is 2.5 g / m 2 or more, necessary coloring can be obtained, and reflectance and decorative properties can be effectively provided.
  • the content of the pigment in the colored layer is 12 g / m 2 or less, the planar shape of the colored layer is easily maintained and the film strength is excellent.
  • the reflective layer preferably contains white inorganic particles in the range of 4 to 12 g / m 2 .
  • the content of the white inorganic particles is 4 g / m 2 or more, the required reflectance is easily obtained, and when the content is 12 g / m 2 or less, the weight of the back sheet can be reduced.
  • a more preferable content of white inorganic particles in the reflective layer is in the range of 5 to 11 g / m 2 .
  • the reflective layer contains two or more types of white inorganic particles, the total content of all white inorganic particles in the reflective layer is preferably in the range of 4 to 12 g / m 2 .
  • the average particle diameter of the pigment is preferably 0.03 to 0.8 ⁇ m, more preferably about 0.15 to 0.5 ⁇ m in volume average particle diameter. When the average particle size is within the above range, the light reflection efficiency is high.
  • the volume average particle diameter is a value measured by a laser analysis / scattering particle size distribution measuring apparatus LA950 (manufactured by Horiba, Ltd.).
  • a polyester resin, a polyurethane resin, an acrylic resin, a polyolefin resin, a silicone resin, or the like can be used as the binder constituting the colored layer.
  • acrylic resin and polyolefin resin are preferable from the viewpoint of ensuring high adhesiveness.
  • Composite resins may be used, for example acrylic / silicone composite resins are also preferred binders.
  • the content of the binder component is preferably in the range of 15 to 200% by mass and more preferably in the range of 17 to 100% by mass with respect to the pigment. When the content of the binder is 15% by mass or more, the strength of the colored layer is sufficiently obtained, and when it is 200% by mass or less, the reflectance and the decorativeness can be kept good.
  • crosslinking agent examples include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents. Details of the crosslinking agent, particularly details and preferred embodiments of the carbodiimide-based crosslinking agent and oxazoline-based crosslinking agent, are as described in the first polymer layer.
  • the addition amount of the crosslinking agent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, based on the binder in the layer.
  • surfactant known surfactants such as anionic and nonionic surfactants can be used.
  • the details and preferred embodiments of the surfactant are as described in the first polymer layer.
  • the content is preferably 0.1 to 15 mg / m 2 , more preferably 0.5 to 5 mg / m 2 .
  • filler known fillers such as colloidal silica and titanium dioxide can be used.
  • the content of the filler is preferably 20% by mass or less, more preferably 15% by mass or less per binder of the colored layer.
  • the colored layer can be formed by a method in which a polymer sheet containing a pigment is bonded to a support, a method in which a colored layer is co-extruded during substrate formation, a method by coating, or the like.
  • the colored layer can be formed by bonding, co-extrusion, coating or the like directly on the surface of the support or through an undercoat layer having a thickness of 2 ⁇ m or less.
  • the formed colored layer may be in a state of being in direct contact with the surface of the support or in a state of being laminated via an undercoat layer.
  • the method by coating is preferable because it is simple and can be formed in a thin film with uniformity.
  • the coating solution may be an aqueous system using water as an application solvent, or a solvent system using an organic solvent such as toluene or methyl ethyl ketone. Among these, from the viewpoint of environmental burden, it is preferable to use water as a solvent.
  • a coating solvent may be used individually by 1 type, and may mix and use 2 or more types. Specifically, for example, when a reflective layer is formed, white inorganic particles, a binder, and other components are included as necessary on the surface of the polymer support on which the first and second polymer layers are not formed. It can form by apply
  • an easy-adhesive layer that is easily adhesive to the organic component may be provided on one side of the support.
  • the resin film of the present invention may be, for example, a solar cell backsheet in which an easy-adhesion layer is provided (particularly on the colored layer).
  • the easy-adhesion layer is a layer for easily adhering firmly to the sealing material that seals the solar cell element of the battery side substrate (battery body) provided with the solar cell element.
  • the easy-adhesion layer can be formed using a binder and inorganic fine particles, and may further include other components such as additives as necessary.
  • the easy-adhesion layer is used for a sealing material (for example, ethylene-vinyl acetate (EVA; ethylene-vinyl acetate copolymer), polyvinyl butyral (PVB), epoxy resin, etc.) that seals the power generation element of the battery side substrate.
  • EVA ethylene-vinyl acetate
  • PVB polyvinyl butyral
  • epoxy resin etc.
  • It is preferably configured to have an adhesive force of 10 N / cm or more (preferably 20 N / cm or more). When the adhesive force is 10 N / cm or more, it is easy to obtain wet heat resistance capable of maintaining adhesiveness.
  • the adhesive strength can be adjusted by a method of adjusting the amount of the binder and inorganic fine particles in the easy-adhesive layer, a method of applying a corona treatment to the surface of the back sheet that adheres to the sealing material, and the like.
  • the easy-adhesion layer can contain at least one binder.
  • the binder suitable for the easy-adhesive layer include polyester, polyurethane, acrylic resin, polyolefin, and the like. Among these, acrylic resin and polyolefin are preferable from the viewpoint of durability.
  • acrylic resin a composite resin of acrylic and silicone is also preferable.
  • binders examples include Chemipearl S-120 and S-75N (both manufactured by Mitsui Chemicals) as specific examples of polyolefins, and Jurimer ET-410 and SEK-301 (both Nippon Pure Chemical (both manufactured by Mitsui Chemicals, Inc.)).
  • Jurimer ET-410 and SEK-301 both Nippon Pure Chemical (both manufactured by Mitsui Chemicals, Inc.)
  • Ceranate WSA1060, WSA1070 both manufactured by DIC Corporation
  • H7620, H7630, H7650 both manufactured by Asahi Kasei Chemicals Corporation
  • the content of the binder in the easy-adhesive layer is preferably in the range of 0.05 to 5 g / m 2 . In particular, the range of 0.08 to 3 g / m 2 is more preferable.
  • the content of the binder, 0.05 g / m 2 or more is desired as easy adhesion obtained to that, better surface state is obtained when the is 5 g / m 2 or less.
  • the easily adhesive layer can contain at least one kind of inorganic fine particles.
  • the inorganic fine particles include silica, calcium carbonate, magnesium oxide, magnesium carbonate, and tin oxide.
  • fine particles of tin oxide and silica are preferable in that the decrease in adhesiveness when exposed to a humid heat atmosphere is small.
  • the particle size of the inorganic fine particles is preferably about 10 to 700 nm, more preferably about 20 to 300 nm in terms of volume average particle size. When the particle size is within this range, better easy adhesion can be obtained.
  • the particle size is a value measured by a laser analysis / scattering particle size distribution measuring apparatus LA950 (manufactured by Horiba, Ltd.).
  • the shape of the inorganic fine particles is not particularly limited, and any shape such as a spherical shape, an irregular shape, or a needle shape can be used.
  • the content of the inorganic fine particles is preferably in the range of 5 to 400% by mass with respect to the binder in the easy-adhesive layer.
  • the content of the inorganic fine particles is preferably in the range of 50 to 300% by mass.
  • the easily adhesive layer can contain at least one crosslinking agent.
  • the crosslinking agent suitable for the easily adhesive layer include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents.
  • an oxazoline-based cross-linking agent is particularly preferable from the viewpoint of ensuring adhesiveness after wet heat aging. Details of the crosslinking agent, particularly details and preferred embodiments of the carbodiimide-based crosslinking agent and oxazoline-based crosslinking agent, are as described in the first polymer layer.
  • Epocros K2010E, K2020E, K2030E, WS-500, WS-700 (all manufactured by Nippon Shokubai Co., Ltd.), etc. can be used. It is.
  • the content of the crosslinking agent in the easy-adhesive layer is preferably 5 to 50% by mass, more preferably 20 to 40% by mass, based on the binder in the easy-adhesive layer.
  • the content of the crosslinking agent is 5% by mass or more, a good crosslinking effect can be obtained, and the strength and adhesiveness of the colored layer can be maintained.
  • the content is 50% by mass or less, the pot life of the coating liquid Can be kept long.
  • the easily adhesive layer may further contain a known matting agent such as polystyrene, polymethylmethacrylate, or silica, or a known surfactant such as anionic or nonionic.
  • a known matting agent such as polystyrene, polymethylmethacrylate, or silica
  • a known surfactant such as anionic or nonionic.
  • the formation of the easy-adhesion layer includes a method of bonding a polymer sheet having easy adhesion to a support or a method by coating. Especially, the method by application
  • a coating method for example, a known coating method such as a gravure coater or a bar coater can be used.
  • the coating solvent used for preparing the coating solution may be water or an organic solvent such as toluene or methyl ethyl ketone.
  • a coating solvent may be used individually by 1 type, and may mix and use 2 or more types.
  • the thickness of the easy-adhesion layer is not particularly limited, but is usually preferably 0.05 to 8 ⁇ m, more preferably 0.1 to 5 ⁇ m.
  • the thickness of the easy-adhesion layer is 0.05 ⁇ m or more, necessary easy adhesion can be suitably obtained, and when it is 8 ⁇ m or less, the surface shape becomes better.
  • the easily adhesive layer of the present invention needs to be transparent so as not to reduce the effect of the colored layer.
  • the resin film of the present invention is configured by providing a support.
  • a support a conventionally known support substrate can be appropriately selected.
  • a polymer substrate is preferred.
  • the polymer base material include base materials using polyester, polyolefins such as polypropylene and polyethylene, or fluorine-based polymers such as polyvinyl fluoride.
  • a polyester base material is preferable from the viewpoint of cost and mechanical strength.
  • the polyester used as the support in the present invention is a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
  • Specific examples of such polyester include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-naphthalate and the like. Of these, polyethylene terephthalate or polyethylene-2,6-naphthalate is particularly preferable from the viewpoint of balance between mechanical properties and cost.
  • the polyester may be a homopolymer or a copolymer. Further, the polyester may be blended with a small amount of another type of resin such as polyimide.
  • an Sb-based, Ge-based or Ti-based compound as a catalyst from the viewpoint of keeping the carboxyl group content below a predetermined range, and among these, a Ti-based compound is particularly preferable.
  • a Ti-based compound an embodiment is preferred in which the Ti-based compound is polymerized by using it as a catalyst so that the Ti element conversion value is in the range of 1 ppm to 30 ppm, more preferably 3 ppm to 15 ppm.
  • the amount of Ti compound used is within the above range in terms of Ti element, the terminal carboxyl group can be adjusted to the following range, and the hydrolysis resistance of the polymer substrate can be kept low.
  • Examples of the synthesis of polyester using a Ti compound include Japanese Patent Publication No. 8-301198, Japanese Patent No. 2543624, Japanese Patent No. 3335683, Japanese Patent No. 3717380, Japanese Patent No. 397756, Japanese Patent No. 39622626, and Japanese Patent No. 39786666.
  • No. 3, Patent No. 3,996,871, Patent No. 40000867, Patent No. 4053837, Patent No. 4,127,119, Patent No. 4,134,710, Patent No. 4,159,154, Patent No. 4,269,704, Patent No. 4,313,538 and the like can be applied.
  • the carboxyl group content in the polyester is preferably 50 equivalents / t or less, more preferably 35 equivalents / t or less.
  • the lower limit of the carboxyl group content is preferably 2 equivalents / t in terms of maintaining adhesion between the layer formed on the polyester (for example, a colored layer).
  • the carboxyl group content in the polyester can be adjusted by the polymerization catalyst species and the film forming conditions (film forming temperature and time). In the present specification, “equivalent / ton” represents a molar equivalent per ton.
  • the polyester in the present invention is preferably solid-phase polymerized after polymerization.
  • Solid-phase polymerization may be a continuous method (a method in which a tower is filled with a resin, which is slowly heated for a predetermined time and then sent out), or a batch method (a resin is charged into a container). , A method of heating for a predetermined time).
  • Japanese Patent No. 2621563, Japanese Patent No. 3121876, Japanese Patent No. 3136774, Japanese Patent No. 3603585, Japanese Patent No. 3616522, Japanese Patent No. 3617340, Japanese Patent No. 3680523, Japanese Patent No. 3717392 are disclosed.
  • the method described in Japanese Patent No. 4167159 can be applied.
  • the temperature of the solid phase polymerization is preferably 170 ° C. or higher and 240 ° C. or lower, more preferably 180 ° C. or higher and 230 ° C. or lower, and further preferably 190 ° C. or higher and 220 ° C. or lower.
  • the solid phase polymerization time is preferably 5 hours to 100 hours, more preferably 10 hours to 75 hours, and still more preferably 15 hours to 50 hours.
  • the solid phase polymerization is preferably performed in a vacuum or in a nitrogen atmosphere.
  • the polyester base material in the present invention is obtained by melt-extruding the above polyester into a film shape and then cooling and solidifying it with a casting drum to form an unstretched film.
  • the unstretched film is subjected to a longitudinal direction at Tg to (Tg + 60) ° C.
  • a biaxially stretched film that has been stretched once or twice or so so that the total magnification is 3 to 6 times, and then stretched so that the magnification is 3 to 5 times in the width direction at Tg to (Tg + 60) ° C.
  • heat treatment may be performed at 180 to 230 ° C. for 1 to 60 seconds as necessary.
  • Tg represents a glass transition temperature and can be measured based on JIS K7121 or ASTM D3418-82. For example. In the present invention, measurement is performed using a differential scanning calorimeter (DSC) manufactured by Shimadzu Corporation. Specifically, 10 mg of a polymer such as polyester is weighed as a sample, set in an aluminum pan, and heated at a rate of temperature increase of 10 ° C./min from room temperature to a final temperature of 300 ° C., with a DSC device, the amount of heat relative to temperature Was measured as the glass transition temperature.
  • DSC differential scanning calorimeter
  • the thickness of the polymer substrate (particularly the polyester substrate) is preferably about 25 to 300 ⁇ m. If the thickness is 25 ⁇ m or more, the mechanical strength is good, and if it is 300 ⁇ m or less, it is advantageous in terms of cost.
  • the polyester base material has a tendency to deteriorate the hydrolysis resistance as the thickness increases and cannot withstand long-term use. In the present invention, the thickness of the polyester base material is 120 ⁇ m or more and 300 ⁇ m or less, and When the content of the carboxyl group in the polyester is 2 to 50 equivalent / t, the effect of improving the wet heat durability is further exhibited.
  • the resin film of the present invention is configured by providing a polymer layer forming step as described above.
  • a specific manufacturing method for example, (1) adding and emulsifying and dispersing an oil phase containing the compound represented by the general formula (1) in an aqueous phase containing a water-soluble resin (eg, PVA); (2) Contains an emulsion obtained by the above emulsification dispersion, a fluorine-based polymer and / or a silicone-based polymer, and, if necessary, a crosslinking agent or a surfactant, and preferably 50% by mass or more of the solvent is water.
  • a water-soluble resin eg, PVA
  • the adhesiveness after wet heat aging can be enhanced by curing the polymer layer.
  • a step for forming another layer can be further provided in addition to the above step.
  • a coating liquid containing the components constituting the other layer is applied on the polymer substrate (for example, the side opposite to the side on which the polymer layer of the polymer substrate is formed).
  • coating is mentioned. Examples thereof include the methods described above as the method for forming the easily adhesive layer and the colored layer.
  • the resin film of this invention is used suitably for the use of the solar cell backsheet.
  • solar cell backsheets include: (1) A reflection containing a polymer layer on one side of a polymer substrate and a white pigment on the other side opposite to the side on which the polymer layer is coated (2) A polymer layer is coated on one side of the polymer substrate, and the other side opposite to the side on which the polymer layer is coated is colored The thing etc. which the colored layer containing a pigment was coated can be mentioned.
  • the polymer layer of the polymer base material is not coated with a sheet or film having one or more layers having a desired function.
  • the method of bonding to the other side is mentioned.
  • the sheet or film in this case is a sheet or film having one or more other layers. Specifically, a polymer layer is applied and formed on one side of a polymer substrate, and a white pigment (or a colored pigment other than white) is formed on the other side opposite to the side on which the polymer layer is formed.
  • a coating solution for forming a polymer layer may be applied to the polymer substrate after biaxial stretching, or the polymer after uniaxial stretching After the coating liquid for forming the polymer layer is applied to the substrate and dried, it may be stretched in a direction different from the direction of uniaxial stretching. Further, the coating solution may be applied to an unstretched polymer support and dried, and then stretched in two directions.
  • Example 1 -Fabrication of support- (1) Synthesis of polyester A slurry of 100 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals) and 45 kg of ethylene glycol (manufactured by Nippon Shokubai Co., Ltd.) was charged with about 123 kg of bis (hydroxyethyl) terephthalate in advance and the temperature was 250 The esterification reaction tank maintained at a temperature of 1.2 ° C. and a pressure of 1.2 ⁇ 10 5 Pa was sequentially supplied over 4 hours, and the esterification reaction was carried out over an additional hour after the completion of the supply. Thereafter, 123 kg of the obtained esterification reaction product was transferred to a polycondensation reaction tank.
  • JP-A-2005-340616 was used. Five minutes later, a 10% by mass ethylene glycol solution of ethyl diethylphosphonoacetate was added so as to be 5 ppm with respect to the resulting polymer.
  • the reaction system was gradually heated from 250 ° C. to 285 ° C. and the pressure was reduced to 40 Pa. The time to reach the final temperature and final pressure was both 60 minutes. The reaction was continued for 3 hours, and then the reaction system was purged with nitrogen and returned to normal pressure to stop the polycondensation reaction. Then, the obtained polymer melt was discharged into cold water in a strand form and immediately cut to produce polymer pellets (diameter: about 3 mm, length: about 7 mm).
  • undercoat layer-forming coating solution was applied to one surface of a PET support so that the amount of the binder was 0.1 g / m 2 and applied at 180 ° C for 1 minute.
  • An undercoat layer having a dry thickness of about 0.1 ⁇ m was formed by drying.
  • Titanium Dioxide Dispersion Components in the following composition were mixed, and the mixture was subjected to dispersion treatment for 1 hour using a dynomill type disperser.
  • composition of coating solution > ⁇ Titanium dioxide dispersion: 800.0 parts ⁇ Polyolefin binder: 108.0 parts (Arrow Base SE1010, manufactured by Unitika Ltd., solid content: 20% by mass) Polyoxyalkylene alkyl ether 30.0 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass) Oxazoline compound: 20.0 parts (Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., solid content: 25%; crosslinking agent) ⁇ Distilled water ... 42.0 parts
  • the oil phase liquid was added while stirring the obtained aqueous phase liquid at 500 rpm using a dissolver. After the addition, stirring was continued for another 5 minutes to obtain a uniform mixed solution.
  • the resulting mixed liquid (25 ° C.) was further stirred using a dissolver at 20,000 rpm for 10 minutes at 25 ° C. to obtain an emulsion (emulsion) 1.
  • the average particle size of the obtained emulsion 1 was measured by a laser analysis / scattering particle size distribution measuring apparatus LA950 (manufactured by Horiba, Ltd.), and the median size was 120 nm.
  • the organic solvent was distilled off from the emulsion 1 using an evaporator to obtain a dispersion 1.
  • the amount of the remaining organic solvent was measured by gas chromatography and found to be 0.7% by mass or less.
  • the concentration of Compound A-1 in Dispersion 1 was 13% by mass.
  • the average particle diameter of Dispersion 1 was measured by the same method as described above, the median diameter was 121 nm.
  • the obtained coating solution for forming the back layer 1 is coated with a binder coating amount of 3.0 g / m 2 on the support surface opposite to the side on which the reflective layer of the PET support is formed. Then, the compound A-1 was applied in an amount of 1.1 g / m 2 and dried at 180 ° C. for 1 minute to form a back layer 1 (polymer layer) having a dry thickness of about 3 ⁇ m.
  • Adhesion was performed under the condition that a vacuum laminator was evacuated at 128 ° C. for 3 minutes, then pressure-bonded for 2 minutes to perform temporary adhesion, and further in a dry oven at 150 ° C. for 30 minutes. In this way, a crystalline solar cell module was produced. When power generation operation was performed using the produced solar cell module, it showed good power generation performance as a solar cell.
  • Example 1 (Examples 2 to 10)
  • a backsheet sample was prepared and evaluated in the same manner as in Example 1 except that the concentration and coating amount of Compound A-1, and the binder concentration were changed as shown in Table 1 below.
  • a battery module was produced. The evaluation results are shown in Table 1 below.
  • Example 8 (Examples 11 to 14, Comparative Examples 1 to 3)
  • the compound A-1 used for the preparation of the coating solution for forming the back layer 1 was changed to the following compounds A-2 to A-5 and A-101 to A-103.
  • a backsheet sample was prepared and evaluated, and a solar cell module was prepared. The evaluation results are shown in Table 1 below.
  • Example 15 In Example 8, on the surface of the back layer 1 (polymer layer) formed on the surface opposite to the side on which the reflective layer of the PET support is provided, the back layer 2 forming application is performed according to the following procedure. A backsheet sample was prepared and evaluated in the same manner as in Example 8 except that the back layer 2 (protective polymer layer) was further formed by applying the liquid, and a solar cell module was prepared. The evaluation results are shown in Table 1 below.
  • Example 15 a backsheet sample was prepared and evaluated in the same manner as in Example 15 except that the binder type or ultraviolet absorber type of the back layer 1 was changed as shown in Table 1 below. A module was produced. The evaluation results are shown in Table 1 below.
  • each backsheet sample was measured using a spectroscopic color difference meter “Spectro Color Meter SE2000” manufactured by Nippon Denshoku Industries Co., Ltd. Thereafter, each backsheet sample was irradiated with ultraviolet light at an illuminance of 900 W / m 2 for 48 hours using a light resistance tester “I Super UV Tester W-151” manufactured by Iwasaki Electric Co., Ltd. However, environmental conditions at the time of ultraviolet light irradiation were 63 ° C. and 50% RH.
  • YI value (YI-2) of each backsheet sample was measured again using the same spectral color difference meter (Spectro Color Meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.).
  • YI (YI ⁇ 2) ⁇ (YI ⁇ 1) was determined from the measured values, and was used as an index indicating the degree of coloring of each backsheet sample, and was ranked according to the following evaluation criteria based on the YI value. Of these, ranks 3 to 5 are practically acceptable.
  • sample A was sandwiched between upper and lower clips with Tensilon (produced by ORIENTEC, RTC-1210A), peeling angle 180 °, pulling speed A tensile test was performed at 300 mm / min.
  • the length of the sample A to be stretched was 10 cm, and the tensile speed was 20 mm / min.
  • the elongation at break of the sample A obtained in this study and L 0.
  • the sample B was subjected to a wet heat treatment in an atmosphere of 120 ° C. and 100% RH for 50 hours, and then a tensile test was performed in the same manner as the sample A.
  • the elongation at break of Sample B at this time is L 1.
  • Adhesiveness- [A] Adhesiveness before wet heat aging Each backsheet sample was cut into a width of 20 mm ⁇ 150 mm to prepare two sample pieces. These two sample pieces are arranged so that the reflection layer side is inside, and an EVA sheet (EVA sheet manufactured by Mitsui Chemicals Fabro Co., Ltd .: SC50B) cut between 20 mm width ⁇ 100 mm length is sandwiched between them It was made to adhere to EVA by hot pressing using a laminator (vacuum laminator manufactured by Nisshinbo Co., Ltd.). The bonding conditions at this time were as follows. Using a vacuum laminator, evacuation was performed at 128 ° C.

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Abstract

La présente invention concerne un procédé de fabrication d'un film de résine qui forme un film de revêtement qui revêt bien une surface et présente une excellente adhésion à un matériau organique adjacent. Ledit procédé comprend une étape lors de laquelle un fluide de revêtement contenant au moins un composé représenté par la formule générale (1) et un polymère liant est appliqué sur un support, formant une couche polymère. (R1a à R1e représentent chacun un substituant monovalent autre qu'un groupe hydroxy (au moins un radical parmi R1a à R1e représente un substituant pour lequel σρ dans l'équation de Hammett vaut au moins 0,3, et les substituants représentés par R1a à R1e peuvent être reliés les uns aux autres, formant un cycle), et R1g à R1k, R1m, R1n et R1p représentent chacun un atome d'hydrogène ou un substituant monovalent (lesdits substituants peuvent être reliés les uns aux autres, formant un cycle).)
PCT/JP2011/076319 2010-12-08 2011-11-15 Film de résine et son procédé de fabrication WO2012077469A1 (fr)

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JP6451452B2 (ja) * 2015-03-30 2019-01-16 大日本印刷株式会社 転写シート及びこれを用いた加飾樹脂成形品
CN112492876B (zh) * 2018-07-17 2022-05-31 富士胶片株式会社 医疗用润滑性部件以及相关层叠材料用组合物、层叠材料、医疗器材、层叠材料的制造方法

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