WO2015119218A1 - 樹脂組成物およびその成形体 - Google Patents
樹脂組成物およびその成形体 Download PDFInfo
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- WO2015119218A1 WO2015119218A1 PCT/JP2015/053301 JP2015053301W WO2015119218A1 WO 2015119218 A1 WO2015119218 A1 WO 2015119218A1 JP 2015053301 W JP2015053301 W JP 2015053301W WO 2015119218 A1 WO2015119218 A1 WO 2015119218A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/12—Optical coatings produced by application to, or surface treatment of, optical elements by surface treatment, e.g. by irradiation
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
Definitions
- the present invention relates to a resin composition containing a methacrylic resin and a polycarbonate resin.
- the present invention also relates to a molded body and a resin film formed by molding the resin composition, and a stretched film formed by stretching the resin film.
- this invention relates to the polarizer protective film which consists of a resin film or a stretched film.
- this invention relates to the polarizing plate containing a polarizer and a polarizer protective film.
- Aromatic polycarbonate resins generally have excellent high temperature stability, dimensional stability, impact resistance, rigidity, transparency, and the like. However, scratch resistance and long-term UV resistance are insufficient, and there is a disadvantage that stress birefringence occurs.
- methacrylic resins are known to have excellent transparency, surface hardness, UV resistance, weather resistance, chemical resistance, and the like. However, dimensional stability, impact resistance, low temperature resistance and the like are insufficient.
- a resin composition containing an aromatic polycarbonate resin and a methacrylic resin is expected to compensate for the disadvantages of each component and provide a material that can be used in various applications.
- a resin composition containing an aromatic polycarbonate resin and a methacrylic resin is opaque and cannot be used for applications requiring transparency. Therefore, in order to obtain a transparent resin composition containing an aromatic polycarbonate resin and a methacrylic resin, a method using a methacrylic resin containing a specific monomer component as a methacrylic resin has been proposed.
- Patent Document 1 an aromatic polycarbonate resin, 5 to 95% by weight of a methyl methacrylate monomer unit, 5 to 95% by weight of a methacrylic acid ester monomer unit having a carbocyclic group as an ester group, and ⁇ , ⁇ A resin composition containing a methacrylic resin obtained by polymerizing 0 to 40% by weight of unsaturated monomer units is described.
- a resin composition containing an aromatic polycarbonate resin and a methacrylic resin usually has a property of becoming cloudy when heated above a certain temperature (sometimes referred to as LCST behavior).
- the temperature at which the cloudiness occurs is a molding method for molding a resin composition such as an injection molding method, a press molding method, and a melt extrusion molding method. May fall below the normal temperature range. Therefore, when the resin composition is molded in the molding method, the resulting molded body may become cloudy and opaque.
- An object of the present invention is to provide a resin composition capable of obtaining a molded article in which the occurrence of white turbidity is suppressed and excellent in transparency.
- a resin composition containing a methacrylic resin and an aromatic polycarbonate resin The methacrylic resin is 69 to 85% by weight of methyl methacrylate with respect to the total of 100% by weight of the monomer components.
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an alkyl group substituted with a cycloalkyl group, a cycloalkyl group, a cycloalkyl group substituted with an alkyl group, or an alkyl group substituted with a phenyl group.
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an alkyl group substituted with a cycloalkyl group, a cycloalkyl group, a cycloalkyl group substituted with an alkyl group, or an alkyl group substituted with a phenyl group.
- the aromatic polycarbonate resin has a weight average molecular weight of 20000 to 60000,
- the content of methacrylic resin and aromatic polycarbonate resin is 50 to 95 parts by weight of methacrylic resin and 5 to 50 parts by weight of aromatic polycarbonate resin with respect to 100 parts by weight of the total of methacrylic resin and aromatic polycarbonate resin.
- Resin composition is 50 to 95 parts by weight of methacrylic resin and 5 to 50 parts by weight of aromatic polycarbonate resin with respect to 100 parts by weight of the total of methacrylic resin and aromatic polycarbonate resin.
- the (meth) acrylic acid ester represented by the formula (I) is at least one selected from the group consisting of cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate and naphthyl methacrylate.
- ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the alkyl acrylate is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, and butyl acrylate.
- ⁇ 5> A resin film obtained by molding the resin composition according to any one of ⁇ 1> to ⁇ 3>.
- ⁇ 6> A stretched film obtained by stretching the resin film according to ⁇ 5>.
- ⁇ 7> A polarizer protective film comprising the resin film according to ⁇ 5>.
- ⁇ 8> A polarizer protective film comprising the stretched film according to ⁇ 6>.
- a polarizing plate comprising ⁇ 9> a polarizer and the polarizer protective film according to ⁇ 7> or ⁇ 8>, which is disposed on at least one surface of the polarizer.
- production of cloudiness and can obtain the molded object which is excellent in transparency is obtained. Furthermore, according to this invention, the molded object and resin film which shape
- the resin composition of the present invention it is possible to obtain a molded body and a resin film that are suppressed in white turbidity and excellent in transparency.
- the resin composition of the present invention contains a specific methacrylic resin and a specific polycarbonate resin at a predetermined ratio.
- the methacrylic resin used in the present invention comprises 59 to 90% by weight of methyl methacrylate based on the following formula (I) with respect to 100% by weight of the total monomer components.
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an alkyl group substituted with a cycloalkyl group, a cycloalkyl group, a cycloalkyl group substituted with an alkyl group, or an alkyl group substituted with a phenyl group.
- (meth) acryl means “acryl” or “methacryl”.
- methyl methacrylate a commercially available product may be used as it is, or a product synthesized separately according to a conventionally known method may be used.
- Methyl methacrylate is contained in a proportion of 59 to 90% by weight with respect to the total of 100% by weight of the monomer components constituting the methacrylic resin, from the viewpoint that the transparency and weather resistance of the methacrylic resin are good. Is contained in a proportion of 65 to 85% by weight.
- R 1 represents a hydrogen atom or a methyl group, preferably a methyl group.
- the (meth) acrylic acid ester represented by the above formula (I) has at least one alicyclic hydrocarbon group or aromatic hydrocarbon group, and a commercially available product may be used as it is or conventionally known. Those synthesized separately according to the above method may be used.
- R 2 represents “an alkyl group substituted with a cycloalkyl group”, “cycloalkyl group”, “a cycloalkyl group substituted with an alkyl group”, “an alkyl group substituted with a phenyl group”.
- the “alkyl group” of the “alkyl group substituted with a cycloalkyl group” represented by R 2 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group. , N-butyl group, isobutyl group, tert-butyl group and the like, and the “cycloalkyl group” as the substituent is preferably a cycloalkyl group having 5 to 12 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, and the like.
- R 1 Cyclobutyl group, cyclooctyl group, cyclododecyl group and the like.
- cycloalkyl groups substituent groups and the substitution positions in the alkyl groups.
- alkyl group substituted with a cycloalkyl group represented by R 1 include, for example, a methyl group or an ethyl group in which at least one hydrogen atom (H) is substituted with the above cycloalkyl group having 5 to 12 carbon atoms.
- the “cycloalkyl group” represented by R 2 is preferably a cycloalkyl group having 5 to 12 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, a cyclooctyl group, and a cyclododecyl group. Further, it may be further substituted with a substituent such as a hydroxyl group, an amino group, or a sulfone group, if necessary.
- the “cycloalkyl group” of the “cycloalkyl group substituted with an alkyl group” represented by R 2 is preferably a cycloalkyl group having 5 to 12 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, a cyclooctyl group. Group, cyclododecyl group and the like.
- alkyl group an alkyl group having 1 to 4 carbon atoms is preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n -Butyl group, isobutyl group, tert-butyl group and the like.
- alkyl groups that are substituent groups and the substitution positions in the cycloalkyl groups.
- Examples of the “cycloalkyl group substituted with an alkyl group” represented by R 1 include, for example, a cyclopentyl group, a cyclohexyl group, wherein at least one hydrogen atom (H) is substituted with the above alkyl group having 1 to 4 carbon atoms, A cyclobutyl group, a cyclooctyl group, a cyclododecyl group, etc. are mentioned.
- the “alkyl group” of the “alkyl group substituted with a phenyl group” represented by R 2 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples thereof include an n-butyl group, an isobutyl group, and a tert-butyl group.
- Examples of the “alkyl group substituted with a phenyl group” represented by R 1 include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n group in which at least one hydrogen atom (H) is substituted with a phenyl group.
- -Butyl group, isobutyl group, tert-butyl group and the like for example, benzyl group, phenethyl group, etc.).
- the “phenyl group” represented by R 2 is not particularly limited, and may be further substituted with a substituent such as a hydroxyl group, an amino group, or a sulfone group.
- alkyl group that is a substituent of the phenyl group of the “phenyl group substituted with an alkyl group” represented by R 2 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, n -Propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and the like.
- the number of “alkyl groups” that are substituents and the position of substitution in the phenyl group include an o-tolyl group, an m-tolyl group, and a p-tolyl group.
- the “alkyl group” of the “alkyl group substituted with a naphthyl group” represented by R 2 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples thereof include an n-butyl group, an isobutyl group, and a tert-butyl group. There are no particular restrictions on the number of “naphthyl groups” that are substituent groups and the substitution positions in the alkyl groups.
- Examples of the “alkyl group substituted with a naphthyl group” represented by R 1 include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n group in which at least one hydrogen atom (H) is substituted with a naphthyl group.
- -Butyl group, isobutyl group, tert-butyl group and the like for example, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylmethyl group, 2-naphthylethyl group, etc.).
- the “naphthyl group” represented by R 2 is not particularly limited, and may be further substituted with a substituent such as a hydroxyl group, an amino group, or a sulfone group.
- the “alkyl group” that is a substituent of the naphthyl group of the “naphthyl group substituted with an alkyl group” represented by R 2 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, n -Propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and the like.
- Examples of the “naphthyl group substituted with an alkyl group” represented by R 1 include a methylnaphthyl group and an ethylnaphthyl group.
- the “dicyclopentanyl group” and “dicyclopentenyl group” represented by R 2 may be further substituted with a substituent such as an alkyl group, a hydroxyl group, an amino group, or a sulfone group.
- the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. .
- R 2 is preferably a cycloalkyl group (preferably a cyclohexyl group), a benzyl group, a phenyl group, or a naphthyl group, more preferably a cyclohexyl group or a phenyl group, and particularly preferably a phenyl group.
- the (meth) acrylic acid ester represented by the formula (I) is preferably cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, or naphthyl methacrylate, more preferably cyclohexyl methacrylate or methacrylic acid. It is a phenyl acid, Especially preferably, it is a phenyl methacrylate.
- the (meth) acrylic acid ester represented by the formula (I) may be used alone or in combination of two or more.
- the (meth) acrylic acid ester represented by the formula (I) is contained in a proportion of 10 to 40% by weight with respect to a total of 100% by weight of the monomer components constituting the methacrylic resin.
- the content of the (meth) acrylic acid ester represented by the formula (I) is less than 10% by weight, the compatibility of the methacrylic resin with the aromatic polycarbonate resin is lowered, and the transparency of the resin composition and the molded product thereof is lowered. In addition, the weather resistance of the resin composition and the molded body thereof may be reduced.
- the (meth) acrylic acid ester represented by the formula (I) is preferably contained in an amount of 15 to 30% by weight with respect to 100% by weight of the total monomer components constituting the methacrylic resin.
- alkyl acrylate a commercially available product may be used as it is, or a product synthesized separately according to a conventionally known method may be used.
- the alkyl acrylate is not particularly limited as long as it is copolymerizable with methyl methacrylate and / or the (meth) acrylic acid ester represented by the formula (I).
- Alkyl acrylate having a linear or branched or cyclic alkyl group of ⁇ 12 for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, butyl acrylate (n-butyl acrylate, And isobutyl acrylate, tert-butyl acrylate, sec-butyl acrylate) and 2-ethylhexyl acrylate.
- alkyl acrylate having an alkyl group having 1 to 4 carbon atoms is preferable, and methyl acrylate, ethyl acrylate, and butyl acrylate are more preferable.
- alkyl acrylate may be used independently and may use 2 or more types together.
- the alkyl acrylate is contained in a proportion of 0.4 to 0.8% by weight with respect to 100% by weight of the total monomer components constituting the methacrylic resin.
- the resin composition suppresses the occurrence of white turbidity even when the upper limit temperature of the temperature range in the molding process is set to a higher temperature.
- a molded article having excellent transparency can be obtained.
- a molded body and a resin film formed by molding such a resin composition are suppressed in white turbidity and excellent in transparency.
- the content of alkyl acrylate is less than 0.4% by weight or more than 0.8% by weight, the transparency of the resulting molded article is not improved in any case.
- a resin composition having an alkyl acrylate content of 0.4 to 0.8% by weight is used when the alkyl acrylate content in the resin composition is less than 0.4% by weight or more than 0.8% by weight. Compared with the above, it is possible to obtain a molded article having a high cloud point and suppressing the occurrence of white turbidity even in molding under a higher temperature condition and having excellent transparency.
- the alkyl acrylate is preferably contained in an amount of 0.4 to 0.6% by weight with respect to 100% by weight of the total monomer components constituting the methacrylic resin.
- a monomer component which comprises a methacryl resin as long as the effect of this invention is not impaired, other than said methyl methacrylate, (meth) acrylic acid ester shown by Formula (I), and alkyl acrylate A monomer may be included.
- the polymerization method for polymerizing the monomer component is not particularly limited, and for example, known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be employed.
- a radical polymerization initiator is usually used, and preferably a radical polymerization initiator and a chain transfer agent are used.
- polymerization initiator for example, azo compounds such as azobisisobutyronitrile, radical polymerization initiators such as organic peroxides such as lauroyl peroxide and 1,1-di (t-butylperoxy) cyclohexane are preferable. Used.
- a polymerization initiator may be used independently and may use 2 or more types together. What is necessary is just to determine the quantity of a polymerization initiator suitably according to the kind of monomer, its ratio, etc.
- chain transfer agent for example, mercaptans such as n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, 2-ethylhexyl thioglycolate are preferably used.
- a chain transfer agent may be used independently and may use 2 or more types together. The amount of the chain transfer agent may be appropriately determined according to the type of monomer and the ratio thereof.
- the polymerization temperature and polymerization time for polymerizing the monomer components are not particularly limited, and may be appropriately set according to the type of monomer, the ratio of the monomer, and the like.
- the methacrylic resin has a weight average molecular weight of preferably 60,000 to 300,000, more preferably 80,000 to 200,000.
- the methacrylic resin has a weight average molecular weight in such a range, it has excellent fluidity, and is easy to melt and knead when producing a resin composition, thereby improving workability. Moreover, the transparency and mechanical strength of the resulting resin composition and molded article are also improved.
- the methacrylic resin has a melt mass flow rate (MFR) at 230 ° C. measured at a load of 3.8 kg, preferably 0.1 to 50 g / 10 minutes, more preferably 0.2 to 30 g / 10 minutes. .
- MFR melt mass flow rate
- the methacrylic resin includes a mold release agent, an ultraviolet absorber, a dye, a pigment, a polymerization inhibitor, an antioxidant, a flame retardant, and a reinforcing material.
- the content of the copolymer with respect to 100 parts by weight of the total amount of methacrylic resin is preferably 95 to 99.995 parts by weight.
- the aromatic polycarbonate resin used in the present invention has a weight average molecular weight of 20,000 to 60,000.
- weight average molecular weight of the aromatic polycarbonate resin is less than 20000, the impact resistance and heat resistance of the molded product obtained by molding the resin composition are lowered.
- viscosity average molecular weight of the polycarbonate resin exceeds 40000, the compatibility with the methacrylic resin is lowered.
- the polycarbonate resin preferably has a weight average molecular weight of 20,000 to 40,000.
- an aromatic polycarbonate resin for example, one obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method or a melt transesterification method; a carbonate prepolymer is polymerized by a solid phase transesterification method or the like And the like obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.
- dihydric phenol examples include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis ⁇ (4-hydroxy-3,5-dimethyl) phenyl ⁇ methane, 1,1- Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis ⁇ (4-hydroxy-3-methyl) phenyl ⁇ propane, 2,2-bis ⁇ (4-hydroxy-3,5-dimethyl) phenyl ⁇ propane, 2,2-bis ⁇ (4-hydroxy-3,5-dibromo ) Phenyl ⁇ propane, 2,2-bis ⁇ (3-isopropyl-4-hydroxy) phenyl ⁇ propane, 2,2-bis ⁇ (4 -Hydroxy-3-phenyl) phenyl ⁇ propane, 2,2-bis (4-hydroxyphenyl)
- bisphenol A 2,2-bis ⁇ (4-hydroxy-3-methyl) phenyl ⁇ propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4 -Hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-Hydroxyphenyl) -3,3,5-trimethylcyclohexane and ⁇ , ⁇ ′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferred.
- carbonylating agent examples include carbonyl halide (such as phosgene), carbonate ester (such as diphenyl carbonate), and haloformate (such as dihaloformate of dihydric phenol). These may be used alone or in combination of two or more.
- Aromatic polycarbonate resin has a melt volume rate at 300 ° C. as measured by 1.2kg load (MVR) is preferably 2 ⁇ 100cm 3/10 min, more preferably 10 ⁇ 85cm 3/10 minutes.
- MVR melt volume rate at 300 ° C. as measured by 1.2kg load
- additives such as a mold release agent, an ultraviolet absorber, a dye, a pigment, a polymerization inhibitor, an antioxidant, a flame retardant, and a reinforcing material are contained within a range that does not impair the effects of the present invention. May be.
- the resin composition of the present invention comprises methacrylic resin and aromatic polycarbonate resin in a proportion of 50 to 95 parts by weight of methacrylic resin and 5 to 50 parts by weight of aromatic polycarbonate resin with respect to 100 parts by weight of the total. contains.
- the content of the aromatic polycarbonate resin is less than 5 parts by weight, the mechanical strength of the molded product obtained by molding the resin composition becomes insufficient.
- the content of the aromatic polycarbonate resin exceeds 50 parts by weight, the transparency of the resin composition and the molded product obtained by molding is lowered.
- the methacrylic resin is preferably contained in a proportion of 50 to 80 parts by weight
- the aromatic polycarbonate resin is preferably contained in a proportion of 20 to 50 parts by weight.
- an ultraviolet absorber in addition to the methacrylic resin and the aromatic polycarbonate resin, as long as the effects of the present invention are not impaired, an ultraviolet absorber, an antioxidant, a compatibilizer, a stabilizer, a colorant, a foaming agent, Conventional additives such as lubricants, mold release agents, antistatic agents, flame retardants, and flame retardant aids may be blended. Moreover, you may add a small amount of other thermoplastic resins. These additives may be added at the time of melt kneading of the resin mixture containing the methacrylic resin and the aromatic polycarbonate resin, or may be added before or after the melt kneading. When the additive is added, the total content of methacrylic resin and aromatic polycarbonate resin with respect to 100 parts by weight of the total resin composition is preferably 70 to 99.995 parts by weight.
- UV absorbers examples include triazine UV absorbers, benzophenone UV absorbers, benzotriazole UV absorbers, benzoate UV absorbers, and cyanoacrylate UV absorbers. These may be used alone or in combination of two or more.
- triazine ultraviolet absorbers examples include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy- 4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy- 4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- ( 2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5 Triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphen
- benzophenone UV absorber examples include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2 ', 4,4' -Tetrahydroxy-benzophenone and the like.
- benzotriazole ultraviolet absorbers examples include 2- (2′-hydroxy-5-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole.
- 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy- 3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3' , 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 '-(3 ", 4", 5 , 6 ′′ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2-
- benzoate ultraviolet absorber examples include 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, 2,6-di-t-butylphenyl- 3 ', 5'-di-t-butyl-4'-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate and n-octadecyl-3,5-di-t-butyl -4-hydroxybenzoate and the like.
- cyanoacrylate-based ultraviolet absorbers examples include 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3- (3 ′, 4′-methylenedioxyphenyl) -acrylate, and the like. Is mentioned.
- UV absorber examples include “Kemisorb 102” manufactured by Chemipro Kasei Co., Ltd., “Adekastab LAF70” manufactured by ADEKA Co., Ltd., and “Adekastab” manufactured by ADEKA Co., Ltd. as a benzotriazole-based UV absorber.
- Commercial products such as “LA31” are also included.
- the weight average molecular weight of the ultraviolet absorber is preferably 500 to 1000, more preferably 550 to 700. If the weight average molecular weight is too small, it tends to volatilize during molding, and if the molecular weight is too large, the compatibility with methacrylic resins and aromatic polycarbonate resins tends to decrease.
- the ultraviolet absorber preferably has a molar extinction coefficient at a wavelength of absorption maximum of 10 L / mol ⁇ cm or more, more preferably 15 L / mol ⁇ cm or more.
- the ultraviolet absorbing ability is further improved, and the content of the ultraviolet absorber can be reduced.
- antioxidants examples include hindered phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. These may be used alone or in combination of two or more.
- hindered phenol-based antioxidant examples include “Irganox 1010”, “Irganox 1035”, “Irganox 1076”, “Irganox 1222” manufactured by Ciba Geigy Co., Ltd., “Antigene P”, “Antigene 3C” manufactured by Sumitomo Chemical Co., Ltd.
- Commercial products such as “Antigene FR”, “Sumilyzer S”, “Sumilyzer GA80”, “Adeka Stub AO70”, “Adeka Stub AO80”, “Adeka Stub AO503” manufactured by ADEKA Corporation are listed.
- phosphorus antioxidants examples include tris (2,4-di-t-butylphenyl) phosphite, 2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d.
- sulfur antioxidants include dimethyl disulfide, diethyl disulfide, di-n-propyl disulfide, di-n-butyl disulfide, di-sec-butyl disulfide, di-tert-butyl disulfide, di-tert-amyl disulfide. , Dicyclohexyl disulfide, di-tert-octyl disulfide, di-n-dodecyl disulfide, di-tert-dodecyl disulfide and the like. Among these, di-tert-alkyl disulfide is preferable, and di-tert-dodecyl disulfide is more preferable.
- the resin composition of the present invention is obtained, for example, by melt-kneading a resin mixture containing a methacrylic resin and an aromatic polycarbonate resin.
- melt kneading is usually performed at a temperature of 180 to 320 ° C., preferably 200 to 300 ° C., and usually at a shear rate of 10 to 200 sec ⁇ 1 , preferably 30 to 150 sec ⁇ 1. At a shear rate of.
- an ordinary mixer, kneader, or the like can be used as an apparatus used for melt kneading.
- an ordinary mixer, kneader, or the like can be used.
- Specific examples include a single screw kneading extruder, a twin screw kneading extruder, a ribbon blender, a Henschel mixer, a Banbury mixer, and a drum tumbler.
- a twin-screw kneading extruder is preferable.
- the melt-kneading can be performed in an atmosphere of an inert gas such as nitrogen gas, argon gas, helium gas, if necessary.
- a resin composition can be obtained in which the formation of white turbidity is suppressed and a molded article excellent in transparency can be obtained. Moreover, the resin composition is excellent in transparency.
- the resin composition of the present invention it is possible to obtain a molded article that is suppressed in cloudiness and excellent in transparency.
- the resin composition of the present invention is processed into a desired shape and processed into a molded body.
- the molded body is formed by molding a resin composition.
- the molded body obtained by molding the resin composition of the present invention is excellent in transparency because the occurrence of white turbidity is suppressed. Further, the molded body has excellent mechanical properties.
- a resin composition obtained by melting and kneading a methacrylic resin and an aromatic polycarbonate resin may be used as it is, or after the resin composition is made into a predetermined shape such as a pellet, A resin composition having a shape may be used.
- the molding method is not particularly limited, and examples thereof include an injection molding method, a press molding method, and a melt extrusion molding method.
- the molded body is useful as, for example, an electro-optical material (a material such as a lens, an optical disk substrate, or a light guide plate), a cover material (a material such as a cover such as a display), or a resin glazing material.
- an electro-optical material a material such as a lens, an optical disk substrate, or a light guide plate
- a cover material a material such as a cover such as a display
- resin glazing material a resin glazing material.
- the resin film is formed by molding a resin composition, and is a film-like molded body.
- the resin film is formed by molding a resin composition.
- the resin film formed by molding the resin composition of the present invention is excellent in transparency because the occurrence of white turbidity is suppressed.
- the thickness of the resin film is preferably 10 to 1000 ⁇ m, more preferably 20 to 500 ⁇ m, and further preferably 20 to 300 ⁇ m.
- the method for molding the resin composition to obtain a resin film is not particularly limited.
- a resin composition containing a methacrylic resin and an aromatic polycarbonate resin is obtained, and then the resin composition is Examples of the method include molding by a melt extrusion molding method, a solution casting film forming method, and a hot pressing method. Among them, the melt extrusion molding method is preferable.
- melt extrusion molding method for example, first, a methacrylic resin and an aromatic polycarbonate resin are mixed, and if necessary, the other components described above are further mixed to obtain a resin composition, and then obtained.
- the obtained resin composition is melt-kneaded by a single-screw or twin-screw extruder, and the molten resin is continuously extruded from the T die into a film shape.
- a polarizer protective film can be obtained by sandwiching between a pair of smooth metal rolls and molding and cooling.
- the method for mixing methacrylic resin, aromatic polycarbonate resin, and other components as required is not particularly limited, and any known method may be used, and a super mixer or Banbury mixer may be used. These may be melt-kneaded with a single-screw or twin-screw extruder or a combination thereof.
- the resin film is preferably a film having a single layer structure, but may be a film having a multilayer structure of two or more layers as long as the effects of the present invention are not impaired.
- each layer may be formed from a resin composition having the same composition, or may be formed from resin compositions having different compositions.
- Resin compositions with different compositions are those containing different types of resin, the same type of resin but different contents of each resin, the same type and content of resin, but the additive It includes all cases such as different ones.
- the resin film can be suitably used as a polarizer protective film.
- the resin film is, for example, an architectural lighting member such as a window or a carport roof material, a vehicle lighting member such as a window, an agricultural lighting member such as a greenhouse, an illumination member, a front filter, etc. It can be used by being laminated on a display member or the like.
- the stretched film is formed by stretching a resin film. Since the stretched film is formed by stretching a resin film, the occurrence of white turbidity is suppressed and the transparency is excellent similarly to the resin film. Moreover, since the stretched film is stretched, it has excellent mechanical properties.
- stretching examples include uniaxial stretching and biaxial stretching. Among these, biaxial stretching is preferable.
- biaxial stretching examples include sequential stretching and simultaneous biaxial stretching.
- the stretching direction include a machine flow direction of an unstretched film (that is, a resin film), a direction orthogonal to the machine flow direction, and a direction oblique to the machine flow direction. The draw ratio is preferably 1.1 to 3.0 times.
- the machine flow direction is defined as the longitudinal direction
- the stretching in the longitudinal direction is defined as the longitudinal stretching
- the direction orthogonal to the machine flow direction is defined as the transverse direction
- the stretching in the transverse direction is defined as the transverse stretching.
- the stretched film may be subjected to a surface treatment, and examples of the surface treatment include a hard coat treatment, an antiglare treatment, and an antifouling treatment.
- the stretched film can be suitably used as a polarizer protective film.
- the stretched film includes, for example, architectural daylighting members such as windows and carport roofing materials, vehicle daylighting members such as windows, agricultural daylighting members such as greenhouses, lighting members, and front filters. It can be used by being laminated on a display member or the like.
- a resin film or a stretched film can be arranged as a polarizer protective film on at least one surface of the polarizer to form a polarizing plate.
- a polarizing plate includes a polarizer and a polarizer protective film disposed on at least one surface of the polarizer. It is preferable that the polarizer protective film and the polarizer are bonded.
- a polarizer is a step of uniaxially stretching a polyvinyl alcohol resin film according to a known method, a step of adsorbing the dichroic dye by dyeing the polyvinyl alcohol resin film with a dichroic dye, It can be manufactured through a process of treating the adsorbed polyvinyl alcohol-based resin film with a boric acid aqueous solution and a step of washing with water after the treatment with the boric acid aqueous solution.
- the polarizer thus obtained has an absorption axis in the uniaxially stretched direction.
- polyvinyl alcohol resin a saponified polyvinyl acetate resin
- examples of the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith.
- examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
- the saponification degree of the polyvinyl alcohol-based resin is preferably 85 to 100 mol%, and more preferably 98 mol% or more.
- the polyvinyl alcohol resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can be used.
- the degree of polymerization of the polyvinyl alcohol-based resin is preferably 1000 to 10,000, and more preferably 1500 to 5000.
- a film made of such a polyvinyl alcohol resin is used as a raw film of a polarizer.
- the method for forming the polyvinyl alcohol-based resin into a film is not particularly limited, and a known method is employed.
- the film thickness of the polyvinyl alcohol-based raw film is preferably 10 to 150 ⁇ m.
- the uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with the dichroic dye, simultaneously with dyeing, or after dyeing.
- this uniaxial stretching may be performed before boric acid treatment or during boric acid treatment.
- uniaxial stretching can also be performed in these several steps.
- Uniaxial stretching may be performed by passing between spaced rolls having different peripheral speeds, or may be performed by sandwiching with hot rolls. Further, this uniaxial stretching may be dry stretching in which stretching is performed in the air, or wet stretching in which a polyvinyl alcohol-based resin film is stretched using a solvent such as water or an organic solvent. May be.
- the draw ratio is preferably 3 to 8 times.
- the dyeing of the polyvinyl alcohol resin film with the dichroic dye can be performed, for example, by a method of immersing the polyvinyl alcohol resin film in an aqueous solution containing the dichroic dye.
- the dichroic dye iodine or a dichroic organic dye is used.
- the polyvinyl alcohol-type resin film performs the immersion process to water before a dyeing process.
- iodine When iodine is used as the dichroic dye, a method of dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide is usually employed.
- the iodine content in this aqueous solution is preferably 0.01-1 part by weight per 100 parts by weight of water, and the potassium iodide content is 0.5-20 parts by weight per 100 parts by weight of water.
- the temperature of the aqueous solution used for dyeing is preferably 20 to 40 ° C.
- the immersion time (dyeing time) in this aqueous solution is preferably 20 to 1800 seconds.
- a method of dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic organic dye is usually employed.
- the content of the dichroic organic dye in this aqueous solution is preferably 0.0001 to 10 parts by weight, more preferably 0.001 to 1 part by weight per 100 parts by weight of water.
- This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing assistant.
- the temperature of the aqueous dichroic dye solution used for dyeing is preferably 20 to 80 ° C.
- the immersion time (dyeing time) in this aqueous solution is preferably 10 to 1800 seconds.
- the boric acid treatment after dyeing with the dichroic dye can be performed by a method of immersing the dyed polyvinyl alcohol resin film in a boric acid-containing aqueous solution.
- the amount of boric acid in the boric acid-containing aqueous solution is preferably 2 to 15 parts by weight and more preferably 5 to 12 parts by weight per 100 parts by weight of water.
- the boric acid-containing aqueous solution preferably contains potassium iodide.
- the amount of potassium iodide in the boric acid-containing aqueous solution is preferably 0.1 to 15 parts by weight and more preferably 5 to 12 parts by weight per 100 parts by weight of water.
- the immersion time in the boric acid-containing aqueous solution is preferably 60 to 1200 seconds, more preferably 150 to 600 seconds, and further preferably 200 to 400 seconds.
- the temperature of the boric acid-containing aqueous solution is preferably 50 ° C. or higher, more preferably 50 to 85 ° C., and still more preferably 60 to 80 ° C.
- the polyvinyl alcohol resin film after the boric acid treatment is usually washed with water.
- the water washing treatment is performed, for example, by immersing a boric acid-treated polyvinyl alcohol resin film in water.
- the temperature of water in the water washing treatment is preferably 5 to 40 ° C.
- the immersion time is preferably 1 to 120 seconds.
- a drying process is performed to obtain a polarizer.
- the drying process can be performed using a hot air dryer or a far infrared heater.
- the temperature for the drying treatment is preferably 30 to 100 ° C., more preferably 50 to 80 ° C.
- the drying treatment time is preferably 60 to 600 seconds, and more preferably 120 to 600 seconds.
- the moisture content of the polarizer is reduced to a level that does not cause a problem in actual use.
- the moisture content is preferably 5 to 20% by weight, more preferably 8 to 15% by weight.
- the moisture content is less than 5% by weight, the flexibility of the polarizer is lost, and the polarizer may be damaged or broken after drying.
- the moisture content exceeds 20% by weight, the thermal stability of the polarizer may be insufficient.
- the thickness of the polarizer to which the dichroic dye thus obtained is adsorbed and oriented is preferably 5 to 40 ⁇ m.
- a transparent resin film may be disposed on the other surface.
- the transparent resin film and the polarizer are preferably bonded in the same manner as in the case of the polarizer protective film and the polarizer.
- the transparent resin film include a triacetyl cellulose film, a polycarbonate film, a polyethylene terephthalate film, an acrylic resin film, a laminated film of an acrylic resin and a polycarbonate resin, and an olefin resin film.
- an adhesive for bonding between the polarizer protective film and the polarizer and bonding between the polarizer and the transparent resin film.
- the adhesive By using the adhesive, the polarizer protective film and the polarizer, and the polarizer and the transparent resin film are bonded via the adhesive layer.
- at least one of the bonding surfaces is preferably subjected to corona discharge treatment, plasma irradiation treatment, electron beam irradiation treatment, and other surface activation treatment.
- the adhesive for forming the adhesive layer can be arbitrarily selected and used from those exhibiting an adhesive force with respect to each member.
- a water-based adhesive that is, an active energy ray-curable adhesive containing an adhesive component dissolved in water or an adhesive component dispersed in water, or a component that cures upon irradiation with active energy rays is used.
- an active energy ray-curable adhesive is preferable from the viewpoint of productivity.
- water-based adhesive for example, a composition using a polyvinyl alcohol resin or a urethane resin as a main component can be mentioned as a preferable adhesive.
- a polyvinyl alcohol resin When a polyvinyl alcohol resin is used as the main component of the aqueous adhesive, examples of the polyvinyl alcohol resin include partially saponified polyvinyl alcohol and fully saponified polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, and acetoacetyl group-modified polyvinyl alcohol. And modified polyvinyl alcohol resins such as methylol group-modified polyvinyl alcohol and amino group-modified polyvinyl alcohol.
- the adhesive When using a polyvinyl alcohol-based resin as the adhesive component, the adhesive is often prepared as an aqueous solution of a polyvinyl alcohol-based resin.
- the concentration of the polyvinyl alcohol resin in the adhesive aqueous solution is preferably 1 to 10 parts by weight, and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of water.
- a curable component such as glyoxal or a water-soluble epoxy resin or a crosslinking agent
- water-soluble epoxy resins include polyamide polyamines obtained by reacting a polyalkylene polyamine such as diethylenetriamine or triethylenetetramine with a polycarboxylic acid such as adipic acid and epichlorohydrin. An epoxy resin etc. are mentioned.
- Commercially available products may be used as the polyamide polyamine epoxy resin, for example, “Smiles Resin 650” and “Smiles Resin 675” manufactured by Sumika Chemtex Co., Ltd., “WS-525” manufactured by Japan PMC Co., Ltd.
- the addition amount of the curable component or the crosslinking agent is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin.
- the addition amount is small, the effect of improving the adhesiveness is reduced, while when the addition amount is large, the adhesive layer may become brittle.
- a suitable adhesive composition is a mixture of a polyester ionomer type urethane resin and a compound having a glycidyloxy group.
- the polyester ionomer type urethane resin here is a urethane resin having a polyester skeleton, into which a small amount of ionic component (hydrophilic component) is introduced.
- An ionomer type urethane resin is directly emulsified in water without using an emulsifier and becomes an emulsion, so that it is preferable as an aqueous adhesive.
- curable component a component that is cured by irradiation of an active energy ray constituting the adhesive
- curable component includes an epoxy compound, an okitacene compound, and an acrylic type. Compound etc. are mentioned.
- a cationically polymerizable compound such as an epoxy compound or an okitacene compound
- a cationic polymerization initiator is blended.
- a radical polymerizable compound such as an acrylic compound
- a radical polymerization initiator is blended.
- an adhesive having an epoxy compound as one of the curable components is preferable, and an adhesive having an alicyclic epoxy compound in which an epoxy group is directly bonded to a saturated carbocycle as one of the curable components is more preferable. Moreover, you may use an oxetane compound together.
- epoxy compound commercially available products may be used.
- “Epicoat” series manufactured by Japan Epoxy Resin Co., Ltd. “Epicron” series manufactured by DIC Corporation, “Epototo” series manufactured by Toto Kasei Co., Ltd.
- Examples include the “ADEKA RESIN” series manufactured by ADEKA, the “Denacol” series manufactured by Nagase ChemteX Corporation, the “Dow Epoxy” series manufactured by Dow Chemical Co., and the “TEPIC” manufactured by Nissan Chemical Industries, Ltd.
- alicyclic epoxy compound in which the epoxy group is directly bonded to the saturated carbocyclic ring a commercially available product may be used.
- a commercially available product may be used.
- oxetane compound Commercially available products may be used as the oxetane compound, and examples thereof include “Aron Oxetane” series manufactured by Toagosei Co., Ltd., “ETERRNACOLL” series manufactured by Ube Industries, Ltd., and the like.
- cationic polymerization initiator commercially available products may be used.
- “Kayarad” series manufactured by Nippon Kayaku Co., Ltd. “Syracure” series manufactured by Union Carbide Co., Ltd.
- a certain "CPI” series, “TAZ”, “BBI” and “DTS” photoacid generators manufactured by Midori Chemical Co., Ltd. “Adekaoptomer” series manufactured by ADEKA Co., Ltd., "RHODORSIL” series manufactured by Rhodia Etc.
- the active energy ray-curable adhesive can contain a photosensitizer as necessary.
- a photosensitizer By using a photosensitizer, the reactivity is improved, and the mechanical strength and adhesive strength of the cured product layer can be further improved.
- the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, anthracene compounds, halogen compounds, and photoreducible dyes.
- the active energy ray-curable adhesive can be blended with various additives as long as the adhesiveness is not impaired.
- the additive include an ion trap agent, an antioxidant, a chain transfer agent, a tackifier, a thermoplastic resin, a filler, a flow regulator, a plasticizer, and an antifoaming agent.
- a curable component that cures by a reaction mechanism different from cationic polymerization can be blended within a range that does not impair the adhesion.
- the active energy ray-curable adhesives described above may have the same composition or different compositions, but it is preferable to perform irradiation of active energy rays for curing both at the same time.
- Examples of active energy rays include X-rays, ultraviolet rays, and visible rays.
- ultraviolet rays are preferable from the viewpoints of ease of use, ease of preparation of the active energy ray-curable adhesive, stability, and curing performance.
- Examples of the ultraviolet light source include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, and a metal halide lamp.
- the thickness of the adhesive layer obtained using the active energy ray-curable adhesive is preferably 1 to 50 ⁇ m, and more preferably 1 to 10 ⁇ m.
- the polarizing plate can be attached to a liquid crystal cell to form a liquid crystal panel used in a liquid crystal display device. It is preferable that the polarizing plate and the liquid crystal cell are bonded via an adhesive layer using an adhesive.
- This pressure-sensitive adhesive layer is generally formed of an acrylic pressure-sensitive adhesive having an acrylic resin mainly composed of an acrylate ester and an acrylic resin copolymerized with a functional group-containing acrylic monomer.
- a liquid crystal panel in which a polarizing plate is bonded to a liquid crystal cell via an adhesive layer can be used for a liquid crystal display device.
- ⁇ Cloud point> The resin composition was dried at 90 ° C. for 12 hours, and then press-molded at a press temperature of 220 ° C. using a press molding machine (“Shindo ASF hydraulic press” manufactured by Shindo Metal Industry Co., Ltd.). A 3 mm molded piece was obtained. Subsequently, the obtained molded piece was press-molded at respective press temperatures of 270 ° C., 275 ° C., 280 ° C., 285 ° C., and 290 ° C. to obtain 40 mm square test pieces having a thickness of 2 mm. The appearance of each of the obtained test pieces was visually evaluated, and the highest press temperature among the press temperatures at which a transparent test piece without white turbidity was obtained was taken as the cloud point of the resin composition.
- a monomer component was obtained by mixing methyl methacrylate (MMA), cyclohexyl methacrylate (CHMA) and methyl acrylate (MA) in the composition shown in Table 1.
- MMA methyl methacrylate
- CHMA cyclohexyl methacrylate
- MA methyl acrylate
- lauryl peroxide as a polymerization initiator is 0.2 parts by weight based on the sum of the monomer components
- 1-dodecyl mercaptan as a chain transfer agent is 0% relative to the sum of the monomer components. .41 parts by weight were added and dissolved.
- 0.05 parts by weight of sodium polyacrylate as a suspension stabilizer 0.24 parts by weight of anhydrous sodium phosphate and 0% of dibasic sodium phosphate heptahydrate as suspension stabilizers with respect to 100 parts by weight of ion-exchanged water.
- 150 parts by weight of the aqueous phase was added to 100 parts by weight of the monomer component, and suspension polymerization was performed.
- the obtained slurry-like reaction liquid was dehydrated and washed with a dehydrator and then dried to obtain a bead-like methacrylic resin.
- Examples 1 to 10, Comparative Examples 1 and 2 Production of Resin Composition
- Table 3 shows the cloud point measured for each of the obtained resin compositions.
- Examples 1 to 10, Comparative Examples 1 and 2 Production of molded bodies
- Each of the obtained resin compositions (Examples 1 to 10 and Comparative Examples 1 and 2) was dried at 90 ° C. for 12 hours, and then a press molding machine (“Shindo ASF hydraulic press manufactured by Shindo Metal Industry Co., Ltd.). )), Press molding was performed at a pressing temperature of 220 ° C. to obtain a molded piece having a thickness of 3 mm. Subsequently, the obtained molded piece was press-molded at respective press temperatures of 270 ° C., 275 ° C., and 280 ° C. to obtain each molded body having a thickness of 2 mm and a 40 mm square.
- Table 3 shows the results of evaluating the appearance of the obtained molded articles.
- Examples 11 to 12 Production of resin composition
- 30 parts by weight were mixed and melt kneaded at a rotation speed of 60 rpm and a cylinder temperature of 240 ° C. using a single-screw kneading extruder (“Labo Plast Mill” manufactured by Toyo Seiki Co., Ltd.).
- the melt was extruded into a strand shape, cooled, and then cut with a strand cutter to prepare a pellet-shaped resin composition.
- Table 4 shows the cloud point measured for the obtained resin composition.
- Examples 11 to 12 Production of molded body
- a press molding machine Shindo ASF hydraulic press manufactured by Shindo Metal Industry Co., Ltd.
- Press molding was performed at a pressing temperature of 220 ° C. to obtain a molded piece having a thickness of 3 mm.
- the obtained molded piece was press-molded at respective press temperatures of 270 ° C., 280 ° C., and 290 ° C. to obtain each molded body having a thickness of 2 mm and a 40 mm square.
- Table 4 shows the results of evaluating the appearance of the obtained test pieces.
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Abstract
Description
本発明は、メタクリル樹脂とポリカーボネート樹脂とを含有する樹脂組成物に関する。また、本発明は、この樹脂組成物を成形加工してなる成形体および樹脂フィルム、ならびにこの樹脂フィルムを延伸してなる延伸フィルムに関する。また、本発明は、樹脂フィルムまたは延伸フィルムからなる偏光子保護フィルムに関する。さらに、本発明は、偏光子と偏光子保護フィルムとを含む偏光板に関する。
<1>メタクリル樹脂と芳香族ポリカーボネート樹脂とを含有する樹脂組成物であって、
メタクリル樹脂が、単量体成分の合計100重量%に対して、メタクリル酸メチル69~85重量%、下式(I)
(式中、R1は水素原子またはメチル基を表し、R2はシクロアルキル基で置換されたアルキル基、シクロアルキル基、アルキル基で置換されたシクロアルキル基、フェニル基で置換されたアルキル基、フェニル基、アルキル基で置換されたフェニル基、ナフチル基で置換されたアルキル基、ナフチル基、アルキル基で置換されたナフチル基、ジシクロペンタニル基またはジシクロペンテニル基を表す。)
で示される(メタ)アクリル酸エステル10~40重量%、およびアクリル酸アルキル0.4~0.8重量%を含む単量体成分を重合して得られる樹脂であり、
芳香族ポリカーボネート樹脂の重量平均分子量が、20000~60000であり、
メタクリル樹脂と芳香族ポリカーボネート樹脂の含有量が、メタクリル樹脂と芳香族ポリカーボネート樹脂の合計100重量部に対して、メタクリル樹脂が50~95重量部、芳香族ポリカーボネート樹脂が5~50重量部である、樹脂組成物。
<2>前記式(I)で示される(メタ)アクリル酸エステルが、メタクリル酸シクロヘキシル、メタクリル酸ベンジル、メタクリル酸フェニルおよびメタクリル酸ナフチルからなる群より選ばれる少なくとも1種である前記<1>に記載の樹脂組成物。
<3>前記アクリル酸アルキルが、アクリル酸メチル、アクリル酸エチルおよびアクリル酸ブチルからなる群より選ばれる少なくとも1種である前記<1>または<2>に記載の樹脂組成物。
<4>前記<1>~<3>のいずれかに記載の樹脂組成物を成形加工してなる成形体。
<5>前記<1>~<3>のいずれかに記載の樹脂組成物を成形加工してなる樹脂フィルム。
<6>前記<5>に記載の樹脂フィルムを延伸してなる延伸フィルム。
<7>前記<5>に記載の樹脂フィルムからなる偏光子保護フィルム。
<8>前記<6>に記載の延伸フィルムからなる偏光子保護フィルム。
<9>偏光子と、前記偏光子の少なくとも一方の面に配置される前記<7>または<8>に記載の偏光子保護フィルムとを含む偏光板。
本発明の樹脂組成物を成形加工することで、白濁の発生が抑制され透明性に優れる成形体および樹脂フィルムが得られる。
本発明に用いられるメタクリル樹脂は、単量体成分の合計100重量%に対して、メタクリル酸メチル59~90重量%、下式(I)
(式中、R1は水素原子またはメチル基を表し、R2はシクロアルキル基で置換されたアルキル基、シクロアルキル基、アルキル基で置換されたシクロアルキル基、フェニル基で置換されたアルキル基、フェニル基、アルキル基で置換されたフェニル基、ナフチル基で置換されたアルキル基、ナフチル基、アルキル基で置換されたナフチル基、ジシクロペンタニル基またはジシクロペンテニル基を表す。)
で示される(メタ)アクリル酸エステル10~40重量%、およびアクリル酸アルキル0.4~0.8重量%を含む単量体成分を重合して得られる樹脂である。
本発明に用いられる芳香族ポリカーボネート樹脂は、重量平均分子量が20000~60000である。芳香族ポリカーボネート樹脂の重量平均分子量が20000未満の場合、樹脂組成物を成形して得られる成形体の耐衝撃性および耐熱性が低下する。一方、ポリカーボネート系樹脂の粘度平均分子量が40000を超える場合、メタクリル樹脂に対する相溶性が低下する。ポリカーボネート樹脂は、好ましくは20000~40000の重量平均分子量を有する。
本発明の樹脂組成物は、メタクリル樹脂と芳香族ポリカーボネート樹脂とを、これらの合計100重量部に対して、メタクリル樹脂が50~95重量部、芳香族ポリカーボネート樹脂が5~50重量部の割合で含有する。芳香族ポリカーボネート樹脂の含有量が5重量部未満の場合、樹脂組成物を成形して得られる成形体の機械的強度が不十分となる。一方、芳香族ポリカーボネート樹脂の含有量が50重量部を超える場合、樹脂組成物および成形して得られる成形体の透明性が低下する。
メタクリル樹脂は、好ましくは50~80重量部の割合で含有され、芳香族ポリカーボネート樹脂は、好ましくは20~50重量部の割合で含有される。
これらの樹脂を均一に溶融混練するために、溶融混練は、通常180~320℃、好ましくは200~300℃の温度条件下、通常10~200sec-1の剪断速度、好ましくは30~150sec-1の剪断速度で行われる。
本発明の樹脂組成物は、所望の形状に加工され、成形体に加工される。成形体は、樹脂組成物を成形加工してなるものである。本発明の樹脂組成物を成形加工してなる成形体は、白濁の発生が抑制され透明性に優れる。また、成形体は、機械的性質が優れる。
樹脂フィルムは、樹脂組成物を成形加工してなるものであり、フィルム状の成形体である。樹脂フィルムは、樹脂組成物を成形加工してなるものである。本発明の樹脂組成物を成形加工してなる樹脂フィルムは、白濁の発生が抑制され透明性に優れる。
延伸フィルムは、樹脂フィルムを延伸してなるものである。延伸フィルムは、樹脂フィルムを延伸してなるものであることから、樹脂フィルムと同様に、白濁の発生が抑制され透明性に優れる。また、延伸フィルムは、延伸されていることから、機械的性質が優れる。
二軸延伸としては、逐次延伸、同時二軸延伸などが挙げられる。延伸方向としては、未延伸フィルム(すなわち樹脂フィルム)の機械流れ方向、機械流れ方向に直交する方向、機械流れ方向に斜交する方向などが挙げられる。延伸倍率は、1.1~3.0倍であることが好ましい。ここで、本明細書において、機械流れ方向を縦方向、この縦方向の延伸を縦延伸と定義し、機械流れ方向に直交する方向を横方向、この横方向の延伸を横延伸と定義する。
偏光子の少なくとも一方の面に、樹脂フィルムや延伸フィルムを偏光子保護フィルムとして配置して偏光板とすることができる。かかる偏光板は、偏光子と、前記偏光子の少なくとも一方の面に配置される偏光子保護フィルムとを含む。偏光子保護フィルムと偏光子は、貼合されていることが好ましい。
また浸漬時間は、1~120秒であることが好ましい。
なお、得られた樹脂組成物および成形体の各種物性は、下記の方法によって測定および評価した。
樹脂組成物を、90℃で12時間乾燥した後、プレス成形機((株)神藤金属工業所製「シンドー式ASF型油圧プレス」)を用いて、220℃のプレス温度でプレス成形を行い厚みが3mmの成形片を得た。次いで、得られた成形片を、270℃、275℃、280℃、285℃、290℃の各プレス温度でそれぞれプレス成形を行い、厚みが2mmで40mm角の各試験片を得た。得られた各試験片について外観を目視で評価し、白濁がなく透明な試験片が得られたプレス温度のうち、最も高いプレス温度を、当該樹脂組成物の曇点とした。
得られた成形体について、目視にて外観を評価した。成形体が白濁がなく透明であるものを○と判定し、成形体が一部に白濁があり半透明であるものを△と判定し、成形体が全体に白濁があり不透明であるものを×と判定した。
メタクリル酸メチル(MMA)、メタクリル酸シクロヘキシル(CHMA)およびアクリル酸メチル(MA)を表1に示す組成で混合して単量体成分を得た。この単量体成分に、重合開始剤としてラウリルパーオキサイドを単量体成分の総和に対して0.2重量部と、連鎖移動剤として1-ドデシルメルカプタンを単量体成分の総和に対して0.41重量部とを添加し、これらを溶解させた。一方、イオン交換水100重量部に対し懸濁安定剤としてポリアクリル酸ナトリウムを0.05重量部、無水第一リン酸ナトリウムを0.24重量部ならびに第二リン酸ナトリウム7水和物を0.28重量部溶解させ懸濁重合水相としたうえで、上記単量体成分100重量部に対し水相150重量部を添加し、懸濁重合を行った。得られたスラリー状の反応液を脱水機により脱水、洗浄したのち、乾燥し、ビーズ状のメタクリル樹脂を得た。
CHMAをメタクリル酸フェニル(PhMA)に変更し、1-ドデシルメルカプタンの添加量を単量体成分の総和に対して0.30重量部とし、さらにMMA、PhMAおよびMAの組成を表2に示すようにした以外は、合成例1~12と同様にしてビーズ状のメタクリル樹脂を得た。
表3に示す各メタクリル樹脂(合成例1~12)70重量部と、芳香族ポリカーボネート(PC)としてCalibre301-40(住化スタイロンポリカーボネート株式会社製、重量平均分子量(Mw)=31000、MVR=40cm3/10min.)30重量部とを混合し、単軸混練押出機(東洋精機(株)製「ラボプラストミル」)を用いて、回転数60rpm、240℃のシリンダー温度にて溶融混練した。溶融物をストランド状に押出し、冷却したのちにストランドカッターで切断し、ペレット状の樹脂組成物を作製した。得られた各樹脂組成物について、曇点を測定した結果を表3に示す。
得られた各樹脂組成物(実施例1~10、比較例1~2)を、90℃で12時間乾燥した後、プレス成形機((株)神藤金属工業所製「シンドー式ASF型油圧プレス」)を用いて、220℃のプレス温度でプレス成形を行い厚みが3mmの成形片を得た。次いで、得られた成形片を、270℃、275℃、280℃の各プレス温度でそれぞれプレス成形を行い、厚みが2mmで40mm角の各成形体を得た。得られた各成形体について、外観を評価した結果を表3に示す。
表4に示す各メタクリル樹脂(合成例13~14)70重量部と、芳香族ポリカーボネート(PC)としてCalibre301-40(住化スタイロンポリカーボネート株式会社製、重量平均分子量(Mw)=31000、MVR=40g/10min.)30重量部とを混合し、単軸混練押出機(東洋精機(株)製「ラボプラストミル」)を用いて、回転数60rpm、240℃のシリンダー温度にて溶融混練した。溶融物をストランド状に押出し、冷却したのちにストランドカッターで切断し、ペレット状の樹脂組成物を作製した。得られた樹脂組成物について、曇点を測定した結果を表4に示す。
得られた各樹脂組成物(実施例11~12)を、90℃で12時間乾燥した後、プレス成形機((株)神藤金属工業所製「シンドー式ASF型油圧プレス」)を用いて、220℃のプレス温度でプレス成形を行い厚みが3mmの成形片を得た。次いで、得られた成形片を、270℃、280℃、290℃の各プレス温度でそれぞれプレス成形を行い、厚みが2mmで40mm角の各成形体を得た。得られた各試験片について、外観を評価した結果を表4に示す。
Claims (9)
- メタクリル樹脂と芳香族ポリカーボネート樹脂とを含有する樹脂組成物であって、
メタクリル樹脂が、単量体成分の合計100重量%に対して、メタクリル酸メチル59~90重量%、下式(I)
で示される(メタ)アクリル酸エステル10~40重量%、およびアクリル酸アルキル0.4~0.8重量%を含む単量体成分を重合して得られる樹脂であり、
芳香族ポリカーボネート樹脂の重量平均分子量が、20000~60000であり、
メタクリル樹脂と芳香族ポリカーボネート樹脂の含有量が、メタクリル樹脂と芳香族ポリカーボネート樹脂の合計100重量部に対して、メタクリル樹脂が50~95重量部、芳香族ポリカーボネート樹脂が5~50重量部である、樹脂組成物。 - 前記式(I)で示される(メタ)アクリル酸エステルが、メタクリル酸シクロヘキシル、メタクリル酸ベンジル、メタクリル酸フェニルおよびメタクリル酸ナフチルからなる群より選ばれる少なくとも1種である請求項1に記載の樹脂組成物。
- 前記アクリル酸アルキルが、アクリル酸メチル、アクリル酸エチルおよびアクリル酸ブチルからなる群より選ばれる少なくとも1種である請求項1または2に記載の樹脂組成物。
- 請求項1~3のいずれかに記載の樹脂組成物を成形加工してなる成形体。
- 請求項1~3のいずれかに記載の樹脂組成物を成形加工してなる樹脂フィルム。
- 請求項5に記載の樹脂フィルムを延伸してなる延伸フィルム。
- 請求項5に記載の樹脂フィルムからなる偏光子保護フィルム。
- 請求項6に記載の延伸フィルムからなる偏光子保護フィルム。
- 偏光子と、前記偏光子の少なくとも一方の面に配置される請求項7または8に記載の偏光子保護フィルムとを含む偏光板。
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KR20160118255A (ko) | 2016-10-11 |
JP2015147858A (ja) | 2015-08-20 |
CN105980473B (zh) | 2017-11-17 |
US20160347947A1 (en) | 2016-12-01 |
EP3103837A4 (en) | 2017-09-20 |
EP3103837A1 (en) | 2016-12-14 |
CN105980473A (zh) | 2016-09-28 |
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