JP5408885B2 - Resin composition, film and polarizing plate - Google Patents

Resin composition, film and polarizing plate Download PDF

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JP5408885B2
JP5408885B2 JP2008047036A JP2008047036A JP5408885B2 JP 5408885 B2 JP5408885 B2 JP 5408885B2 JP 2008047036 A JP2008047036 A JP 2008047036A JP 2008047036 A JP2008047036 A JP 2008047036A JP 5408885 B2 JP5408885 B2 JP 5408885B2
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resin composition
resin
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JP2009203348A (en
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直明 中西
伸二 小澤
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株式会社カネカ
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Description

  The present invention relates to a resin composition and an optical film comprising the resin composition.

  Acrylic resins are used as films, sheets and general molded products because they have excellent transparency and are easy to process.

  An acrylic resin having a glutaric anhydride structure, a glutarimide structural unit, or the like is excellent in transparency and heat resistance, and has a small photoelastic coefficient, so that application as an optical material is being studied. For example, Patent Document 1 discloses an optical film made of glutarimide acrylic resin. Patent Document 2 discloses a retardation plate made of glutarimide acrylic resin. However, glutarimide acrylic resins generally have a problem that their mechanical strength is not always sufficient.

Various studies have been made on improving the mechanical strength of glutarimide acrylic resins. In particular, for improving impact resistance, an impact resistance improver called “core / shell” type, which is obtained by graft polymerization of a vinyl monomer or the like on a rubbery polymer, is preferably used. Specific examples of the rubbery polymer include butadiene, acrylic, and polyorganosiloxane. However, when butadiene rubber is used, there is a problem that the weather resistance of the obtained resin is significantly impaired. Patent Document 3 discloses improvement in impact resistance by adding a polyorganosiloxane rubber, but there is a problem that the transparency of the obtained resin is impaired.
JP-A-6-256537 JP-A-6-11615 JP-A-1-75553

  The problem to be solved by the present invention is to provide a resin composition having heat resistance and excellent mechanical strength as a film, in particular, excellent bending resistance, and an optical film using the resin composition. It is.

  In order to solve the above problems, the present inventors have conducted intensive studies. As a result, for the acrylic resin with high heat resistance and high refractive index, in the graft copolymer having “core / shell” type structure, the composition of the core made of rubber-like copolymer is adjusted, and the glass transition temperature is adjusted. By setting the refractive index of the graft copolymer to a value close to the refractive index of the acrylic resin, while maintaining the transparency of the acrylic resin, In particular, the inventors have found that a resin composition excellent in bending resistance can be obtained, and have reached the present invention.

  That is, according to the present invention, the following composition, film and method thereof are provided.

1. A resin composition comprising the following components (A) and (B):
(A) 99 to 70% by weight of an acrylic resin having a glass transition temperature of 120 ° C. or higher and a refractive index of 1.50 or higher,
(B) A rubber-like polymer having a glass transition temperature of 0 ° C. or lower obtained by copolymerizing an acrylic ester, a methacrylic ester, an aromatic vinyl compound, and a monomer copolymerizable therewith, a vinyl group 1 to 30% by weight of a graft copolymer obtained by graft polymerization of a containing compound, wherein the difference from the refractive index of the acrylic resin is 0.03 or less.

  2. 2. The resin composition as described in 1 above, wherein the refractive index of the acrylic resin is 1.52 to 1.56.

  3. 1 or 2 above, wherein the acrylic resin (A) is a glutarimide acrylic resin having a unit represented by the following general formula (1) and a unit represented by the following general formula (2). The resin composition described in 1.

(In the formula, R 1 and R 2 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 3 is hydrogen, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 3 to 12 carbon atoms. A cycloalkyl group or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)

(In the formula, R 4 and R 5 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 6 is an alkyl group having 1 to 18 carbon atoms or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)
4). 4. The resin composition as described in 3 above, wherein the acrylic resin further comprises a unit represented by the following general formula (3).

(In the formula, R 7 is hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 8 is an aryl group having 6 to 10 carbon atoms.)
5. The graft copolymer (B) is obtained by graft-polymerizing 50 to 15% of a rubber-like polymer and 50 to 15% of a graft component.
The rubber-like polymer comprises 50 to 100% by weight of acrylic acid ester, 0 to 30% by weight of methacrylic acid ester, 0 to 20% by weight of aromatic vinyl, and 0 to 20% by weight of monomer copolymerizable therewith ( The total of these is 100% by weight)
The graft component is 0-30 wt% acrylic ester, 30-100 wt% methacrylic ester, 0-60 wt% aromatic vinyl, and 0-30 wt% monomer copolymerizable therewith (these The total is 100% by weight) and is obtained by graft copolymerization.
5. The resin composition according to any one of 1 to 4 above.

6). 6. The resin composition as described in any one of 1 to 5 above, wherein the acrylic ester that is a component of the rubber-like polymer of the graft copolymer (B) contains 2-phenoxyethyl acrylate. The component of the rubber-like polymer in the graft copolymer (B) is 50 to 99.5% by weight of 2-phenoxyethyl acrylate, 0 to 50% by weight of n-butyl acrylate, and 0.5 to 2% by weight of allyl methacrylate. (The total of these is 100% by weight), and the graft component in the graft copolymer (B) is 0 to 20% by weight of n-butyl acrylate, 30 to 70% by weight of methyl methacrylate, 30 to 30% of styrene. The resin composition according to any one of 1 to 6 above, comprising 60% by weight and 0 to 20% by weight of monomers copolymerizable therewith (the total of these being 100% by weight).

  8). 8. The resin composition as described in any one of 1 to 7 above, wherein the rubbery polymer of the graft copolymer (B) has an average particle size of 80 to 400 nm.

  9. A film comprising the resin composition according to any one of 1 to 8 above.

  10. It consists of the resin composition in any one of said 1-9, The film for optics characterized by the above-mentioned.

  11. 11. The optical film as described in 10 above, which is a film obtained by a melt extrusion method.

  12 12. The optical film as described in 10 or 11 above, which is a stretched film.

  13. 13. The optical film as described in any one of 10 to 12 above, wherein the in-plane retardation is 10 nm or less and the thickness direction retardation is 50 nm or less.

  14 A polarizer protective film comprising the optical film according to any one of 10 to 13 above.

  15. A retardation film using the optical film as described in any one of 10 to 12 above.

  16. A polarizing plate using the polarizer protective film described in 14 or 15 above.

  The resin composition of the present invention is transparent and heat resistant, and has improved mechanical strength, in particular, film bending resistance, and is particularly useful as a resin composition for optical films.

  An embodiment of the present invention will be described as follows. Note that the present invention is not limited to this.

  The acrylic resin (A) used in the present invention is an acrylic resin having a glass transition temperature of 120 ° C. or higher and a refractive index of 1.50 or higher. Specific examples include acrylic resins having a glutarimide structure, a glutaric anhydride structure, and a lactone structure as main units in the molecule. Among these, those having a refractive index of 1.52 to 1.56 are preferable, and acrylic resins having a glutarimide structure (hereinafter referred to as glutarimide acrylic resins) are preferably used.

  More specifically, for example, the following general formula (1)

(In the formula, R 1 and R 2 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 3 is hydrogen, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 3 to 12 carbon atoms. A cycloalkyl group or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)
(Hereinafter also referred to as “glutarimide unit”),
The following general formula (2)

(In the formula, R 4 and R 5 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 6 is an alkyl group having 1 to 18 carbon atoms or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)
A glutarimide resin containing a unit represented by (hereinafter also referred to as “(meth) acrylic acid ester unit”) can be suitably used.

  Moreover, the said glutarimide resin is the following general formula (3) as needed.

(In the formula, R 7 is hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 8 is an aryl group having 6 to 10 carbon atoms.)
(Hereinafter also referred to as “aromatic vinyl unit”).

In the general formula (1), R 1 and R 2 are each independently hydrogen or a methyl group, R 3 is preferably hydrogen, a methyl group, a butyl group, or a cyclohexyl group, and R 1 is a methyl group. More preferably, R 2 is hydrogen and R 3 is a methyl group.

The glutarimide resin may contain only a single type as a glutarimide unit, or may contain a plurality of types in which R 1 , R 2 , and R 3 in the general formula (1) are different. .

  In addition, a glutarimide unit can be formed by imidating the (meth) acrylic acid ester unit represented by the said General formula (2).

  In addition, acid anhydrides such as maleic anhydride, or half esters of such acid anhydrides and linear or branched alcohols having 1 to 20 carbon atoms, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itacone The glutarimide unit can also be formed by imidizing an α, β-ethylenically unsaturated carboxylic acid such as acid, itaconic anhydride, crotonic acid, fumaric acid, citraconic acid or the like.

In the general formula (2), R 4 and R 5 are each independently hydrogen or a methyl group, preferably R 6 is hydrogen or a methyl group, R 4 is hydrogen, and R 5 is methyl. And R 6 is more preferably a methyl group.

The glutarimide acrylic resin may contain only a single type as a (meth) acrylic acid ester unit, or a plurality of types in which R 4 , R 5 and R 6 in the general formula (2) are different. May be included.

  The glutarimide resin preferably contains styrene, α-methylstyrene, or the like as the aromatic vinyl unit represented by the general formula (3), and more preferably contains styrene.

Further, the glutarimide acrylic resin, aromatic vinyl units, may include only a single type, R 7 and R 8 may contain a plurality of different resins.

In the glutarimide acrylic resin, the content of the glutarimide unit represented by the general formula (1) is not particularly limited and is preferably changed depending on, for example, the structure of R 3 .

  Generally, the content of the glutarimide unit is preferably 20% by weight or more of the glutarimide acrylic resin, more preferably 20% to 95% by weight, and 40% to 90% by weight. More preferably, it is more preferable to set it as 50 to 80 weight%.

  If the content of the glutarimide unit is within the above range, the heat resistance and transparency of the resulting glutarimide acrylic resin will be reduced, or the moldability and mechanical strength when processed into a film will be extremely reduced. There is nothing to do.

  On the other hand, when the content of the glutarimide unit is less than the above range, the resulting glutarimide resin tends to be insufficient in heat resistance or impaired in transparency. On the other hand, if the amount is larger than the above range, the heat resistance and melt viscosity are unnecessarily increased, the molding processability is deteriorated, the mechanical strength during film processing is extremely lowered, or the transparency is impaired. Tend.

  In the glutarimide acrylic resin, the content of the aromatic vinyl unit represented by the general formula (3) is not particularly limited, but is preferably 0 to 50% by weight of the glutarimide acrylic resin, It is more preferable to set it as 0 to 20 weight%, and it is especially preferable to set it as 0 to 15 weight%. When there is more content of an aromatic vinyl unit than the said range, there exists a tendency for the heat resistance of the glutarimide acrylic resin obtained to be insufficient.

  The glutarimide acrylic resin may further be copolymerized with other units other than the glutarimide unit, the (meth) acrylic acid ester unit, and the aromatic vinyl unit, if necessary.

  Other units include, for example, (meth) acrylic acid units such as acrylic acid and methacrylic acid, amide-based units such as acrylamide and methacrylamide, glutaric anhydride units, nitrile monomers such as acrylonitrile and methacrylonitrile, Mention may be made of polymer units of maleimide-based polymers such as maleimide, N-methylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide.

  These other units may be directly copolymerized or graft copolymerized in the glutarimide resin.

  In addition, these other units may use the monomer constituting the unit as a copolymerization component with respect to a resin that is a raw material for obtaining a glutarimide resin and / or a glutarimide acrylic resin. When the imidation reaction is performed, the above-mentioned other units may be present as by-products, and introduced into the glutarimide acrylic resin by copolymerizing a monomer containing other units. May be.

Although the weight average molecular weight of the said glutarimide acrylic resin is not specifically limited, It is preferable that it is 1 * 10 < 4 > -5 * 10 < 5 >. If it is in the said range, moldability will not fall or the mechanical strength at the time of film processing will not be insufficient.

  On the other hand, when the weight average molecular weight is smaller than the above range, the mechanical strength when formed into a film tends to be insufficient. Moreover, when larger than the said range, the viscosity at the time of melt-extrusion is high, there exists a tendency for the moldability to fall and for the productivity of a molded article to fall.

  Moreover, it is preferable that the glass transition temperature of the said glutarimide acrylic resin is 120 degreeC or more, and it is more preferable that it is 130 degreeC or more. When the glass transition temperature is lower than the above range, the application range is limited in applications where heat resistance is required.

  In the glutarimide acrylic resin, the content (in other words, the ratio) of the units represented by the general formulas (1) to (3) is not particularly limited, and physical properties required for the glutarimide acrylic resin. Alternatively, it may be determined according to the characteristics required for a film formed by molding the thermoplastic resin composition according to the present invention.

  For example, when a film formed by molding the thermoplastic resin composition according to the present invention is used for optical applications, it may be determined according to optical characteristics required for the obtained film.

  Here, although one Embodiment of the manufacturing method of the said glutarimide resin is described, this invention is not limited to this.

  First, a (meth) acrylic acid ester polymer is produced by polymerizing a (meth) acrylic acid ester. In addition, when the said glutarimide resin contains an aromatic vinyl unit, a (meth) acrylic acid ester and aromatic vinyl are copolymerized and a (meth) acrylic acid ester-aromatic vinyl copolymer is manufactured.

  In this step, examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic acid t. -Butyl, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate are preferably used, and methyl methacrylate is more preferably used.

  These (meth) acrylic acid esters may be used alone or in combination of two or more. By using multiple types of (meth) acrylic acid esters, it is possible to give multiple types of (meth) acrylic acid ester units to the finally obtained glutarimide resin.

  Moreover, when the said glutarimide resin contains an aromatic vinyl unit, the ratio of an aromatic vinyl unit can be adjusted by adjusting the polymerization rate of (meth) acrylic acid ester and aromatic vinyl.

  The structures of the (meth) acrylic acid ester-aromatic vinyl copolymer and the (meth) acrylic acid ester polymer are not particularly limited as long as the imidization reaction is possible. Specifically, any of a linear (linear) polymer, a block polymer, a core-shell polymer, a branched polymer, a ladder polymer, and a crosslinked polymer may be used.

  In the case of a block polymer, it may be any of AB type, ABC type, ABA type, and other types of block polymers. In the case of the core-shell polymer, it may be composed of only one core and only one shell, or each may be composed of multiple layers.

  Next, a primary amine (that is, an imidizing agent) is added to the (meth) acrylic acid ester polymer or the (meth) acrylic acid ester-aromatic vinyl copolymer to perform imidization. Thereby, the said glutarimide resin can be manufactured.

  The primary amine, that is, the imidizing agent is not particularly limited as long as the glutarimide unit represented by the general formula (1) can be generated. Specifically, for example, an aliphatic hydrocarbon group-containing amine such as ammonia, methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, tert-butylamine, n-hexylamine, Mention may be made of aromatic hydrocarbon group-containing amines such as aniline, benzylamine, toluidine and trichloroaniline, and alicyclic hydrocarbon group-containing amines such as cyclohexylamine.

  In addition, urea-based compounds that generate amines exemplified above by heating, such as urea, 1,3-dimethylurea, 1,3-diethylurea, and 1,3-dipropylurea, can also be used.

  Of the imidizing agents exemplified above, methylamine, ammonia, and cyclohexylamine are preferably used from the viewpoint of cost and physical properties, and methylamine is particularly preferably used.

  In this imidization step, a ring closure accelerator may be added as necessary in addition to the primary amine.

  In the imidization step, the ratio of the glutarimide unit and the (meth) acrylate unit in the obtained glutarimide resin can be adjusted by adjusting the ratio of the primary amine added.

  Further, by adjusting the degree of imidization, the physical properties of the obtained glutarimide resin, the optical properties of an optical film formed by molding the thermoplastic resin composition according to the present invention, and the like can be adjusted.

  The method for imidizing the (meth) acrylic acid ester-aromatic vinyl copolymer or the (meth) acrylic acid ester polymer is not particularly limited, and any conventionally known method can be used. For example, the (meth) acrylic acid ester-aromatic vinyl copolymer or (meth) acrylic acid ester polymer may be imidized by an extruder or a method using a batch type reaction vessel (pressure vessel) or the like. it can.

  When manufacturing the said glutarimide resin using an extruder, the extruder to be used is not specifically limited, Various extruders can be used. Specifically, for example, a single screw extruder, a twin screw extruder, a multi-screw extruder, or the like can be used.

  Among these, it is preferable to use a twin screw extruder. According to the twin screw extruder, when using an imidizing agent (ring closure accelerator) for the raw material polymer (that is, (meth) acrylic acid ester-aromatic vinyl copolymer or (meth) acrylic acid ester polymer), Mixing of an imidizing agent and a ring closure accelerator) can be promoted.

  Examples of the twin-screw extruder include a non-meshing type same direction rotating type, a meshing type same direction rotating type, a non-meshing type different direction rotating type, and a meshing type different direction rotating type. Among them, it is preferable to use a meshing type co-rotating type. Since the meshing type co-rotating twin-screw extruder can rotate at a high speed, mixing of the imidizing agent (in the case of using a ring closure accelerator and an imidization agent and a ring closure accelerator) with the raw polymer is further improved. Can be promoted.

  The above-exemplified extruders may be used alone, or a plurality of the extruders may be connected in series.

  The extruder is preferably equipped with a vent port that can be reduced to atmospheric pressure or lower. According to such a configuration, unreacted imidizing agent, or by-products such as methanol and monomers can be removed.

  For the production of the glutarimide resin, instead of an extruder, for example, a horizontal biaxial reactor such as a Violac manufactured by Sumitomo Heavy Industries, Ltd. or a vertical biaxial agitation tank such as Super Blend is used. Viscosity-compatible reactors can also be suitably used.

  When manufacturing the said glutarimide resin using a batch type reaction tank (pressure vessel), the structure of the batch type reaction vessel (pressure vessel) is not specifically limited.

  Specifically, it has a structure in which the raw material polymer can be melted by heating and stirred, and an imidizing agent (in the case of using a ring closure accelerator, an imidizing agent and a ring closure accelerator) can be added. However, it is preferable to have a structure with good stirring efficiency.

  According to such a batch-type reaction vessel (pressure vessel), it is possible to prevent the polymer viscosity from increasing due to the progress of the reaction and the stirring to be insufficient. As a batch type reaction tank (pressure vessel) having such a structure, for example, a stirred tank Max Blend manufactured by Sumitomo Heavy Industries, Ltd. can be exemplified.

  According to the method as described above, a glutarimide resin in which the ratio of glutarimide units, (meth) acrylic acid ester units, and aromatic vinyl units is controlled as desired can be easily produced.

  Next, the graft copolymer which is the component (B) in the present invention will be described.

  The graft copolymer having a multilayer structure has a glass transition temperature of 0 ° C. or less obtained by copolymerizing an acrylic ester, a methacrylic ester, an aromatic vinyl compound, and a monomer copolymerizable therewith. A graft copolymer obtained by graft polymerization of a vinyl group-containing compound to a rubbery polymer, the refractive index of the graft copolymer, and the refractive index of the acrylic resin as the component (A) The difference is 0.03 or less.

  A smaller difference between the refractive index of the component (A) and the refractive index of the component (B) is preferably from the viewpoint of transparency, and is 0.03 or less, more preferably 0.01 or less.

  Moreover, the glass transition temperature of the rubber-like copolymer of the said (B) component has preferable 0 degrees C or less, More preferably, it is -20 degrees C or less. When the glass transition temperature exceeds 0 ° C., the mechanical strength such as bending resistance is lowered, which is not preferable.

  (B) As a monomer which forms the rubber-like copolymer of the graft copolymer, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, acrylic acid Acrylic esters such as benzyl, cyclohexyl acrylate, 2-phenoxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, etc. And aromatic vinyl compounds such as styrene and α-methylstyrene. Among these, ethyl acrylate, n-butyl acrylate, 2-phenoxyethyl acrylate, methyl methacrylate, styrene, and the like are preferably used. Among them, n-butyl acrylate and 2-phenoxyethyl acrylate are preferably used in order to have a high refractive index and a glass transition temperature of 0 ° C. or lower.

  The monomers copolymerizable with these monomers include acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, maleic anhydride, maleimide, N-methylmaleimide, and N-phenylmaleimide. , N-cyclohexylmaleimide, and the like.

  As a means for obtaining a rubbery crosslinked polymer of the graft copolymer of component (B), a monomer having two or more polymerizable unsaturated bonds in the molecule that can be copolymerized with the monomer is used. . Specific examples include allyl acrylate, allyl methacrylate, diallyl itaconate, diallyl phthalate, divinylbenzene, triallyl cyanurate, triallyl isocyanurate, butanediol diacrylate, and butanediol dimethacrylate. Of these, allyl methacrylate is preferably used.

  When the refractive index of the acrylic resin of the component (A) is as high as 1.52 or more, in order to match the refractive index of the rubbery copolymer of the component (B) in order to ensure the transparency of the resin composition, an acrylic resin is used. Copolymerizes a monomer mixture comprising 50 to 100% by weight of an acid ester, 0 to 30% by weight of a methacrylic acid ester, 0 to 30% of an aromatic vinyl, and 0 to 20% by weight of a monomer copolymerizable therewith. It is good to let them. At this time, when 2-phenoxyethyl acrylate, benzyl acrylate, or the like is used as the acrylate ester, the glass transition temperature of the rubber-like copolymer is effectively lowered while maintaining the refractive index of the rubber-like polymer high. can do. Preferable specific examples include 50 to 99.5% by weight of 2-phenoxyethyl acrylate, 0 to 50% by weight of n-butyl acrylate, and 0.5 to 2% by weight of allyl methacrylate (the total of which is 100% by weight). ) Is preferably mixed and copolymerized, and further, 70 to 99.5% by weight of 2-phenoxyethyl acrylate, 0 to 30% by weight of n-butyl acrylate, and 0.5 to 2% by weight of allyl methacrylate ( The total of these is preferably 100% by weight) and copolymerized.

  Next, the graft component in the graft copolymer of component (B) will be described. For the graft component, acrylic acid ester, methacrylic acid ester, aromatic vinyl, and monomers copolymerizable therewith can be used. Specifically, the monomers listed in the rubber-like polymer are used. In addition, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, glycidyl acrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-methoxyethyl methacrylate, glycidyl methacrylate Etc. are used.

  More preferable examples of the graft component include 0 to 30% by weight of acrylic acid ester, 30 to 100% by weight of methacrylic acid ester, 0 to 60% by weight of aromatic vinyl, and 0 to 30% of monomer copolymerizable therewith. More preferable examples include n-butyl acrylate 0 to 20% by weight, methyl methacrylate 30 to 70% by weight, styrene 30 to 60% by weight, and monomers 0 to 20 copolymerizable therewith. For example, a monomer mixture by weight%.

  The average particle size of the rubber-like polymer in the graft copolymer (B) is preferably 80 to 400 nm, more preferably 100 to 300 nm. If the average particle diameter of the rubber polymer is less than 80 nm, the strength may not be exhibited, which is not preferable. If the average particle diameter is more than 400 nm, the transparency of the resulting resin composition may be impaired. Therefore, it is not preferable.

  The proportion of the rubber-like polymer component in the graft copolymer (B) is preferably 50 to 85% by weight, more preferably 60 to 80% by weight. If the ratio of the rubber-like polymer component is less than 50% by weight, not only the mechanical strength of the resulting resin composition cannot be easily obtained, but also the viscosity at the time of melting of the resin composition increases, so that the moldability decreases. And the smoothness of the surface of the obtained molded article is lost, which is not preferable. Further, when the proportion of the rubbery polymer component exceeds 85% by weight, the dispersibility of the graft copolymer of the component (B) with respect to the acrylic resin of the component (A) may be impaired, and the obtained molded product The surface smoothness may not be obtained, which is not preferable.

  As a method for obtaining the graft copolymer, a known method such as emulsion polymerization can be used. As a specific example, a monomer component capable of forming a rubber-like polymer is reacted in the presence of water and an emulsifier, and then a monomer component capable of forming a graft component is added and polymerized.

  The proportion of the component (A) in the resin composition in the present invention is 99% to 70% by weight, preferably 97% to 80% by weight. When the proportion of the component (A) exceeds 99% by weight, the effect of improving the bending resistance due to the addition of the component (B) is not sufficient. It is not preferable because it may decrease.

  In addition, you may contain well-known additives, such as a lubricant, a plasticizer, a ultraviolet absorber, a stabilizer, a filler, and other resin with respect to the resin composition of this invention as needed.

  The resin composition of the present invention can be used as a film by utilizing properties such as heat resistance, transparency, and bending resistance. Specifically, food / pharmaceutical protection / preservation films, food molded sheets, agricultural moisture and heat insulation, electrical insulation for capacitors and motors, anti-electricity prevention, heat ray blocking, UV blocking, etc. Functional films, tapes, labels, seals, and other industrial and general decorative films, and storage media films such as negative films and video tapes.

  Moreover, the film which can be utilized as an optical film can be manufactured using the resin composition of this invention. The optical film in the present invention may be formed by molding the above-described resin composition, but is preferably a stretched film, that is, a stretched film. In addition, in the case of a stretched film, it may be a uniaxially stretched film that has been uniaxially stretched, or may be a biaxially stretched film that is obtained by combining stretching processes.

  As a method for molding a molded body comprising the resin composition of the present invention, any conventionally known method is possible, for example, injection molding, melt extrusion film molding, inflation molding, blow molding, compression molding, spinning molding and the like. Can be mentioned. Further, a solution casting method or a spin coating method in which the resin composition of the present invention is dissolved in a meltable solvent and then molded is also possible. Any of these methods can be employed, but a melt extrusion film forming method that does not use a solvent is preferable from the viewpoint of production costs and the influence of the solvent on the global environment and working environment.

  The thickness of the optical film according to the present invention is not particularly limited, but is preferably 10 μm to 200 μm, more preferably 15 μm to 150 μm, and further preferably 20 μm to 100 μm.

  When the thickness of the film is within the above range, an optical film having uniform optical characteristics and good haze can be obtained.

  On the other hand, if the thickness of the film exceeds the above range, the cooling of the film becomes non-uniform and the optical characteristics tend to be non-uniform. Moreover, when the thickness of a film is less than the said range, handling of a film may become difficult.

  The optical film according to the present invention has a haze of preferably 3% or less, more preferably 2% or less, and particularly preferably 1% or less.

  If the haze of the optical film according to the present invention is within the above range, the transparency of the film can be increased. Therefore, the optical film according to the present invention can be suitably used for applications requiring transparency.

  The optical film according to the present invention preferably has a total light transmittance of 85% or more, and more preferably 88% or more.

  If the total light transmittance is within the above range, the transparency of the film can be increased. Therefore, the optical film according to the present invention can be suitably used for applications requiring transparency.

  Moreover, when the optical film concerning this invention is used for a polarizer protective film, it is preferable that optical anisotropy is small. In particular, it is preferable that not only the optical anisotropy in the in-plane direction (length direction, width direction) of the film but also the optical anisotropy in the thickness direction is small. In other words, it is preferable that both the in-plane retardation and the thickness direction retardation are small.

  More specifically, the in-plane retardation is preferably 10 nm or less, more preferably 6 nm or less, and further preferably 5 nm or less.

  Further, the thickness direction retardation is preferably 50 nm or less, more preferably 20 nm or less, and further preferably 10 nm or less.

  If it is set as the structure which has such an optical characteristic, the optical film concerning this invention can be used as a polarizer protective film with which the polarizing plate of a liquid crystal display device is equipped.

  On the other hand, when the in-plane retardation of the film exceeds 10 nm or the thickness direction retardation exceeds 50 nm, the polarizer protective film using the optical film according to the present invention is used as a polarizing plate of a liquid crystal display device. In some cases, problems such as a decrease in contrast occur in the liquid crystal display device.

  The in-plane retardation (Re) and the thickness direction retardation (Rth) can be calculated by the following equations, respectively. That is, in an ideal film that is completely optically isotropic in the three-dimensional direction, both the in-plane retardation Re and the thickness direction retardation Rth are zero.

Re = (nx−ny) × d
Rth = | (nx + ny) / 2−nz | × d
In the above formula, nx, ny, and nz are respectively the direction in which the in-plane refractive index is the maximum as the X axis, the direction perpendicular to the X axis as the Y axis, and the thickness direction of the film as the Z axis. Represents the refractive index in each axial direction. D represents the thickness of the film, and || represents an absolute value.

In addition, the optical film according to the present invention preferably has an orientation birefringence value of 0 to 0.1 × 10 −3 , and more preferably 0 to 0.01 × 10 −3 .

  If the orientation birefringence is within the above range, stable optical characteristics can be obtained without causing birefringence during molding even when the environment changes.

  In the present specification, unless otherwise specified, “orientation birefringence” is intended to mean birefringence that develops when stretched 100% at a temperature 5 ° C. higher than the glass transition temperature of a thermoplastic resin. The orientation birefringence (Δn) is defined by Δn = nx−ny = Re / d and can be measured by a phase difference meter, using nx and ny described above.

In the optical film according to the present invention, the absolute value of the photoelastic coefficient is preferably 20 × 10 −12 m 2 / N or less, more preferably 10 × 10 −12 m 2 / N or less, More preferably, it is 5 × 10 −12 m 2 / N or less.

  If the photoelastic coefficient is within the above range, even if the optical film according to the present invention is used in a liquid crystal display device, phase difference unevenness occurs, contrast at the periphery of the display screen decreases, or light leakage occurs. There is nothing to do.

On the other hand, when the absolute value of the photoelastic coefficient is larger than 20 × 10 −12 m 2 / N, when the optical film according to the present invention is used in a liquid crystal display device, unevenness in phase difference occurs, There is a tendency that the contrast of the light is reduced or light leakage is likely to occur. This tendency becomes particularly remarkable in a high temperature and high humidity environment.

  In addition, when an external force is applied to an isotropic solid to generate stress (ΔF), it temporarily exhibits optical anisotropy and exhibits birefringence (Δn). By “photoelastic coefficient” is intended the ratio of stress to birefringence. That is, the photoelastic coefficient (c) is calculated by the following equation.

c = △ n / △ F
However, in the present invention, the photoelastic coefficient is a value measured at 23 ° C. and 50% RH at a wavelength of 515 nm by the Senarmon method.

  The optical film according to the present invention may be subjected to surface treatment as necessary. Specifically, for example, when the optical film according to the present invention is used by applying surface processing such as coating processing to the surface or laminating another film on the surface, the optical film according to the present invention is used. It is preferable to perform a surface treatment.

  By performing such a surface treatment, mutual adhesion between the optical film according to the present invention and another film to be coated or laminated can be improved.

  In addition, the objective of the surface treatment with respect to the optical film concerning this invention is not limited to what aims at an effect. That is, the optical film according to the present invention may be subjected to a surface treatment regardless of its use.

  The surface treatment is not particularly limited, and examples thereof include corona treatment, plasma treatment, ultraviolet irradiation, and alkali treatment. Among these, corona treatment is preferable.

  Moreover, according to the thermoplastic resin composition concerning this invention, a film with a big retardation can be manufactured by changing the composition ratio of the structural unit represented by the said General Formula (1)-(3). it can. That is, the thermoplastic resin composition according to the present invention can be suitably used for producing an optical compensation film such as a retardation film.

  Since the optical film according to the present invention has the characteristics as described above, it can be used as it is as a final product for various applications. Moreover, the range of uses can be expanded by performing various processes as described above.

  Although the use of the optical film according to the present invention is not particularly limited, specifically, for example, imaging fields such as cameras, VTRs, projectors, viewfinders, filters, prisms, and Fresnel lenses, CDs, etc. Optical field for optical discs such as optical discs for CD players, DVD players, MD players, liquid crystal light guide plates, polarizer protective films, retardation films, etc. Information equipment field such as LCD display film and surface protection film, optical communication field such as optical fiber, optical switch and optical connector, automotive field such as automobile headlight, tail lamp lens, inner lens, instrument cover, sunroof, glasses and contact Len , Endoscopic lenses, medical devices such as medical supplies that require sterilization, road translucent plates, pair glass lenses, lighting windows and carports, lighting lenses and covers, and building material sizing It can be suitably used in the field of building materials, microwave cooking containers (tableware) and the like.

  As described above, the optical film according to the present invention is excellent in optical characteristics such as optical homogeneity and transparency. Therefore, it can use especially suitably for well-known optical uses, such as a liquid crystal display periphery, such as an optically isotropic film, a polarizer protective film, and a transparent conductive film, using these optical characteristics.

  The optical film of the present invention can be used as a polarizing plate by being attached to a polarizer. That is, the optical film according to the present invention can be used as a polarizer protective film for a polarizing plate. The polarizer is not particularly limited, and any conventionally known polarizer can be used. Specific examples include a polarizer obtained by containing iodine in stretched polyvinyl alcohol.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this Example. In addition, the part in description of the synthesis example of each component shows a weight part.

The imidation ratio was calculated as follows using IR. That is, the pellet of the product was dissolved in methylene chloride, and the IR spectrum of the solution was measured at room temperature using Travel IR manufactured by SensIR Technologies. From the obtained IR spectrum, and absorption intensity (Abs Ester) attributed to the ester carbonyl group of 1720 cm -1, the absorption intensity assignable to an imide carbonyl group of 1660cm -1 (Abs imide) and imidization ratio from the ratio of (Im% (IR)) was determined. Here, the “imidization rate” refers to the ratio of the imide carbonyl group in the total carbonyl group.

  The glass transition temperature of each composition was determined by a midpoint method using a differential scanning calorimeter DSC-50 model, Shimadzu Corporation, measured in a nitrogen atmosphere at a heating rate of 20 ° C./min.

  The refractive index of each composition was measured using an Atago Precision Abbe Refractometer after processing each composition into a sheet.

  The haze and total light transmittance of the film were measured by the method described in JIS K7105 using Nippon Denshoku Industries NDH-300A.

  The film was stretched at 140 ° C. using a biaxial stretching apparatus SS-70 (Shibayama Scientific Instruments).

  The bending resistance of the film was measured according to the method of JIS C5016 using a MIT folding fatigue tester manufactured by Toyo Seiki Seisakusho. The measurement conditions were R = 0.38 and a load of 100 g.

(1) Synthesis of glutarimide acrylic resin (A-1) An imidized resin was produced using methyl methacrylate-styrene copolymer (styrene content 11 mol%) as a raw material resin and monomethylamine as an imidizing agent. .

  The extruder used was a meshing type co-rotating twin screw extruder having a diameter of 15 mm. The set temperature of each temperature control zone of the extruder was 230 ° C., and the screw rotation speed was 150 rpm. A methyl methacrylate-styrene copolymer (hereinafter also referred to as “MS resin”) was supplied at 2 kg / hr, and the resin was melted and filled with a kneading block, and then 25 parts by weight of monomethyl with respect to the resin from the nozzle. Amine (Mitsubishi Gas Chemical Co., Ltd.) was injected. A reverse flight was placed at the end of the reaction zone to fill the resin. By-products and excess methylamine after the reaction were removed by reducing the pressure at the vent port to -0.092 MPa. The resin that emerged as a strand from the die provided at the exit of the extruder was cooled in a water tank and then pelletized with a pelletizer to obtain an imidized MS resin (1).

  Next, in a meshing type co-rotating twin screw extruder with a diameter of 15 mm, the set temperature of each temperature control zone of the extruder was 230 ° C. and the screw rotation speed was 150 rpm. The imidized MS resin (1) obtained from the hopper was supplied at 1 kg / hr, and the resin was melted and filled with the kneading block, and then 8 parts by weight of dimethyl carbonate and 2 parts by weight of the resin from the nozzle. A mixture of triethylamine was injected to reduce the carboxyl groups in the resin. A reverse flight was placed at the end of the reaction zone to fill the resin. The by-product after reaction and excess dimethyl carbonate were removed by reducing the pressure at the vent port to -0.092 MPa. The resin coming out as a strand from the die provided at the exit of the extruder was cooled in a water tank and then pelletized with a pelletizer to obtain an imidized MS resin (2) having a reduced acid value.

  Further, the imidized MS resin (2) is applied to a meshing type co-rotating twin screw extruder having a diameter of 15 mm, the set temperature of each temperature control zone of the extruder is 230 ° C., the screw rotation speed is 150 rpm, and the supply amount is 1 kg / hr. It was put in the condition of. The vent port pressure was reduced to -0.095 MPa, and volatile components such as unreacted auxiliary materials were removed again. The devolatilized imide resin that emerged as a strand from the die provided at the exit of the extruder was cooled in a water tank and then pelletized with a pelletizer to obtain glutarimide acrylic resin A-1.

  The obtained glutarimide acrylic resin A-1 is a glutamylimide unit represented by the general formula (1) described in the above embodiment and a (meth) acrylic acid represented by the general formula (2). It corresponds to a glutarimide acrylic resin in which an ester unit and an aromatic vinyl unit represented by the general formula (3) are copolymerized.

  About glutarimide acrylic resin A-1, the imidation ratio, the glass transition temperature, and the refractive index were measured according to said method. As a result, the imidation ratio was 70 mol%, the glass transition temperature was 140 ° C., and the refractive index was 1.53.

(2) Synthesis of graft copolymer (B-1) 182 parts of ion exchange water and 0.045 part of sodium dodecylbenzenesulfonate were placed in a reaction vessel, and the temperature was raised to 50 ° C. while stirring in a nitrogen stream. Subsequently, 20% of the mixed liquid consisting of 49 parts of 2-phenoxyethyl acrylate, 21 parts of butyl acrylate, 1.05 part of allyl methacrylate, and 0.025 part of t-butyl hydroperoxide is collectively collected. The mixture was stirred for 10 minutes. Thereafter, 0.32 part of sodium formaldehydesulfoxylate, 0.006 part of sodium ethylenediaminetetraacetate and 0.002 part of ferrous sulfate heptahydrate were added and stirred as they were for 30 minutes. Subsequently, 0.15 part of sodium lauryl sulfate was added and stirred for 10 minutes, and then the remaining 80% of the mixed solution was continuously added over 3 hours. After completion of the addition, the temperature was maintained for 30 minutes to complete the polymerization. The average particle diameter in the obtained crosslinked polymer latex was 212 nm, and the polymerization conversion rate was 98%.

  The crosslinked polymer latex obtained above was kept at 50 ° C. while stirring under a nitrogen stream, and after adding 0.15 part of sodium lauryl sulfate and stirring for 10 minutes, 3 parts of butyl acrylate and methyl methacrylate 13.4 were added. Part, 13.7 parts of styrene and 0.15 part of t-butyl hydroperoxide were continuously added over 75 minutes. After completion of the addition, the mixture was stirred at the same temperature for 75 minutes to complete the polymerization, and a graft copolymer latex was obtained. This graft copolymer latex was subjected to salting out coagulation, heat treatment, and drying by a known method to obtain a white powdered graft copolymer B-1. The obtained graft copolymer had a glass transition temperature of −32 ° C. and a refractive index of 1.53.

(3) Synthesis of graft copolymer (B-2, B-3, B-4) The amount of sodium dodecylbenzenesulfonate was 0.200 parts, 0.010 parts, and 0.005 parts, respectively. Synthesis was performed in the same manner as the synthesis method of graft copolymer B-1, and graft copolymers B-2, B-3, and B-4 were obtained. Average particle sizes in the crosslinked polymer latex at the time of polymerization were 146 nm, 272 nm, and 305 nm, respectively. Moreover, all of the obtained graft copolymers had a glass transition temperature of −32 ° C. and a refractive index of 1.53.

(4) Synthesis of Graft Copolymer (B-5) The composition of the mixed solution continuously added to the crosslinked polymer latex in the same manner as the synthesis method of graft copolymer B-1, , 6.9 parts of methyl methacrylate, 6.6 parts of styrene, 3.6 parts of acrylonitrile, 0.075 part of t-butyl hydroperoxide, as the second stage, 6.9 parts of methyl methacrylate, styrene 6 The white powdered graft copolymer B- was prepared in the same manner as the graft copolymer B-1, except that the additional time for the first and second stages was 42 minutes and 33 minutes for a total of 75 minutes, respectively. 2 was obtained. The obtained graft copolymer had a glass transition temperature of −32 ° C. and a refractive index of 1.53.

(5) Synthesis of graft copolymer (B-6) In the same manner as the synthesis method of graft copolymer B-1, instead of 49 parts of 2-phenoxyethyl acrylate and 21 parts of butyl acrylate, acrylic acid Except for using 70 parts of n-butyl, the same operation was performed to obtain a graft copolymer B-3. The obtained graft copolymer had a glass transition temperature of −54 ° C. and a refractive index of 1.46.

(6) Synthesis of graft copolymer (B-7) In the same manner as the synthesis method of graft copolymer B-1, instead of 49 parts of 2-phenoxyethyl acrylate and 21 parts of butyl acrylate, styrene 51 The graft copolymer B-4 was obtained by performing the same operation except that n parts of acrylate and 49 parts of n-butyl acrylate were used. The obtained graft copolymer had a glass transition temperature of 17 ° C. and a refractive index of 1.53.

(7) Examples and Comparative Examples Using a mesh type co-rotating twin screw extruder with a diameter of 30 mm, setting temperature of the temperature adjustment zone of the extruder is 240 ° C., screw rotation speed is 250 rpm, and glutarimide acrylic resin (A -1) and the graft copolymer mixture were fed at a rate of 10 kg / hr. The resin that came out as a strand from a die provided at the exit of the extruder was cooled in a water tank and pelletized with a pelletizer.

  Using the melt extruder with a T-die connected to the outlet, the pellets obtained were supplied at a temperature setting zone of 280 ° C., a screw rotation speed of 100 rpm, and a resin pellet supply rate of 10 kg / hr. Then, a film having a thickness of about 130 μm was obtained by melt extrusion.

  The above film was biaxially stretched at 145 ° C. to obtain a stretched film.

  Table 1 shows the blending ratio of each component in each Example and Comparative Example, the haze and total light transmittance of the obtained film, and the bending resistance of the stretched film.

Thus, by adding a graft copolymer component having a refractive index close to that of an acrylic resin and a low glass transition temperature to an acrylic resin having a glass transition temperature of 120 ° C. or higher, it is transparent and has a high bending resistance. An excellent resin composition can be obtained.

Claims (14)

  1. A resin composition comprising the following acrylic resin (A) and graft copolymer (B).
    (A) 99 to 70% by weight of an acrylic resin having a glutarimide structure, a glutaric anhydride structure or a lactone structure as a unit in the molecule, a glass transition temperature of 120 ° C. or higher, and a refractive index of 1.50 or higher,
    (B) 50 to 100% by weight of acrylic acid ester containing an acrylic acid 2-phenoxyethyl, methacrylate 0-30% by weight, aromatic vinyl 0-30% by weight, and copolymerizable with these monomers 0 Graft copolymer obtained by graft-polymerizing a vinyl group-containing compound to a rubber-like polymer having a glass transition temperature of 0 ° C. or lower obtained by copolymerizing 20% by weight (the total of which is 100% by weight) 1 to 30% by weight of a graft copolymer having a difference from the refractive index of the acrylic resin (A) of 0.03 or less.
  2.   The resin composition according to claim 1, wherein the acrylic resin (A) has a refractive index of 1.52 to 1.56.
  3. The acrylic resin (A) is a glutarimide acrylic resin having a unit represented by the following general formula (1) and a unit represented by the following general formula (2): 2. The resin composition according to 2.
    (In the formula, R 1 and R 2 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 3 is hydrogen, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 3 to 12 carbon atoms. A cycloalkyl group or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)
    (In the formula, R 4 and R 5 are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 6 is an alkyl group having 1 to 18 carbon atoms or a cycloalkyl having 3 to 12 carbon atoms. Or a substituent containing an aromatic ring having 5 to 15 carbon atoms.)
  4. 4. The resin composition according to claim 3, wherein the acrylic resin further contains a unit represented by the following general formula (3).
    (In the formula, R 7 is hydrogen or an alkyl group having 1 to 8 carbon atoms, and R 8 is an aryl group having 6 to 10 carbon atoms.)
  5. The graft copolymer (B) is obtained by graft-copolymerizing 50 to 85% by weight of a rubber-like polymer with 50 to 15% by weight of a graft component.
    The rubber-like polymer comprises 50 to 100% by weight of acrylic acid ester, 0 to 30% by weight of methacrylic acid ester, 0 to 20% by weight of aromatic vinyl, and 0 to 20% by weight of monomer copolymerizable therewith ( The total of these is 100% by weight)
    The graft component is 0-30 wt% acrylic ester, 30-100 wt% methacrylic ester, 0-60 wt% aromatic vinyl, and 0-30 wt% monomer copolymerizable therewith (these total 100 wt%) Tona characterized Rukoto,
    The resin composition in any one of Claims 1-4.
  6.   The component of the rubber-like polymer in the graft copolymer (B) is 50 to 99.5% by weight of 2-phenoxyethyl acrylate, 0 to 50% by weight of n-butyl acrylate, and 0.5 to 2% by weight of allyl methacrylate. (The total of these is 100% by weight), and the graft component in the graft copolymer (B) is 0 to 20% by weight of n-butyl acrylate, 30 to 70% by weight of methyl methacrylate, 30 to 30% of styrene. The resin composition according to any one of claims 1 to 5, comprising 60% by weight and 0 to 20% by weight of monomers copolymerizable therewith (the total of these being 100% by weight). .
  7.   A film comprising the resin composition according to claim 1.
  8.   An optical film comprising the resin composition according to claim 1.
  9.   The optical film according to claim 8, which is a film obtained by a melt extrusion method.
  10.   The optical film according to claim 8, wherein the optical film is a stretched film.
  11.   The optical film according to any one of claims 8 to 10, wherein an in-plane retardation is 10 nm or less and a thickness direction retardation is 50 nm or less.
  12.   The polarizer protective film using the optical film in any one of Claims 8-11.
  13.   A retardation film using the optical film according to claim 8.
  14.   A polarizing plate using the film according to claim 12 or 13.
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CN103380175B (en) 2011-02-21 2015-11-25 株式会社钟化 Acrylic resin film
JP5988602B2 (en) * 2012-02-16 2016-09-07 テクノポリマー株式会社 Thermoplastic resin composition for forming optical parts
JP6236002B2 (en) * 2012-06-26 2017-11-22 株式会社カネカ Non-birefringent resin material and film
KR20150140327A (en) * 2013-04-05 2015-12-15 가부시키가이샤 가네카 Optical resin material and optical film
TWI515252B (en) * 2013-04-05 2016-01-01 Kaneka Corp Resin composition, and film thereof
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JPWO2015098775A1 (en) * 2013-12-25 2017-03-23 株式会社カネカ Optical resin composition and molded article
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