WO2011138953A1 - 熱可塑性透明樹脂組成物 - Google Patents
熱可塑性透明樹脂組成物 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- 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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- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
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- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
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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
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
- G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
- G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic transparent resin composition that is excellent in transparency and can be used for various optical parts and the like.
- thermoplastic resins such as heat resistance, impact resistance, toughness, surface hardness, hygroscopicity, and the like
- it is widely used to blend two or more resins.
- phase separation may occur when two or more kinds of resins are blended.
- JP 2006-299141 A JP-A-8-208935 Japanese Patent No. 3644330 JP 2005-530003 Gazette
- thermoplastic resin composition that is easy to adjust the refractive index and has high transparency is provided.
- the present inventors have obtained exceptionally high compatibility and transparent thermoplastic resin compositions when blended with a specific thermoplastic resin, It has been found that the refractive index can be easily controlled simply by changing the blend ratio of the thermoplastic resin. That is, the present invention is as follows.
- thermoplastic transparent resin composition obtained by blending the following thermoplastic resin (A) and thermoplastic resin (B).
- Thermoplastic resin (B) at least one structural unit derived from a (meth) acrylic acid ester monomer represented by general formula (1) and at least a structural unit derived from an aromatic vinyl monomer represented by general formula (2)
- a thermoplastic resin containing one kind and the proportion of the structural unit derived from the (meth) acrylic acid ester monomer is 1 to 99 mol% with respect to the total of all the structural units, in the structural unit derived from the aromatic vinyl monomer
- R1 is a hydrogen atom or a methyl group
- R2 is a hydrocarbon group having 1 to 18 carbon atoms.
- R3 is a hydrogen atom or a methyl group
- R4 is a phenyl group which may have a hydrocarbon substituent having 1 to 4 carbon atoms.
- thermoplastic resin (A) the proportion of the structural unit derived from the (meth) acrylic acid ester monomer represented by the general formula (1) is 1 to 80 mol% based on the total of all the structural units.
- thermoplastic resin (B) the proportion of the structural unit derived from the (meth) acrylic acid ester monomer represented by the general formula (1) is 45 to 99 mol% based on the total of all the structural units. Or the thermoplastic transparent resin composition of 2. 4). 4.
- thermoplastic transparent resin composition according to any one of 1 to 4 above, wherein in the general formula (1), R1 and R2 are methyl groups. 6). 6. The thermoplastic transparent resin composition according to any one of 1 to 5, wherein in the general formula (2), R3 is a hydrogen atom and R4 is a phenyl group. 7).
- the proportion of the structural unit derived from the (meth) acrylic acid ester monomer represented by the general formula (1) is 15 to 25 mol% with respect to the total of all the structural units.
- thermoplastic resin (A) in which the proportion of the structural unit derived from the (meth) acrylic acid ester monomer represented by the general formula (1) is 15 to 65 mol% with respect to the total of all the structural units, and the general formula The above-mentioned 7 obtained by blending the thermoplastic resin (B), wherein the proportion of the structural unit derived from the (meth) acrylic acid ester monomer represented by (1) is 65 to 80 mol% with respect to the total of all the structural units.
- the proportion of the structural unit derived from the (meth) acrylic acid ester monomer represented by the general formula (1) is 15 to 55 mol% with respect to the total of all the structural units.
- thermoplastic transparent resin composition comprising any one of 1 to 11 above.
- An extruded thermoplastic resin sheet comprising the thermoplastic transparent resin composition according to any one of 1 to 11 above. 14 12.
- a light guide plate comprising the thermoplastic resin sheet according to 13 or 14 above. 16.
- the lens unit which consists of a board
- the display front panel which consists of a thermoplastic resin sheet of said 13 or 14. 18.
- An injection-molded article comprising the thermoplastic transparent resin composition according to any one of 1 to 11 above. 19. 19.
- thermoplastic resin composition having excellent transparency can be obtained simply by blending a specific thermoplastic resin without requiring special molecular design or blending of additives.
- the refractive index of the thermoplastic resin composition can be easily adjusted by changing the blend ratio. Since it has the above characteristics, the thermoplastic transparent resin composition of the present invention is suitable for various optical components.
- thermoplastic resin (A) a thermoplastic resin (B) and refractive index in Example 1 is shown.
- the thermoplastic transparent resin composition of the present invention is a resin composition obtained by blending the following thermoplastic resin (A) and thermoplastic resin (B).
- the thermoplastic resin (A) is composed of at least one structural unit derived from a (meth) acrylic acid ester monomer represented by the following general formula (1) and an aromatic vinyl monomer represented by the following general formula (2).
- the thermoplastic resin contains at least one unit and the proportion of the structural unit derived from the (meth) acrylic acid ester monomer is 1 to 99 mol% with respect to the total of all the structural units.
- the thermoplastic resin (B) is composed of at least one structural unit derived from a (meth) acrylic acid ester monomer represented by the following general formula (1) and an aromatic vinyl monomer represented by the following general formula (2).
- thermoplastic resin containing at least one unit and the proportion of the structural unit derived from the (meth) acrylic acid ester monomer is 1 to 99 mol% with respect to the total of all the structural units, the structure derived from the aromatic vinyl monomer It is a thermoplastic resin obtained by hydrogenating 70% or more of aromatic double bonds in a unit.
- R1 is a hydrogen atom or a methyl group
- R2 is a hydrocarbon group having 1 to 18 carbon atoms.
- R3 is a hydrogen atom or a methyl group
- R4 is a phenyl group which may have a hydrocarbon substituent having 1 to 4 carbon atoms.
- R2 is a hydrocarbon group having 1 to 18 carbon atoms, specifically, a methyl group, an ethyl group, a butyl group. And alkyl groups such as lauryl group, stearyl group, cyclohexyl group and isobornyl group, and aryl groups such as benzyl group and phenyl group.
- R2 is preferably a structural unit derived from a (meth) acrylic acid ester monomer having a methyl group and / or an ethyl group, and more preferably, R1 is a methyl group and R2 is a methyl group. It is a structural unit.
- the thermoplastic resin (A) and the thermoplastic resin (B) may contain at least one structural unit derived from the (meth) acrylic acid ester monomer represented by the general formula (1). You may contain.
- R3 is a hydrogen atom or a methyl group
- R4 is a phenyl group or a phenyl group having a hydrocarbon substituent having 1 to 4 carbon atoms. is there.
- it is a structural unit derived from styrene, wherein R3 is a hydrogen atom and R4 is a phenyl group.
- thermoplastic resin (A) and the thermoplastic resin before hydrogenating the aromatic double bond of the thermoplastic resin (B) (hereinafter sometimes referred to as “thermoplastic resin (B 0 )”) As long as at least one structural unit derived from the aromatic vinyl monomer represented by the general formula (2) is included, two or more structural units may be included.
- the proportion of the structural units derived from the (meth) acrylic acid ester monomer is 1 to 99 mol% with respect to the total of all the structural units of the thermoplastic resin (A), and 1 to 80 mol%. It is preferably 1 to 70 mol%, more preferably 15 to 65 mol%.
- the proportion of the structural unit derived from the (meth) acrylic acid ester monomer is 1 to 80 mol%, the compatibility with the thermoplastic resin (B) is particularly high.
- the proportion of the structural units derived from the (meth) acrylic acid ester monomer is 1 to 99 mol% with respect to the total of all the structural units of the thermoplastic resin (B), and 45 to 99 mol%. It is preferably 55 to 99 mol%, more preferably 55 to 80 mol%.
- the proportion of the structural unit derived from the (meth) acrylic acid ester monomer is 45 to 99 mol%, the compatibility with the thermoplastic resin (A) is particularly high.
- thermoplastic resin (A) and the thermoplastic resin (B 0 ) used in the thermoplastic transparent resin composition of the present invention constitute the structural units represented by the general formulas (1) and (2), ) It can be produced by polymerizing an acrylate monomer and an aromatic vinyl monomer.
- a known method can be used for the polymerization of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer, and for example, it can be produced by a bulk polymerization method, a solution polymerization method, or the like.
- the bulk polymerization method is carried out by a method in which the monomer composition containing the monomer and the polymerization initiator is continuously supplied to a complete mixing tank and continuously polymerized at 100 to 180 ° C.
- the monomer composition may contain a chain transfer agent as necessary.
- the polymerization initiator is not particularly limited, but t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, t-hexylperoxyisopropyl monocarbonate, t-amylperoxynormal Organic peroxides such as octoate, t-butylperoxyisopropyl monocarbonate, di-t-butyl peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile) ), 2,2'-azobis (2,4-dimethylvaleronitrile) and
- the chain transfer agent is used as necessary, and examples thereof include ⁇ -methylstyrene dimer.
- Examples of the solvent used in the solution polymerization method include hydrocarbon solvents such as toluene, xylene, cyclohexane and methylcyclohexane, ester solvents such as ethyl acetate and methyl isobutyrate, ketone solvents such as acetone and methyl ethyl ketone, tetrahydrofuran, Examples include ether solvents such as dioxane and alcohol solvents such as methanol and isopropanol.
- hydrocarbon solvents such as toluene, xylene, cyclohexane and methylcyclohexane
- ester solvents such as ethyl acetate and methyl isobutyrate
- ketone solvents such as acetone and methyl ethyl ketone
- tetrahydrofuran examples include ether solvents such as dioxane and alcohol solvents such as methanol and isopropanol.
- thermoplastic resin (B) used in the thermoplastic transparent resin composition of the present invention is obtained by polymerizing a (meth) acrylate monomer and an aromatic vinyl monomer to obtain a thermoplastic resin (B 0 ). It is obtained by hydrogenating 70% or more of the aromatic double bond in the structural unit derived from the aromatic vinyl monomer in the plastic resin (B 0 ).
- the solvent used for the hydrogenation reaction may be the same as or different from the polymerization solvent.
- hydrocarbon solvents such as cyclohexane and methylcyclohexane
- ester solvents such as ethyl acetate and methyl isobutyrate
- ketone solvents such as acetone and methyl ethyl ketone
- ether solvents such as tetrahydrofuran and dioxane
- alcohol solvents such as methanol and isopropanol A solvent etc.
- the method for hydrogenation is not particularly limited, and a known method can be used. For example, it can be carried out batchwise or continuously with a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250 ° C. By setting the temperature to 60 ° C. or higher, the reaction time does not take too long, and by setting the temperature to 250 ° C. or lower, there is little occurrence of molecular chain cleavage or ester site hydrogenation.
- Examples of the catalyst used in the hydrogenation reaction include metals such as nickel, palladium, platinum, cobalt, ruthenium, and rhodium or oxides or salts or complex compounds of these metals, carbon, alumina, silica, silica / alumina, and diatomaceous earth. And a solid catalyst supported on a porous carrier.
- the thermoplastic resin (B) is obtained by hydrogenating 70% or more of the aromatic double bond in the structural unit derived from the aromatic vinyl monomer in the thermoplastic resin (B 0 ). That is, the ratio of the aromatic double bond remaining in the structural unit derived from the aromatic vinyl monomer is 30% or less. If it is in a range exceeding 30%, the transparency of the thermoplastic resin (B) is lowered, and as a result, the transparency of the thermoplastic transparent resin composition may be lowered.
- the ratio of the aromatic double bond remaining in the structural unit derived from the aromatic vinyl monomer is preferably less than 10%, more preferably less than 5%.
- the weight average molecular weight of the thermoplastic resin (A) is not particularly limited, but is preferably 40,000 to 500,000, and preferably 50,000 to 300,000 from the viewpoint of strength and moldability. More preferred.
- the weight average molecular weight of the thermoplastic resin (B) is not particularly limited, but is preferably 40,000 to 500,000, and preferably 50,000 to 300,000 from the viewpoint of strength and moldability. It is more preferable.
- the said weight average molecular weight is a weight average molecular weight of standard polystyrene conversion measured by gel permeation chromatography (GPC).
- thermoplastic resin (A) and the thermoplastic resin (B) can be produced by melt-mixing by a method known in the art, for example, a single screw extruder, a twin screw extruder, A kneader or the like can be used.
- the blend ratio of the thermoplastic resin (A) and the thermoplastic resin (B) is not particularly limited, but the mass ratio of the thermoplastic resin (A) / thermoplastic resin (B) is 1/99 to 99/1. Preferably, it is in the range of 5/95 to 95/5, more preferably in the range of 10/90 to 90/10.
- thermoplastic transparent resin composition of the present invention has a proportion of the structural unit derived from the (meth) acrylic acid ester monomer represented by the general formula (1) with respect to the total of all the structural units, from the viewpoint of transparency.
- the ratio of the thermoplastic resin (A) of 15 to 65 mol% and the structural unit derived from the (meth) acrylic acid ester monomer represented by the general formula (1) is 55 to 80 mol based on the total of all the structural units.
- % Of a thermoplastic resin composition (B) is preferable.
- the proportion of the structural unit derived from the (meth) acrylic acid ester monomer represented by the general formula (1) is relative to the total of all the structural units.
- a thermoplastic resin (A) in which the proportion of structural units derived from monomers is 15 to 65 mol%, preferably 15 to 55 mol%, based on the total of all the structural units;
- Acrylic acid More preferably the amount of the structural unit derived from the ester monomer is a thermoplastic resin (B) and formed by blending a thermoplastic resin composition is 65 to 80 mol% based on the total of all the structural units.
- thermoplastic resin (A) and the thermoplastic resin (B) When the combination of the thermoplastic resin (A) and the thermoplastic resin (B) is in the above range, the compatibility between the thermoplastic resin (A) and the thermoplastic resin (B) is high, and the heat obtained by blending them. The transparency of the plastic resin composition is particularly good.
- thermoplastic transparent resin composition of the present invention can be blended with other resins as long as the transparency is not impaired.
- examples thereof include polymethyl methacrylate, polystyrene, polycarbonate, cycloolefin (co) polymer, various elastomers, and the like.
- the thermoplastic transparent resin composition of the present invention can be used by mixing various additives.
- the additive include an antioxidant, an ultraviolet absorber, an anticolorant, an antistatic agent, a release agent, a lubricant, a dye, and a pigment.
- the method of mixing is not particularly limited, and a method of compounding the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used.
- thermoplastic transparent resin composition of the present invention transmits light in the visible light region satisfactorily, the appearance is transparent.
- the haze is preferably 5% or less, depending on the application.
- higher transparency may be required, more preferably 3% or less, particularly preferably 2% or less, and most preferably 1.8% or less.
- thermoplastic transparent resin composition of the present invention can be heated and melted to have a desired shape. Molding can be performed by a known injection molding method or extrusion molding method. Specific uses of the molded body include an extrusion-molded thermoplastic resin sheet comprising the thermoplastic transparent resin composition, a co-extrusion multilayer thermoplastic resin sheet having a layer comprising the thermoplastic transparent resin composition, and the thermoplastic A substrate made of a resin sheet, and a lens unit made of at least one lens formed on one or both surfaces of the substrate, a display front panel, various light guide plates, various light guides, a plastic lens, an optical fiber, an optical filter, a prism, Examples thereof include a transparent substrate material, a transparent protective material, an optical recording medium substrate, and various optical components.
- thermoplastic transparent resin compositions obtained in Examples and Comparative Examples were evaluated as follows.
- a disk-shaped sample having a diameter of 50 ⁇ and 3.2 mm was prepared by NP7-1F injection molding manufactured by Nissei Plastic Industry Co., Ltd., and measured by a transmission method using COH-400 manufactured by Nippon Denshoku Industries Co., Ltd.
- a sample having a haze of 5% or less is defined as “transparent”.
- the disk-shaped sample produced in the haze measurement was cut into a length of 40 mm, a width of 8 mm, and a thickness of 3.2 mm with REFINE SAW, Lo manufactured by Refine Tech Co., Ltd.
- the refractive index of the sample was measured with a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd.
- the measurement temperature was 20 ° C.
- the measurement wavelength was 589 nm
- monobromonaphthalene was used as the intermediate solution.
- Synthesis Example 1 [Production of methyl methacrylate-styrene copolymer resin (thermoplastic resin A1)]
- monomer components purified methyl methacrylate (Mitsubishi Gas Chemical Co., Ltd.) 60.000 mol%, purified styrene (Wako Pure Chemical Industries, Ltd.) 39.998 mol%, and t-amylperoxy- as a polymerization initiator
- Continuous polymerization was performed at a residence time of 2.5 hours and a polymerization temperature of 150 ° C.
- the polymerization tank was continuously withdrawn from the bottom so that the liquid level was constant, and introduced into a solvent removal apparatus to obtain a pellet-shaped methyl methacrylate-styrene copolymer resin (thermoplastic resin A1).
- the ratio of the structural unit derived from methyl methacrylate in the thermoplastic resin A1 was 57 mol%.
- the weight average molecular weight (standard polystyrene conversion) measured by gel permeation chromatography was 147,000.
- thermoplastic resin B1 [Production of methyl methacrylate-styrene-vinylcyclohexane copolymer resin (thermoplastic resin B1)]
- the thermoplastic resin A1 obtained in Synthesis Example 1 was dissolved in methyl isobutyrate (manufactured by Kanto Chemical Co., Inc.) to prepare a 10% by mass methyl isobutyrate solution.
- a 1000 mL autoclave apparatus was charged with 500 parts by mass of a 10% by mass methyl isobutyrate solution of thermoplastic resin A1, and 1 part by mass of 10% by mass Pd / C (manufactured by NE Chemcat) as a hydrogenation catalyst, with a hydrogen pressure of 9 MPa, 200 ° C.
- thermoplastic resin B1 methyl methacrylate-styrene-vinylcyclohexane copolymer resin
- thermoplastic resin B1 the proportion of structural units derived from methyl methacrylate was 57 mol%.
- Synthesis Example 3 [Production of methyl methacrylate-styrene copolymer resin (thermoplastic resin A2)] Continuous polymerization was carried out under the same conditions as in Synthesis Example 1 except that 75.000 mol% of purified methyl methacrylate and 24.998 mol% of purified styrene were used as monomer components to obtain a thermoplastic resin A2.
- the ratio of the structural unit derived from methyl methacrylate in the thermoplastic resin A2 was 73 mol%.
- the weight average molecular weight (standard polystyrene conversion) measured by gel permeation chromatography was 124,000.
- Synthesis Example 4 [Production of methyl methacrylate-styrene-vinylcyclohexane copolymer resin (thermoplastic resin B2)] Under the same conditions as in Synthesis Example 2, the aromatic double bond at the styrene site of the thermoplastic resin A2 obtained in Synthesis Example 3 was hydrogenated. The hydrogenation reaction rate at the styrene site was 99%. In the obtained methyl methacrylate-styrene-vinylcyclohexane copolymer resin (thermoplastic resin B2), the proportion of the structural units derived from methyl methacrylate was 73 mol%.
- Synthesis Example 5 [Production of methyl methacrylate-styrene copolymer resin (thermoplastic resin A3)] Monomer composition comprising 20.000 mol% of purified methyl methacrylate as monomer components, 79.998 mol% of purified styrene, and 0.002 mol% of t-amylperoxy-2-ethylhexanoate as a polymerization initiator The product was continuously supplied at 1 kg / h to a 10 L complete mixing vessel with a helical ribbon blade, and continuous polymerization was performed at an average residence time of 2.5 hours and a polymerization temperature of 150 ° C.
- thermoplastic resin A3 a pellet-shaped methyl methacrylate-styrene copolymer resin.
- the ratio of the structural unit derived from methyl methacrylate in the thermoplastic resin A3 was 20 mol%.
- weight average molecular weight (standard polystyrene conversion) measured by gel permeation chromatography was 225,000.
- Synthesis Example 6 [Production of methyl methacrylate-styrene copolymer resin (thermoplastic resin A4)] Continuous polymerization was carried out under the same conditions as in Synthesis Example 5 except that 30.000 mol% of purified methyl methacrylate and 69.998 mol% of purified styrene were used as monomer components, and a methyl methacrylate-styrene copolymer resin was obtained. (Thermoplastic resin A4) was obtained. The ratio of the structural unit derived from methyl methacrylate in the thermoplastic resin A4 was 29 mol%. Moreover, the weight average molecular weight (standard polystyrene conversion) measured by gel permeation chromatography was 171,000.
- Synthesis Example 7 [Production of methyl methacrylate-styrene copolymer resin (thermoplastic resin A5)] Continuous polymerization was carried out under the same conditions as in Synthesis Example 5 except that 50.000 mol% of purified methyl methacrylate and 49.998 mol% of purified styrene were used as monomer components, and a methyl methacrylate-styrene copolymer resin was obtained. (Thermoplastic resin A5) was obtained. The ratio of the structural unit derived from methyl methacrylate in the thermoplastic resin A5 was 48 mol%. Moreover, the weight average molecular weight (standard polystyrene conversion) measured by gel permeation chromatography was 148,000.
- Table 1 shows a list of thermoplastic resins obtained in Synthesis Examples 1 to 7.
- thermoplastic resin composition obtained by dry blending thermoplastic resin A3 and thermoplastic resin B1 at three mass ratios of 10:90, 50:50, and 90:10 is introduced into the same-direction twin-screw extruder having a shaft diameter of 25 mm. Then, extrusion was performed while kneading under conditions of a cylinder temperature of 250 ° C. and a discharge speed of 5 kg / h. The obtained resin composition was injection molded, and the haze and refractive index of the prepared sample were measured. The results are shown in Table 2. Further, FIG. 1 shows the correlation between the blend ratio and the refractive index when the thermoplastic resins A3 and B1 are blended.
- Examples 2-1 to 2-3 Extrusion was performed using the thermoplastic resin A3 and the thermoplastic resin B2 under the conditions of Examples 1-1 to 1-3, and the obtained resin composition was injection molded. It was measured. The results are shown in Table 2.
- Examples 3-1 to 3-3 Extrusion was performed using the thermoplastic resin A4 and the thermoplastic resin B2 under the conditions of Examples 1-1 to 1-3, and the obtained resin composition was injection-molded. The haze and refractive index of the prepared sample were determined. It was measured. The results are shown in Table 2.
- Example 5 Extrusion was performed under the conditions of Example 1-1 using the thermoplastic resin A4 and the thermoplastic resin B1 at a mass ratio of 10:90, and the obtained resin composition was injection molded. The refractive index was measured. The results are shown in Table 2.
- Example 6 Extrusion was performed under the conditions of Example 1-3 using the thermoplastic resin A1 and the thermoplastic resin B2 at a mass ratio of 90:10, and the obtained resin composition was injection-molded. The refractive index was measured. The results are shown in Table 2.
- Comparative Examples 1-1 to 1-3 Extrusion was carried out under the conditions of Examples 1-1 to 1-3 using Acrypet VH5 (Mitsubishi Rayon Co., Ltd.), which is polymethyl methacrylate, and thermoplastic resin B1, and the resulting resin composition was injected. The haze of the prepared sample was measured. The results are shown in Table 3.
- Comparative Examples 2-1 to 2-3 Extrusion was performed under the conditions of Examples 1-1 to 1-3 using ZEONEX 330R (manufactured by ZEON CORPORATION), which is a cycloolefin polymer, and thermoplastic resin B1, and the resulting resin composition was injection molded. The haze of the prepared sample was measured. The results are shown in Table 3.
- Comparative Examples 3-1 to 3-3 Extrusion was performed using the cycloolefin polymer ZEONEX 480R (manufactured by Nippon Zeon Co., Ltd.) and thermoplastic resin B1 under the conditions of Examples 1-1 to 1-3, and the resulting resin composition was injection molded. The haze of the prepared sample was measured. The results are shown in Table 3.
- Comparative Examples 4-1 to 4-3 Extrusion was performed under the conditions of Examples 1-1 to 1-3 using TOPAS 5013L-10 (manufactured by Polyplastics Co., Ltd.), which is a cycloolefin copolymer, and thermoplastic resin B1, and the resulting resin composition was obtained. The haze of the produced sample was measured by injection molding. The results are shown in Table 3. In Table 3, those with significant white turbidity were indicated as “white turbidity”.
- thermoplastic transparent resin compositions of Examples 1 to 6 can obtain high transparency by blending the specific thermoplastic resin (A) and the thermoplastic resin (B). Moreover, as shown in FIG. 1, the refractive index of a thermoplastic resin composition can be easily adjusted by changing the blend ratio of a thermoplastic resin (A) and a thermoplastic resin (B). On the other hand, as shown in Table 3, the thermoplastic resin compositions of Comparative Examples 1 to 4 in which a resin other than the thermoplastic resin (A) and the thermoplastic resin (B) are blended have low transparency. .
- thermoplastic transparent resin composition of the present invention is a resin composition in which different thermoplastic resins are blended, it has high transparency and can be easily refracted by appropriately changing the blend ratio of the resin. It is possible to adjust the rate.
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Abstract
Description
熱可塑性樹脂(A):一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位を少なくとも1種と、一般式(2)で示される芳香族ビニルモノマー由来の構成単位を少なくとも1種含み、該(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して1~99モル%である熱可塑性樹脂。
熱可塑性樹脂(B):一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位を少なくとも1種と、一般式(2)で示される芳香族ビニルモノマー由来の構成単位を少なくとも1種含み、該(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して1~99モル%である熱可塑性樹脂において、該芳香族ビニルモノマー由来の構成単位中の芳香族二重結合の70%以上を水素化して得られる熱可塑性樹脂。
3. 前記熱可塑性樹脂(B)において、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が、全構成単位の合計に対して45~99モル%である上記1又は2に記載の熱可塑性透明樹脂組成物。
4. 3.2mm厚の成型片を透過法で測定した際、ヘイズが5%以下となる上記1~3のいずれかに記載の熱可塑性透明樹脂組成物。
5. 前記一般式(1)において、R1及びR2がメチル基である上記1~4のいずれかに記載の熱可塑性透明樹脂組成物。
6. 前記一般式(2)において、R3が水素原子であり、R4がフェニル基である上記1~5のいずれかに記載の熱可塑性透明樹脂組成物。
7. 前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して15~65モル%である前記熱可塑性樹脂(A)と、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して55~80モル%である前記熱可塑性樹脂(B)とをブレンドしてなる上記1~6のいずれかに記載の熱可塑性透明樹脂組成物。
8. 前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して15~35モル%である前記熱可塑性樹脂(A)と、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して55モル%以上65モル%未満である前記熱可塑性樹脂(B)とをブレンドしてなる上記7に記載の熱可塑性透明樹脂組成物。
9. 前記熱可塑性樹脂(A)において、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して15~25モル%である上記8に記載の熱可塑性透明樹脂組成物。
10. 前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して15~65モル%である前記熱可塑性樹脂(A)と、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して65~80モル%である前記熱可塑性樹脂(B)とをブレンドしてなる上記7に記載の熱可塑性透明樹脂組成物。
11. 前記熱可塑性樹脂(A)において、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して15~55モル%である上記10に記載の熱可塑性透明樹脂組成物。
12. 上記1~11のいずれかに記載の熱可塑性透明樹脂組成物からなる光学部品。
13. 上記1~11のいずれかに記載の熱可塑性透明樹脂組成物からなる押出成形熱可塑性樹脂シート。
14. 上記1~11のいずれかに記載の熱可塑性透明樹脂組成物からなる層を有する共押出成形多層熱可塑性樹脂シート。
15. 上記13又は14記載の熱可塑性樹脂シートからなる導光板。
16. 上記13又は14記載の熱可塑性樹脂シートからなる基板、及び該基板の片面又は両面に形成された少なくとも1種類のレンズからなるレンズユニット。
17. 上記13又は14記載の熱可塑性樹脂シートからなるディスプレイ前面パネル。
18. 上記1~11のいずれかに記載の熱可塑性透明樹脂組成物からなる射出成形体。
19. 前記射出成形体が、導光板、プラスチックレンズ又は光記録媒体基板である上記18に記載の射出成形体。
熱可塑性樹脂(A)は、下記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位を少なくとも1種と、下記一般式(2)で示される芳香族ビニルモノマー由来の構成単位を少なくとも1種含み、該(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して1~99モル%である熱可塑性樹脂である。
熱可塑性樹脂(B)は、下記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位を少なくとも1種と、下記一般式(2)で示される芳香族ビニルモノマー由来の構成単位を少なくとも1種含み、該(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して1~99モル%である熱可塑性樹脂において、該芳香族ビニルモノマー由来の構成単位中の芳香族二重結合の70%以上を水素化して得られる熱可塑性樹脂である。
これらのうち、好ましくはR2がメチル基及び/又はエチル基の(メタ)アクリル酸エステルモノマー由来の構成単位であり、更に好ましくはR1がメチル基、R2がメチル基である、メタクリル酸メチル由来の構成単位である。
熱可塑性樹脂(A)及び熱可塑性樹脂(B)は、前記一般式(1)で表される(メタ)アクリル酸エステルモノマー由来の構成単位を少なくとも1種含んでいればよく、2種以上を含有していてもよい。
熱可塑性樹脂(A)、及び熱可塑性樹脂(B)の芳香族二重結合を水素化する前の熱可塑性樹脂(以下、これを「熱可塑性樹脂(B0)」と称する場合がある)は、前記一般式(2)で表される芳香族ビニルモノマー由来の構成単位を少なくとも1種含んでいればよく、2種以上を含有していてもよい。
(メタ)アクリル酸エステルモノマー由来の構成単位の割合が1~80モル%であれば、熱可塑性樹脂(B)との相溶性が特に高い。
(メタ)アクリル酸エステルモノマー由来の構成単位の割合が45~99モル%であれば、熱可塑性樹脂(A)との相溶性が特に高い。
(メタ)アクリル酸エステルモノマーと芳香族ビニルモノマーの重合には、公知の方法を用いることができるが、例えば、塊状重合法、溶液重合法などにより製造することができる。
塊状重合法は、上記モノマー、重合開始剤を含むモノマー組成物を完全混合槽に連続的に供給し、100~180℃で連続重合する方法などにより行われる。上記モノマー組成物は、必要に応じて連鎖移動剤を含んでもよい。
上記水素化反応に用いられる溶媒は、前記の重合溶媒と同じであっても異なっていてもよい。例えば、シクロヘキサン、メチルシクロヘキサンなどの炭化水素系溶媒、酢酸エチル、イソ酪酸メチルなどのエステル系溶媒、アセトン、メチルエチルケトンなどのケトン系溶媒、テトラヒドロフラン、ジオキサンなどのエーテル系溶媒、メタノール、イソプロパノールなどのアルコール系溶媒などを挙げることができる。
また、熱可塑性樹脂(B)の重量平均分子量は、特に制限はないが、強度及び成型性の観点から、40,000~500,000であることが好ましく、50,000~300,000であることがより好ましい。
上記重量平均分子量は、ゲル浸透クロマトグラフィー(GPC)により測定される、標準ポリスチレン換算の重量平均分子量である。
上記の中でも、透明性の観点から、本発明の熱可塑性樹脂組成物は、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して15~35モル%、好ましくは15~25モル%である熱可塑性樹脂(A)と、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して55モル%以上65モル%未満である熱可塑性樹脂(B)とをブレンドしてなる熱可塑性樹脂組成物、又は、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して15~65モル%、好ましくは15~55モル%である熱可塑性樹脂(A)と、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して65~80モル%である熱可塑性樹脂(B)とをブレンドしてなる熱可塑性樹脂組成物であることがより好ましい。
熱可塑性樹脂(A)と熱可塑性樹脂(B)の組み合わせが上記範囲であると、熱可塑性樹脂(A)と熱可塑性樹脂(B)との相溶性が高く、これらをブレンドして得られる熱可塑性樹脂組成物の透明性が特に良好である。
実施例および比較例で得られた熱可塑性透明樹脂組成物の評価は以下のように行った。
日精樹脂工業(株)製 NP7-1F射出成型によって、50φ、3.2mm厚の円盤状試料を作製し、日本電色工業(株)製 COH-400で透過法により測定した。なお、ここではヘイズが5%以下の試料を「透明」とする。
日本電子(株)製 JNM-AL400を用いて、1H―NMR(400MHz:溶媒はCDCl3)の測定値から計算した。
水素化反応前後のUVスペクトル測定における260nmの吸収の減少率により求めた。水素化反応前の樹脂の濃度C1における吸光度A1、水素化反応後の樹脂の濃度C2における吸光度A2から、以下の式より算出した。
水素化率=100×[1-(A2×C1)/(A1×C2)]
まず、ヘイズ測定において作製した円盤状試料を、リファインテック(株)製 REFINE SAW,Loで、縦40mm、横8mm、厚さ3.2mmに切断した。その試料の屈折率を、(株)アタゴ製 多波長アッベ屈折計DR-M2で測定した。測定温度は20℃、測定波長は589nmであり、中間液にはモノブロモナフタレンを使用した。
モノマー成分として、精製したメタクリル酸メチル(三菱ガス化学社製)60.000モル%と、精製したスチレン(和光純薬工業社製)39.998モル%、重合開始剤としてt-アミルパーオキシ-2-エチルヘキサノエート(アルケマ吉富社製、商品名:ルペロックス575)0.002モル%からなるモノマー組成物を、ヘリカルリボン翼付き10L完全混合槽に1kg/hで連続的に供給し、平均滞留時間2.5時間、重合温度150℃で連続重合を行った。重合槽の液面が一定となるよう底部から連続的に抜き出し、脱溶剤装置に導入してペレット状のメタクリル酸メチル-スチレン共重合樹脂(熱可塑性樹脂A1)を得た。熱可塑性樹脂A1中のメタクリル酸メチル由来の構成単位の割合は57モル%であった。また、ゲル浸透クロマトグラフィーにより測定した重量平均分子量(標準ポリスチレン換算)は147,000であった。
合成例1で得られた熱可塑性樹脂A1をイソ酪酸メチル(関東化学社製)に溶解し、10質量%イソ酪酸メチル溶液を調製した。1000mLオートクレーブ装置に、熱可塑性樹脂A1の10質量%イソ酪酸メチル溶液を500質量部、水素化触媒として10質量%Pd/C(NEケムキャット社製)を1質量部仕込み、水素圧9MPa、200℃で15時間保持して、熱可塑性樹脂A1のスチレン部位の芳香族二重結合を水素化した。スチレン部位の水素化反応率は99%であった。フィルターにより水素化触媒を除去し、脱溶剤装置に導入してペレット状のメタクリル酸メチル-スチレン-ビニルシクロヘキサン共重合樹脂(熱可塑性樹脂B1)を得た。熱可塑性樹脂B1において、メタクリル酸メチル由来の構成単位の割合は57モル%であった。
モノマー成分として、精製したメタクリル酸メチル75.000モル%と精製したスチレン24.998モル%を用いたこと以外は、合成例1と同じ条件で連続重合を行い、熱可塑性樹脂A2を得た。熱可塑性樹脂A2中のメタクリル酸メチル由来の構成単位の割合は73モル%であった。また、ゲル浸透クロマトグラフィーにより測定した重量平均分子量(標準ポリスチレン換算)は124,000であった。
合成例2と同条件で、合成例3で得られた熱可塑性樹脂A2のスチレン部位の芳香族二重結合を水素化した。スチレン部位の水素化反応率は99%であった。また、得られたメタクリル酸メチル-スチレン-ビニルシクロヘキサン共重合樹脂(熱可塑性樹脂B2)において、メタクリル酸メチル由来の構成単位の割合は73モル%であった。
モノマー成分として、精製したメタクリル酸メチル20.000モル%と、精製したスチレン79.998モル%、重合開始剤としてt-アミルパーオキシ-2-エチルヘキサノエート0.002モル%からなるモノマー組成物を、ヘリカルリボン翼付き10L完全混合槽に1kg/hで連続的に供給し、平均滞留時間2.5時間、重合温度150℃で連続重合を行った。重合槽の液面が一定となるよう底部から連続的に抜き出し、脱溶剤装置に導入してペレット状のメタクリル酸メチル-スチレン共重合樹脂(熱可塑性樹脂A3)を得た。熱可塑性樹脂A3中のメタクリル酸メチル由来の構成単位の割合は20モル%であった。また、ゲル浸透クロマトグラフィーにより測定した重量平均分子量(標準ポリスチレン換算)は225,000であった。
モノマー成分として、精製したメタクリル酸メチル30.000モル%と、精製したスチレン69.998モル%を用いたこと以外は合成例5と同じ条件で連続重合を行い、メタクリル酸メチル-スチレン共重合樹脂(熱可塑性樹脂A4)を得た。熱可塑性樹脂A4中のメタクリル酸メチル由来の構成単位の割合は29モル%であった。また、ゲル浸透クロマトグラフィーにより測定した重量平均分子量(標準ポリスチレン換算)は171,000であった。
モノマー成分として、精製したメタクリル酸メチル50.000モル%と、精製したスチレン49.998モル%を用いたこと以外は合成例5と同じ条件で連続重合を行い、メタクリル酸メチル-スチレン共重合樹脂(熱可塑性樹脂A5)を得た。熱可塑性樹脂A5中のメタクリル酸メチル由来の構成単位の割合は48モル%であった。また、ゲル浸透クロマトグラフィーにより測定した重量平均分子量(標準ポリスチレン換算)は148,000であった。
軸径25mmの同方向2軸押出し機に、熱可塑性樹脂A3と熱可塑性樹脂B1を10:90、50:50、90:10の3種類の質量比でドライブレンドした熱可塑性樹脂組成物を導入し、シリンダ温度250℃、吐出速度5kg/hの条件で混練しながら押出した。得られた樹脂組成物を射出成形し、作製した試料のヘイズ及び屈折率を測定した。結果を表2に示す。
さらに、熱可塑性樹脂A3とB1をブレンドした際の、ブレンド割合と屈折率との相関を図1に示す。
熱可塑性樹脂A3と熱可塑性樹脂B2を用いて、実施例1-1~1-3の条件で押出しを行い、得られた樹脂組成物を射出成形して、作製した試料のヘイズ及び屈折率を測定した。結果を表2に示す。
熱可塑性樹脂A4と熱可塑性樹脂B2を用いて、実施例1-1~1-3の条件で押出しを行い、得られた樹脂組成物を射出成形して、作製した試料のヘイズ及び屈折率を測定した。結果を表2に示す。
熱可塑性樹脂A5と熱可塑性樹脂B2を用いて、実施例1-1~1-3の条件で押出しを行い、得られた樹脂組成物を射出成形して、作製した試料のヘイズ及び屈折率を測定した。結果を表2に示す。
熱可塑性樹脂A4と熱可塑性樹脂B1を10:90の質量比で用いて、実施例1-1の条件で押出しを行い、得られた樹脂組成物を射出成形して、作製した試料のヘイズ及び屈折率を測定した。結果を表2に示す。
熱可塑性樹脂A1と熱可塑性樹脂B2を90:10の質量比で用いて、実施例1-3の条件で押出しを行い、得られた樹脂組成物を射出成形して、作製した試料のヘイズ及び屈折率を測定した。結果を表2に示す。
ポリメタクリル酸メチルであるアクリペットVH5(三菱レイヨン(株)製)と熱可塑性樹脂B1を用いて、実施例1-1~1-3の条件で押出しを行い、得られた樹脂組成物を射出成形して、作製した試料のヘイズを測定した。結果を表3に示す。
シクロオレフィンポリマーであるZEONEX 330R(日本ゼオン(株)製)と熱可塑性樹脂B1を用いて、実施例1-1~1-3の条件で押出しを行い、得られた樹脂組成物を射出成形して、作製した試料のヘイズを測定した。結果を表3に示す。
シクロオレフィンポリマーであるZEONEX 480R(日本ゼオン(株)製)と熱可塑性樹脂B1を用いて、実施例1-1~1-3の条件で押出しを行い、得られた樹脂組成物を射出成形して、作製した試料のヘイズを測定した。結果を表3に示す。
シクロオレフィンコポリマーであるTOPAS 5013L-10(ポリプラスチックス(株)製)と熱可塑性樹脂B1を用いて、実施例1-1~1-3の条件で押出しを行い、得られた樹脂組成物を射出成形して、作製した試料のヘイズを測定した。結果を表3に示す。
なお、表3において、白濁が著しいものは「白濁」と表記した。
これに対し、表3に示すように、熱可塑性樹脂(A)以外の樹脂と熱可塑性樹脂(B)とをブレンドした比較例1~4の熱可塑性樹脂組成物は、いずれも透明性が低い。
Claims (19)
- 下記の熱可塑性樹脂(A)と熱可塑性樹脂(B)とをブレンドしてなる熱可塑性透明樹脂組成物。
熱可塑性樹脂(A):一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位を少なくとも1種と、一般式(2)で示される芳香族ビニルモノマー由来の構成単位を少なくとも1種含み、該(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して1~99モル%である熱可塑性樹脂。
熱可塑性樹脂(B):一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位を少なくとも1種と、一般式(2)で示される芳香族ビニルモノマー由来の構成単位を少なくとも1種含み、該(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して1~99モル%である熱可塑性樹脂において、該芳香族ビニルモノマー由来の構成単位中の芳香族二重結合の70%以上を水素化して得られる熱可塑性樹脂。
- 前記熱可塑性樹脂(A)において、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が、全構成単位の合計に対して1~80モル%である請求項1記載の熱可塑性透明樹脂組成物。
- 前記熱可塑性樹脂(B)において、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が、全構成単位の合計に対して45~99モル%である請求項1又は2に記載の熱可塑性透明樹脂組成物。
- 3.2mm厚の成型片を透過法で測定した際、ヘイズが5%以下となる請求項1~3のいずれかに記載の熱可塑性透明樹脂組成物。
- 前記一般式(1)において、R1及びR2がメチル基である請求項1~4のいずれかに記載の熱可塑性透明樹脂組成物。
- 前記一般式(2)において、R3が水素原子であり、R4がフェニル基である請求項1~5のいずれかに記載の熱可塑性透明樹脂組成物。
- 前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して15~65モル%である前記熱可塑性樹脂(A)と、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して55~80モル%である前記熱可塑性樹脂(B)とをブレンドしてなる請求項1~6のいずれかに記載の熱可塑性透明樹脂組成物。
- 前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して15~35モル%である前記熱可塑性樹脂(A)と、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して55モル%以上65モル%未満である前記熱可塑性樹脂(B)とをブレンドしてなる請求項7に記載の熱可塑性透明樹脂組成物。
- 前記熱可塑性樹脂(A)において、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して15~25モル%である請求項8に記載の熱可塑性透明樹脂組成物。
- 前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して15~65モル%である前記熱可塑性樹脂(A)と、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して65~80モル%である前記熱可塑性樹脂(B)とをブレンドしてなる請求項7に記載の熱可塑性透明樹脂組成物。
- 前記熱可塑性樹脂(A)において、前記一般式(1)で示される(メタ)アクリル酸エステルモノマー由来の構成単位の割合が全構成単位の合計に対して15~55モル%である請求項10に記載の熱可塑性透明樹脂組成物。
- 請求項1~11のいずれかに記載の熱可塑性透明樹脂組成物からなる光学部品。
- 請求項1~11のいずれかに記載の熱可塑性透明樹脂組成物からなる押出成形熱可塑性樹脂シート。
- 請求項1~11のいずれかに記載の熱可塑性透明樹脂組成物からなる層を有する共押出成形多層熱可塑性樹脂シート。
- 請求項13又は14記載の熱可塑性樹脂シートからなる導光板。
- 請求項13又は14記載の熱可塑性樹脂シートからなる基板、及び該基板の片面又は両面に形成された少なくとも1種類のレンズからなるレンズユニット。
- 請求項13又は14記載の熱可塑性樹脂シートからなるディスプレイ前面パネル。
- 請求項1~11のいずれかに記載の熱可塑性透明樹脂組成物からなる射出成形体。
- 前記射出成形体が、導光板、プラスチックレンズ又は光記録媒体基板である請求項18に記載の射出成形体。
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JP2016196522A (ja) * | 2015-04-02 | 2016-11-24 | 三菱瓦斯化学株式会社 | 熱可塑性透明樹脂組成物 |
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