WO2006057355A1 - Multilayer sheet and light diffusion sheet - Google Patents

Multilayer sheet and light diffusion sheet Download PDF

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Publication number
WO2006057355A1
WO2006057355A1 PCT/JP2005/021723 JP2005021723W WO2006057355A1 WO 2006057355 A1 WO2006057355 A1 WO 2006057355A1 JP 2005021723 W JP2005021723 W JP 2005021723W WO 2006057355 A1 WO2006057355 A1 WO 2006057355A1
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Prior art keywords
resin
styrene
mass
copolymer
component
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Application number
PCT/JP2005/021723
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French (fr)
Japanese (ja)
Inventor
Shintaro Watanabe
Takeshi Yamada
Jun Takahashi
Yasuaki Taruta
Original Assignee
Denki Kagaku Kogyo Kabushiki Kaisha
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Application filed by Denki Kagaku Kogyo Kabushiki Kaisha filed Critical Denki Kagaku Kogyo Kabushiki Kaisha
Priority to JP2006547873A priority Critical patent/JP5069908B2/en
Publication of WO2006057355A1 publication Critical patent/WO2006057355A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2559/00—Photographic equipment or accessories

Definitions

  • Multilayer sheet and light diffusion sheet
  • the present invention relates to a multilayer sheet excellent in light diffusibility, dimensional stability, and light resistance.
  • the present invention relates to a light diffusing sheet used as a light diffusing plate for a transmissive screen of a screen such as a projection television or a liquid crystal TV.
  • a screen lens such as a transmissive screen projects an image of a projection television and displays a target image, and is widely used. Since this screen lens is desired to have a bright and wide viewing angle when observed by an observer, the screen lens is generally configured by combining lens moldings such as a lenticular lens and a Fresnel lens.
  • the lens moldings used for these screen lenses are widely used methacrylic resins with excellent transparency, light resistance, scratch resistance, etc., and excellent moldability. It is performed by molding, extrusion molding, cast molding, injection molding, etc.
  • Patent Document 1 describes a mixture of an aromatic vinyl monomer, a (meth) acrylic acid ester monomer, and a polyfunctional unsaturated monomer.
  • a method for obtaining a Fresnel lens by dissolving and polymerizing a styrene-gen copolymer is disclosed.
  • this technique is insufficient to obtain a molded article for a screen lens having an excellent light diffusibility.
  • the methacrylic resin used as the base material for the light diffusing plate of liquid crystal TVs has a high water absorption rate, which causes a change in the dimensions of the light diffusing plate molding, causing warping of the light diffusing plate, and optical characteristics Had the problem of being damaged.
  • the image or lamp light is projected for a long time, there is a problem that discoloration occurs due to deterioration of the resin used in the screen lens and the light diffusion plate, and the image is discolored.
  • Patent Document 1 Japanese Patent Laid-Open No. 5-341101
  • An object of the present invention is to provide a multilayer sheet excellent in dimensional stability, light resistance and light diffusibility, particularly as a light diffusion sheet such as a molded article for a screen lens and a molded article for a light diffusion plate. Is to provide a sheet.
  • the inventors of the present invention contain a specific styrene copolymer mainly composed of a styrene monomer unit and a specific unmelted compound.
  • Copolymers mainly composed of styrene monomer units and (meth) acrylic acid ester monomer units, specific unmelted compounds and specific light resistance The present invention has found that a multilayer sheet having excellent dimensional stability, excellent light resistance, and excellent light diffusibility can be obtained by using a styrene-based resin composition containing an agent as a surface layer and a back layer. Has reached
  • the present invention has the following gist.
  • Component (B) 100 parts by mass of a styrene copolymer and an unmelted material having a refractive index difference of 0.05 to 0.14 and an average particle diameter of 2 to 10 / ⁇ ⁇ A resin composition comprising 1 to 10 parts by mass of a compound.
  • a part of the unmelted compound contained in the component (A) protrudes from the surface of the surface layer a and the back layer c, and forms irregularities on the surface of the surface layer a and the back layer c.
  • the multilayer sheet according to any one of 1) to (4).
  • component (A) is a cross-linked copolymer containing styrene and methyl methacrylate as monomers.
  • a benzoxazole compound is added to at least one of the component (A) and the component (B)
  • the multilayer sheet according to any one of (1) to (10) above, containing 5 to 0.5 parts by mass.
  • Composition power of styrene-based resin of component (A) Furthermore, a polyether ester amide block having a refractive index difference of 0.02 or less with respect to 100 parts by mass of the styrene-based copolymer. 7 to 20 parts by mass of a copolymer, 0 to 2 parts by mass of a Zeon-based surfactant and Z or a non-amine surfactant, or any one of (1) to (12) above Multi-layer sheet.
  • Polyether ester amide block copolymer strength The polyether ester amide block copolymer comprising the following (F—A), (F 2 -B), and (F—C) as monomers: ).
  • R1 is an ethylene oxide group
  • R2 is an ethylene oxide group or propylene oxide group
  • X is a halogen, an alkyl group (carbon number: 1 to 6) or a sulfonic acid group or a metal salt thereof
  • L is 0 to Integer of 4
  • m and n represent an integer of 16 or more.
  • Rl is an ethylene oxide group
  • R2 is an ethylene oxide group or propylene oxide group
  • X is a halogen, an alkyl group (carbon number: 1 to 6) or a sulfone group or a metal salt thereof
  • Y is an alkylene group ( Carbon number: 1-6), alkylidene group (carbon number: 1-6), cycloalkylidene group (carbon number: 7-17), arylealkylidene group (carbon number: 7-17), 0, SO, SO,
  • R1 represents an ethylene oxide group
  • R2 represents an ethylene oxide group or a propylene oxide group
  • m and n represent an integer of 16 or more.
  • the cation surfactant power in component (A) is an organic sulfonic acid metal salt having 10 to 14 carbon atoms, and the non-amine nonionic surfactant is a glycerin fatty acid ester (13) -The multilayer sheet in any one of (15).
  • the multilayer sheet according to 7 The multilayer sheet according to 7).
  • an unprecedented multilayer sheet having excellent light diffusibility can be provided extremely advantageously in the industry. Since the multilayer sheet of the present invention is excellent in light diffusibility, dimensional stability and light resistance, it can be suitably used particularly for optical display applications such as Fresnel lenses, lenticular lenses and light diffusion plates.
  • styrenic monomer used in the present invention examples include styrene, a-methylstyrene, p-methylstyrene, p-t-butylstyrene and the like, and preferably styrene.
  • Examples of the (meth) acrylic acid ester monomer in the present invention include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methyl hexyl acrylate. Rate, 2-ethylhexyl acrylate, octyl acrylate and the like. These may be used alone or in combination of two or more. Preferred is methyl metatalylate, ethyl acrylate, n-butyl acrylate, or a mixture thereof.
  • the styrene copolymer in the component (A) used for the surface layer a and the back layer c of the present invention is 20 to 50% by mass, preferably 22 to 48% by mass, of a styrene monomer unit. and (meth) acrylic acid ester monomer units 80-50 mass 0/0, preferably from 78 to 52 weight 0/0. If the styrene monomer unit is less than 20% by mass, the multilayer sheet may be deformed due to moisture absorption, and if it exceeds 50% by mass, the light resistance is lowered, and the multilayer sheet may be discolored by light irradiation.
  • the styrene copolymer in the component (B) is a copolymer having a styrene monomer unit as a main component, and among them, the styrene monomer unit is 38 to 90% by mass,
  • the copolymer (I) having 50 to 90% by mass and 62 to 10% by mass, preferably 50 to 10% by mass of (meth) acrylic acid ester monomer units is preferred.
  • the styrene monomer unit exceeds 90% by mass, the light resistance is lowered, and the light diffusion sheet may be discolored by light irradiation. If it is less than 50% by mass, the light diffusion sheet may be deformed by moisture absorption.
  • the styrene copolymer in component (B) is a copolymer of a styrene monomer and a (meth) acrylic acid ester monomer, as well as a vinyl monomer copolymerizable therewith.
  • the amount is preferably about 10 parts by mass or less with respect to 100 parts by mass of the total amount of the styrene monomer and the (meth) acrylate monomer.
  • the styrene monomer unit is 50 to 90% by mass, preferably 52 to 88% by mass
  • the (meth) acrylic acid ester monomer unit is 50 to 10% by mass, preferably 48 to 12% by mass. %
  • And copolymerizable vinyl compound monomer units of 0 to 10% by mass, preferably 0 to 8% by mass.
  • this copolymerizable bur monomer examples include cyanide butyl monomers such as acrylonitrile methacrylo-tril; methacrylic acid, acrylic acid, maleic anhydride, maleic acid, itaconic acid, itaconic anhydride, etc. And unsaturated carboxylic acid monomers; maleimide monomers such as maleimide, N-methylmaleimide, N-phenolmaleimide, and the like. These may be used alone or in combination of two or more.
  • styrene copolymer in the component (B) in addition to the above, 80 to 99% by mass of a styrene monomer unit and 20 to 1% by mass of a methacrylic acid monomer unit can be copolymerized.
  • styrene copolymer (11) consisting of 0 to 10% by mass of a vinyl compound monomer unit, 20 to 60% by mass of a styrene monomer unit, a (meth) acrylic acid ester unit
  • a resin mixture composed of 70 to 30 parts by mass referred to as ( ⁇ ) ⁇ 0 ⁇ ) a resin mixture
  • (II) ⁇ 0 ⁇ ) Resin composition If the total amount of styrene monomer in the composition exceeds 90% by mass, the light resistance is lowered and the multilayer sheet may be discolored by light irradiation.
  • the multilayer sheet may be deformed by moisture absorption.
  • (Ii) ⁇ 0 ⁇ ) Using a resin mixture makes it possible to obtain a multilayer sheet having a high heat distortion temperature.
  • the unmelted compound in the component (A) of the present invention partially protrudes from the surface of the surface layer a and the back layer c, and forms irregularities on the surface of the surface layer a and the back layer c. Is preferred. Such irregularities can improve the fluidity and releasability of the multilayer sheet surface.
  • the unmelted compound in component (A) is a compound that does not melt at the melting point of the styrene copolymer of component (A), and is preferably 200 ° C or higher in an atmosphere of 101.3 kPa (l atm). Particularly preferred are compounds having a melting point or soft spot of 220-320 ° C. When the melting point and softening point are less than 200 ° C, the compound melts immediately when melt kneaded with a styrene polymer, or when a styrene resin composition is formed into a sheet or during injection molding, so that excellent optical properties are obtained. I ca n’t hold it! / There may be cases.
  • the unmelted compound in the component (A) has a refractive index difference with respect to the styrene copolymer in the component (A) within 0.005, preferably within 0.003. When the refractive index difference exceeds 0.005, the total light transmittance and light diffusibility of the resulting multilayer sheet are lowered.
  • the unmelted compound in component (A) has an average particle size of 5 to 15 m, preferably 7 to 14 m. When the average particle size is less than 5 ⁇ m, the diffusivity increases and the light diffusivity increases, and when it exceeds 15 ⁇ m, the total light transmittance and the light diffusivity decrease.
  • the average particle size of the unmelted compound is a value obtained by measurement using a Coulter Multisizer (manufactured by Beckman Coulter).
  • the content of the unmelted compound in the component (A) is 1 to 10 parts by weight, preferably 2 to 8 parts by weight, based on 100 parts by weight of the styrene copolymer in the component (A). Part.
  • the content of the unmelted compound is less than 1 part by mass, the haze and diffusivity are reduced and the light diffusibility is reduced.
  • the content exceeds 10 parts by mass the total light transmittance and the diffusivity are reduced, and the light diffusibility is reduced. "I'm going down”.
  • composition of the unmelted compound in component (A) is not particularly limited, but a crosslinked copolymer containing styrene and methyl methacrylate as monomers is preferred.
  • the unmelted compound used for component (B) is a compound that does not melt at the melting point of the styrene copolymer of component (B), and is preferably 200 200 kPa (l atm) in an atmosphere.
  • a compound having a melting point or soft point of not lower than ° C and particularly preferably from 220 to 500 ° C is preferable.
  • the melting point and soft melting point are less than 200 ° C, the unmelted compound melts at the time of melt-kneading with a styrene copolymer or when a styrene-based resin composition is formed into a sheet, and excellent optical characteristics are maintained immediately. You may not be able to hold it.
  • the difference in refractive index between the styrene copolymer and the unmelted compound in component (B) is 0.05 to 0.14, preferably 0.06 to 0.13. If the refractive index difference is less than 0.05, the haze and diffusivity of the resulting multilayer sheet will be small and the light diffusivity will be reduced, and if it exceeds 0.14, the total light transmittance and diffusivity will be reduced.
  • the average particle size of the unmelted compound in component (B) is 2 to: LO m, preferably 3 to 8 m. If the average particle size of the unmelted compound is less than 2 m, the resulting multilayer sheet has a low haze and light diffusibility, and if it exceeds 10 m, the total light transmittance and diffusivity are reduced.
  • the average particle size of the unmelted compound is a value obtained by measurement using a Coulter Multisizer (Beckman Coalter).
  • the content of the unmelted compound in the component (B) is 1 to 10 parts by mass, preferably 2 to 8 parts by mass with respect to 100 parts by mass of the styrene copolymer in the component (B).
  • the content of the unmelted compound is less than 1 part by mass, the haze of the resulting multilayer sheet decreases and the light diffusibility decreases, and when it exceeds 10 parts by mass, the total light transmittance and the diffusivity decrease.
  • composition of the unmelted compound in component (B) is not particularly limited, but a cross-linked copolymer containing methyl methacrylate as a monomer is preferred.
  • examples thereof include polymethyl methacrylate crosslinked beads (hereinafter referred to as “PMMA crosslinked beads”).
  • component (A) 0.1 to 2 parts by mass of a hindered amine compound, preferably 0.2 to 1.8 parts by mass, and 100 parts by mass of a styrene copolymer. It is necessary to contain 0.1 to 2 parts by mass, preferably 0.2 to 1.8 parts by mass of the benzotriazole compound.
  • the hindered amine compound and the benzotriazole compound strength are each less than 0.1 parts by mass, the light resistance of the resulting multilayer sheet is lowered, and when it exceeds 2 parts by mass, the yellowness of the obtained multilayer sheet tends to be strong, It is not preferable.
  • Hindered amine compounds are amamine-based photostabilizers such as bis (2, 2, 6, 6-tetramethyl-1- (octyloxy) -4-piveridyl) ester, decanodioic acid, 1, 1- Dimethylethyl hydroperoxide, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl)-4-hydrido (methyl)] Methyl] butyl malonate, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, methyl 1, 2, 2, 6, 6-pentamethyl 4-piberidyl cenocate, bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate. These may be used alone or in combination of two or more.
  • Benzotriazole compounds are ultraviolet absorbers such as 2- (2H-benzotriazole 2-yl) p cresol, 2- (2H-benzotriazole 2-yl) 4-6 bis (1 Methyl 1-phenyl) phenol, 2- [5 Black mouth (2H) -benzotriazole-2-yl] —4-methyl] -6- (t-butyl) phenol, 2,4-di-tert-butyl-6 — (5 black-mouthed benzotriazole-2-yl) phenol, 2- (2H benzotriazole-2-yl) -4,6 di-t-pentylphenol. These may be used alone or in combination of two or more.
  • the styrenic resin composition used for the surface layer a and the back layer c does not need to be the same and may be different.
  • At least one of component (A) and component (B) is preferably a benzoxazole-based compound that is a so-called fluorescent whitening agent as a colorant. It is desirable to contain parts by mass, particularly preferably 0.005 to 0.05 parts by mass.
  • the content of the benzoxazole-based compound in at least one of the components is 0.0005 part by mass or more, the yellowness of the obtained sheet is reduced and the appearance is further improved as compared with less than 0.005 part by mass.
  • the total light transmittance of the resulting multilayer sheet tends to increase, which is preferable.
  • the amount of 0.5 parts by mass or less is preferable because the light resistance of the resulting multilayer sheet is further improved as compared with the case of exceeding 0.5 parts by mass.
  • benzoxazole compounds include 2,5 thiopheneyl (5 tert-butyl-1,3 benzoxazole, 2,5 thiopheneyl (5-t-butyl-1,3-benzoxazole 10% and dicyclohexyl phthalate). 90% mixture, 4,4′-bis (benzoxazol 2-yl) stilbene and the like may be mentioned, and these may be used alone or in combination.
  • the component (A) has a refractive index difference of 0.02 or less with respect to the styrene copolymer.
  • Tellester amide block copolymer 7 to 20 parts by mass with respect to 100 parts by mass of styrene-based copolymer, 0-on surfactant and Z or non-amine non-one surfactant. It is preferable to contain ⁇ 2 parts by mass.
  • the content of the polyetheresteramide block copolymer is 7 parts by mass or more, the scratch resistance of the resulting multilayer sheet is further improved compared to the case of less than 7 parts by mass, and a sufficient antistatic effect is obtained. Therefore, it is preferable.
  • the content of the polyether ester amide block copolymer is 20 parts by mass or less, the yellowness of the resulting multilayer sheet is further reduced as compared with the case where the content exceeds 20 parts by mass. Further, it is preferable that the difference in refractive index is 0.02 or less because the light transmittance is improved as compared with the case where the refractive index difference exceeds 0.02.
  • the monomer (FA) in the polyetheresteramide block copolymer is an aminocarboxylic acid or ratatam having 6 or more carbon atoms, or a salt of diamine and dicarboxylic acid having 6 or more carbon atoms. is there.
  • aminocarboxylic acids having 6 or more carbon atoms include ⁇ -aminocabrolic acid, ⁇ -amino force prillic acid, ⁇ - aminoenanthic acid, and 1,2-aminododecanoic acid. Prolatatam, Enantolactam, and Power Prillatatum.
  • Examples of the salt of diamine and dicarboxylic acid having 6 or more carbon atoms include hexamethylene diamine adipate, hexamethylene diamine-sebacinate, hexamethylene diamine monoisophthalate, etc. Is mentioned.
  • the monomer (F- ⁇ ) in the polyetheresteramide block copolymer is a diol compound represented by general formulas (Chemical Formula 1) to (Chemical Formula 3).
  • R1 is an ethylene oxide group
  • R2 is an ethylene oxide group or propylene oxide group
  • X is a halogen, an alkyl group (carbon number: 1 to 6)
  • L represents an integer of 0 to 4
  • m and n represent an integer of 16 or more.
  • R1 is an ethylene oxide group
  • R2 is an ethylene oxide group or propylene oxide group
  • X is a halogen, an alkyl group (carbon number: 1 to 6) or a sulfone group or a metal salt thereof
  • Y is an alkylene group ( Carbon number: 1-6), alkylidene group (carbon number: 1-6), cycloalkylidene group (carbon number: 7-17), arylealkylidene group (carbon number: 7-17), 0, SO, SO,
  • R1 represents an ethylene oxide group
  • R2 represents an ethylene oxide group or a propylene oxide group
  • m and n represent an integer of 16 or more.
  • Examples of these diol compounds include ethylene oxide of bisphenol A and Z or propionoxide-containing products, 2,2-bis (4,4'-hydroxycyclohexyl).
  • Carboxy with Z or propylene oxide Ethylene oxide with 4, 4 '(hydroxy) biphenyl and Carboxy with Z or propylene oxide, Ethylene oxide with bis (4-hydroxyphenol) sulfide and Z or propylene oxide Carbide with oxide, Bis (4-hydroxyphenol) methane ethylene oxide and Z or Propylene oxide, Bis (4-hydroxyphenol)
  • the monomer (F-B) diol compound includes hydroquinone ethylene oxide adducts, bisphenol A ethylene oxide adducts, and bisphenolore S ethylene oxide adducts. !], Dihydroxynaphthalene with ethylene oxide!] Or a block polymer thereof. Particularly preferred is an ethylene oxide adduct of bisphenol A.
  • the monomer (F—C) in the polyetheresteramide block copolymer is a dicarboxylic acid, and a dicarboxylic acid having 4 to 20 carbon atoms is preferred.
  • terephthalic acid, isophthalic acid Aromatic dicarboxylic acids such as phthalic acid, naphthalene-1,6 dicarboxylic acid, naphthalene-1,2,7 dicarboxylic acid, etc., 1,4-cyclohexanedicarboxylic acid, 1,2 cyclohexane dicarboxylic acid, etc.
  • succinic acid, oxalic acid, adipic acid, sebacic acid and the like are examples of the like.
  • (F—A), (F—B) and (F—C) are used in proportions of (F—A) of 25 to 85 parts by mass, (F—B) of 15 to 70 parts by mass, (F—C). ) Is preferably 5 to 60 parts by mass.
  • the method of polymerizing the polyetheresteramide block copolymer is, for example, by reacting an aminocarboxylic acid or ratatam (F—A) with a dicarboxylic acid (F—C), and both ends are carboxylic acid groups.
  • a polyamide prepolymer of (F—B) diol compound The reaction in the air and the compounds (F-A), (F-B) and (F-C) are charged into a reaction vessel and reacted at a high temperature to produce a dicarboxylic acid-terminated polyamide prepolymer. Thereafter, there is a method of proceeding polymerization under normal pressure or reduced pressure.
  • component (A) 0 to 2 parts by mass of an ionic surfactant and Z or a non-amine-based surfactant are added to 100 parts by mass of the styrene copolymer. It is desirable to contain it. It is preferable that the amount of the cation-based surfactant and the Z or non-amine-one-based surfactant is 2 parts by mass or less because the yellowishness of the resulting multilayer sheet is further reduced as compared with the case of more than 2 parts by mass. . In addition, when an amine-on-type surfactant having each of primary, secondary and tertiary amine structures is contained, the component (A) exhibits a yellow hue.
  • an organic sulfonic acid metal salt may be mentioned.
  • Specific examples include sodium alkyl sulfonate, lithium alkyl sulfonate, sodium alkylbenzene sulfonate, and lithium alkylbenzene sulfonate.
  • sodium alkyl sulfonate is preferably used. More preferred is sodium alkyl sulfonate having 10 to 14 carbon atoms. These may be used alone or in combination of two or more.
  • non-amine nonionic surfactant examples include polyoxyethylene anolalkyl ether, polyoxyethylene fatty acid ester, and glycerin fatty acid ester. Of these, glycerin fatty acid esters are preferably used. These may be used alone or in combination of two or more.
  • the production method of the styrene copolymer in the component (A) and the styrene copolymer in the component (B) is not particularly limited, but is a bulk polymerization method, suspension polymerization method, solution polymerization method, emulsification A polymerization method can be suitably employed.
  • each material of component (A) and component (B) there are no particular restrictions on the blending method of each material of component (A) and component (B), a method of blending before, during or immediately after the polymerization of each styrene copolymer, and a separated styrene copolymer. Examples include a method of blending with a polymer by melt mixing. [0038] Even when each styrene copolymer is pelletized and then melted and mixed with an unmelted compound, the mixing method is not particularly limited. For example, a known mixing apparatus such as a Henschel mixer or a tumbler mixer may be used.
  • the mixture can be uniformly mixed by melt kneading using an extruder such as a single screw extruder or a twin screw extruder.
  • an extruder such as a single screw extruder or a twin screw extruder.
  • a high-concentration mixture in which an unmelted compound is mixed at a high concentration with a styrene-based copolymer is prepared, and when the sheet is manufactured, the high-concentration mixture and the styrene-based copolymer are driven and unmelted.
  • a material in which the content of the compound becomes a specified concentration may be used as a raw material.
  • Additives may be blended with the styrene copolymer in the component (A) and the styrene copolymer in the component (B), if necessary.
  • plasticizers, lubricants, silicone oils and the like can be blended to improve fluidity and releasability.
  • an antistatic agent can be added to prevent dust from the multilayer sheet.
  • a heat stabilizer can be blended in order to impart heat resistance and heat stability.
  • a coloring agent can also be mix
  • the sheet of the present invention has a multilayer structure, and the thickness of each layer is (A) the surface layer a and the back layer c force which also has component force ⁇ ). 005 to 0.5 mm, preferably 0.01 to 0
  • the intermediate layer b which is 4 mm and (B) component strength, is 1 to 7 mm, preferably 1.2 to 6.8 mm. If the surface layer a and the back layer c are less than 0.05 mm, the resulting multilayer sheet may be discolored by light irradiation, and if it exceeds 0.5 mm, it may be deformed by moisture absorption. If the intermediate layer b is less than 1 mm or more than 7 mm, excellent optical properties (light diffusibility) may not be obtained.
  • the thicknesses of the surface layer a and the back layer c need not be the same and can be different.
  • the multilayer sheet may be a sheet obtained by extruding the surface layer a, the intermediate layer b, and the back layer c separately by heat fusion or the like. -You may extrude at the same time using a hold die.
  • the latter method is not only economically advantageous, but also advantageous in terms of quality, which is easy to prevent damage to the surface of the sheet and mixing of foreign matters during lamination.
  • a first complete mixing tank with a volume of about 5 liters and a second complete mixing tank with a capacity of about 15 liters in series and further connect two first and second devolatilization tanks with a preheater in series.
  • MMA monomer solution composed of 40% styrene and 60% methyl methacrylate
  • 15 parts ethylbenzene, 0.01 parts t-butylperoxyisopropyl monocarbonate, 2, 4 Diphenol-ru 4-Methyl-1-pentene 0.2 part was mixed to make a raw material solution.
  • This raw material solution was supplied to the first complete mixing tank controlled at 135 ° C at 6. Okg per hour.
  • the turnover rate at the outlet of the first complete mixing tank was 28%.
  • the conversion rate at the outlet of the second complete mixing tank was 63%.
  • a styrene copolymer A-2 was obtained in the same manner as the styrene copolymer A-1, except that a monomer solution composed of 80% styrene and 20% MMA was used.
  • Styrene copolymer A-3 was obtained in the same manner as styrene copolymer A-1, except that a monomer solution composed of 10% styrene and 90% MMA was used.
  • Styrene copolymer A-4 was obtained in the same manner as styrene copolymer A-1, except that a monomer solution composed of 95% styrene and 5% MMA was used.
  • composition and refractive index of the resulting styrene copolymer are shown in Table I1.
  • Toshiba Silicone Tospearl 2000B was used as the polyorganosiloxane crosslinked beads.
  • the average particle diameter and refractive index are shown in Table 1-2.
  • D-2 was obtained by the same production method as D-1, except that 1.0 part of tricalcium phosphate was used. In addition, using the same production method as D-1, except that 0.2 part of tribasic calcium phosphate was used. A cross-linked bead D-3 was obtained. Further, bead-like crosslinked beads D-4 were obtained by the same production method as D-1, except that 0.1 part of tricalcium phosphate was used.
  • a beaded PMMA crosslinked bead E-2 was obtained by the same production method as PMMA crosslinked bead E-1, except that 1.5 parts of tribasic calcium phosphate was used. Further, bead-like PMMA cross-linked beads E-3 were obtained by the same production method as E-1, except that 1.0 part of tricalcium phosphate was used. Further, bead-like PMMA cross-linked beads E-4 were obtained by the same production method as E-1, except that 0.2 part of tricalcium phosphate was used. These average particle diameters and refractive indexes are shown in Table I2.
  • Styrene-based copolymers A-1 to ⁇ -4, crosslinked beads B, C, D-1 to D-4, ⁇ -1 to ⁇ -4 as unmelted compounds, bis (2, 2, 6, 6-Tetramethyl 4-piperidyl) sebacate and 2- (2H benzotriazole-2-yl) -4, 6 di tert pentylphenol as benzotriazole compounds are shown in Table 1-3 and Table 1-4. It mixed with the compounding ratio. The obtained mixture was kneaded with a 40 mm diameter single screw extruder at a temperature of 240 ° C. and a screw rotation speed of lOO rpm, and pelletized to obtain pellets of styrene-based resin compositions 1 to 25.
  • the styrene-based resin compositions 1 to 13 in Table 1-3 correspond to the styrene-based resin composition (component (A)) in the surface layer a and the back layer c, and the styrene resin compositions in Table 1-4.
  • the system resin compositions 14 to 25 correspond to the resin composition (component (B)) of the intermediate layer b.
  • Copolymer Copolymer Copolymer Copolymer Amine-based Azol-based Unmelted compound Not-melted compound 0053 A-1 A-2 A-3 Compound Compound Compound type Compound content Styrenic resin composition 1 100--0.30 3 D— 1 3 Styrenic resin composition 2 100-1. 5 1. 5 D- 1 3 Styrenic resin composition 3 100--0. 3 0. 3 D— 1 8 Styrenic resin composition 4 100 -1 0.3 3 0.3 D-3 3 Styrenic resin composition 5 ⁇ 100-0. 3 0. 3 D-1 3 Styrene resin composition 6 ⁇ 100 0. 3 0. 3 D— 1 3 Styrene 7 100-0. 05 0.
  • Tree fat composition lens 1 1 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
  • Tree fat composition Tislen 2 ⁇ > ⁇
  • a three-layered sheet shown in Table I 58 was produced using a T-die type multilayer extruder having a feed block.
  • the multi-layer extruder consists of a single 65mm ⁇ full flight screw single screw extruder for the middle layer and one 30mm ⁇ full flight screw single screw extruder for the front and back layers. Oil is the feed A test extruder that was joined in layers with a lock was used. The temperature of each cylinder of the sheet is 23
  • the resin 1 refers to the styrene-based resin composition 1.
  • the resin 2 to the resin 25 refers to the styrene resin composition 2 to the styrene resin composition 25.
  • the optical characteristics when the haze is 99% or more, the total light transmittance is 60% or more, the diffusivity is 20% or more, and the b value is 1 or less, excellent light diffusibility is exhibited, It can be judged that the characteristics are good.
  • the light resistance has a color difference ⁇ value of less than 1 and the hygroscopicity has a deformation of 1 mm or less, it can be judged that each characteristic is excellent.
  • Examples I 1 to ⁇ 9 are particularly preferred embodiments that combine all of these properties.
  • Examples 1-10, 1-11, 1-27, 1-28, 1-30 are other examples.
  • Examples 1 12 to 1 26, 1-29 are comparative examples.
  • Example II Example of multilayer sheet containing colorant (fluorescent brightener)
  • Example I a monomer solution composed of 10% styrene and 90% methyl methacrylate was used, the same procedure as in Example I (A-1) was performed to obtain a styrene copolymer II (A-1). .
  • Example II Except for using a monomer solution composed of 40% styrene and 60% methyl methacrylate, the same procedure as in Example I (A-1) was carried out to obtain a styrene copolymer II (A-2). .
  • Styrene copolymer II (A-4) was obtained in the same manner as in (A-1) except that a monomer solution composed of 95% styrene and 5% methyl methacrylate was used.
  • Table II 1 shows the resin composition and refractive index of the styrene copolymer II (A-14) obtained as described above. [0061] As the unmelted compound, the crosslinked beads B, C, D-1 to D-4 and E-1 to E4 of Example 1 (Table I2) were used.
  • Colorant (F) is a so-called fluorescent whitening agent, 2,5-thiopheneyl (5-t-butyl-1,3 benzoxazole) (Ubitex OB manufactured by Ciba Specialty Chemicals) (F-1), an inorganic pigment.
  • F-2 2,5-thiopheneyl
  • Dairesin BLUE J made by Mitsubishi Chemical was used as (F-3).
  • Styrene copolymers (A-1) to (A-4), B, C, (D-1) to (D-4), ( ⁇ -1) to ( ⁇ -4) as unmelted compounds ), Bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate as a hindered amine compound, 2- (2H benzotriazole-2-yl) as a benzotriazole compound, -4, 6 di-t-pentylphenol, colored As agents, (F-1;) to (F-3) were mixed at the blending ratios shown in Tables II-2 to 11-5.
  • the styrene-based resin compositions 1-27 in Tables 11 2-11 3 correspond to the styrene-based resin compositions (component (A)) of the surface layer a and the back layer c.
  • the styrene-based resin compositions 28 to 54 of ⁇ 4 to 5 correspond to the resin composition (component (B)) of the intermediate layer b.
  • a sheet having a three-layer structure shown in Tables II-6 to 11-12 was prepared using a ⁇ die type multilayer extruder having a feed block.
  • the multi-layer extruder consists of a single 65mm ⁇ full flight screw single screw extruder for the intermediate layer and a single 30mm ⁇ full flight screw single screw extruder for the front and back layers.
  • a test extruder was used in which the fats were joined and multilayered at the feed block. Each cylinder temperature of sheety was operated and molded at 230 ° C.
  • Example II when the haze is 99% or more, the total light transmittance is 68% or more, the diffusivity is 18% or more, and the b value is 1 or less, it can be determined that the optical characteristics are particularly excellent. Also, light resistance is color If the difference ⁇ value is less than 1 and the dimensional stability is less than 1 mm, the dimensional stability can be judged as excellent. Examples II-1 to 11-18 are particularly preferred examples having all these characteristics. Examples ⁇ -19, ⁇ -20, ⁇ -30, ⁇ -31, ⁇ -38 to ⁇ -45, ⁇ -61 to ⁇ -70 are other examples. Examples ⁇ —21 to ⁇ —29, ⁇ —32 to ⁇ —37, ⁇ —46 to ⁇ —60 are comparative examples.
  • Total light transmittance is 68. 7 74. 2 69. 3 69. 5 70. 3 69. 9 73. 2 62. 4 74. 6 63. 3 65. 2
  • Optical haze is) 99. 4 98. 8 99. 3 99. 3 99. 2 99. 2 98. 9 99. 5 98. 7 99. 5 99. 4 Sex Diffusion rate) 23. 6 16. 5 23 22. 8 21. 9 22. 4 18. 4 28 16. 3 27. 1 26. 3 b Value 0. 3 0. 3 0. 3 0. 2 0. 1 1 0. 3 0. 4 0. 3 0.
  • Thickness (mm) 10 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8
  • Example III (Example of multilayer sheet containing antistatic agent)
  • the crosslinked beads BCD— :! D 4 E— :! E 4 of Example 1 (Table I 2) were used.
  • Production of the polyetheresteramide block copolymer (F) was carried out as follows. A force of 55 parts of prolatatam, 30 parts of bisphenol A with ethylene oxide and 15 parts of adipic acid also gave polyether ester amide (F-1). This polyetheresteramide had a refractive index of 1.530. Further, polyether ester amide (F-2) was obtained from 40 parts of force prolatatam, 45 parts of ethylene oxide adduct of bisphenol A and 15 parts of adipic acid. The refractive index of this polyetheresteramide was 1.490.
  • the ionic surfactant and the non-amine nonionic surfactant (G) include sodium dodecyl sulfonate as the ionic surfactant, non-amine nonionic surfactant, Then, glycerin stearic acid diester was used.
  • Styrenic copolymers (A-1) to (A-4), B, C, (D-1) to (D-4), (4-1) to ( ⁇ -4) as unmelted compounds ), Bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate as a hindered amine compound, 2- (2H benzotriazole-2-yl) as a benzotriazole compound, -4, 6 di-t-pentylphenol, poly As ether ester amide block copolymers (F-1) and (F-2), doonyl sodium sulfonate is used as an ionic surfactant, and glyceryl stearate ester is used as a non-amine ionic surfactant.
  • Z non-amine ionic surfactant 1 OZ 90 parts blended as a composite surfactant with the mixing ratio shown in Table III-2-4 Mixed.
  • the resulting mixture was kneaded with a 40 mm diameter single screw extruder at a temperature of 240 ° C and a screw rotation speed of lOOrpm, pelletized, and the styrene-based resin composition shown in Table III-2 to IV-4 1 to 29 pellets were obtained.
  • the styrene-based resin compositions 1 to 18 in Table III 2 to 3 correspond to the styrene-based resin compositions (component (A)) of the surface layer a and the back layer c.
  • the styrene-based resin compositions 19 to 29 of III-4 correspond to the resin composition (component (B)) of the intermediate layer b.
  • Three-layered sheets shown in Tables III-5 to VIII-8 were prepared by using T-die type multi-layer extruders having a feed block, using styrene-based cocoon yarn composites 1 to 29.
  • the multi-layer extruder consists of a single 65mm ⁇ full flight screw single screw extruder for the intermediate layer and a single 30mm ⁇ full flight screw single screw extruder for the front and back layers. Fat is fee
  • a test extruder that was joined and multilayered with a deblock was used. Each cylinder temperature of sheety was operated and molded at 230 ° C.
  • Example III (example of multilayer sheet containing antistatic agent), if the haze is 99% or more, the total light transmittance is 65% or more, the diffusivity is 23% or more, and the b value is 1 or less, the optical characteristics are It can be judged that it is particularly excellent. It can be judged that light resistance is excellent when the color difference ⁇ value is less than 1, dimensional stability is water absorption warpage of 1 mm or less, and antistatic property is surface resistivity of 10 12 ⁇ or less.
  • Examples 111 1 to 111 8, III-22 are particularly preferred embodiments having all these properties.
  • Examples III-9, 111-10, 111-20, 111-21, 111-23, 111-24, III-31 to ⁇ -34 are other examples.
  • Examples m-11 to m-19, in-25 to m-30 are comparative examples.
  • the scratch resistance of the obtained molded product is improved, and when the composite surfactant is used in combination, the scratch resistance is remarkably improved. Power.
  • Thickness (mm) 0.1 0.1 0.1 0.1 0.01 0.1 0.1 0.1 Resin type Resin 19 Resin 19 Resin 26 Resin 23 Resin 19 Resin 19 Resin 19 Grease 19 Seed 19 Middle layer b
  • Resin 9 10 11 12 13 14 15 16 17 18 19 Type of resin used Resin 1 Resin 1 Resin 11 Resin 10 Resin 2 Resin 3 Resin 4 Resin 5 Resin 6 Resin 8 Resin 9 Resin a
  • Thickness (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Layer structure 1.8 Resin type Resin 12 Resin 13 Resin 15 Resin 17 Resin 18 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin Back layer c 1 Thickness ( mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Total thickness (mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
  • Example IV (Example of multilayer sheet containing fluorescent whitening agent and antistatic agent)
  • polyether ester amide block copolymer (F) in the same manner as in Example III, a polyether ester amide (F-l) having a refractive index of 1.530 and a polyether ester amide having a refractive index of 1.490 (F — I got 2).
  • An anionic surfactant and a non-amine nonionic surfactant (G) are sodium dodecyl sulfonate as an anionic surfactant and glycerin stearic acid as a non-amine nonionic surfactant. Diester was used.
  • the colorant (H) is a so-called fluorescent whitening agent, 2, 5 thiofensyl (5 t butyl — 1, 3 benzoxazole) (Ubitex OB manufactured by Ciba Specialty Chemicals) (H-1), inorganic The pigment DAYGRO ZQ-19 (H-2) and the organic dye Mitsubishi Chemical resin Dairesin BLUE J was used as (H-3).
  • Styrene copolymers (A-1) to (A-4), unmelted compounds B, C, (D-1) to (D-4), ( ⁇ -1) to ( ⁇ ⁇ ⁇ -4) ), Bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate as a hindered amine compound, 2- (2H benzotriazole-2-yl) as a benzotriazole compound, -4, 6 di-t-pentylphenol, poly Ether ester amide block copolymers (F-1) and (F-2), sodium dodecyl sulfonate as an ionic surfactant, and glyceryl stearic acid diester as a non-amine ionic surfactant.
  • the styrene-based resin compositions 1 to 39 in Tables IV-2 to IV-3 correspond to the styrene-based resin compositions (component (A)) of the surface layer a and the back layer c.
  • the styrene-based resin compositions 40 to 66 in Tables IV-4 to IV-5 correspond to the resin composition (component (B)) of the intermediate layer b.
  • Sheets having a three-layer structure shown in Tables IV-6 to IV-13 were prepared by using T-die type multi-layer extruders having feed blocks using styrene-based resin compositions 1 to 66.
  • the multi-layer extruder consists of a single 65mm ⁇ full flight screw single screw extruder for the intermediate layer and one 30mm ⁇ full flight screw single screw extruder for the front and back layers.
  • a test extruder was used in which the feed blocks were joined and multilayered. Each cylinder temperature of sheety was operated and molded at 230 ° C.
  • Example IV (example of multilayer sheet containing fluorescent whitening agent and antistatic agent), when haze is 99% or more, total light transmittance is 67% or more, diffusivity is 18% or more, and b value is less than 1, It can be judged that the optical characteristics are particularly excellent. Light resistance is color difference ⁇ ⁇ value less than 1, dimensional stability Can be judged to be excellent when the water absorption warpage is 1 mm or less and the antistatic property is 10 12 ⁇ or less.
  • Examples IV-1 to IV-22 are particularly preferred embodiments having all these characteristics.
  • Examples IV-23 to IV-26, IV-34 to IV-39, IV-46 to IV-52, IV-53, IV-63 to IV 66, IV-73 to IV-82 are other examples. .
  • Examples IV-27 to IV-33, IV-40 to IV-45, IV-54 to IV-62, and IV-67 to IV-72 are comparative examples.
  • Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Intermediate layer
  • Type Resin 47 Resin 44 Resin 40 Resin 40 Resin 40 Resin 52 Resin 40 Resin 40 Resin 52 Sheet b Thickness (mm ) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8
  • Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Intermediate layer Type Resin 65 Resin 66 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Sheet b Thickness (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8
  • Thickness (mm) 0.1 0. 1 0. 1 0.1 0.1 0.1 0.1 0. 1 0. 1 0.1 0. 1 Intermediate layer
  • Thickness (mm) 0.1 0. 1 0. 1 0.1 0. 1 0.1 0.1 0.1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1
  • Total thickness (mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Total light transmittance is ) 69.9 69.0 67.7 54.3 66.3 64.4 75.1 60.0 74.9 65.2 75.5
  • Optical characteristics Haze is 99.1 99.2 99.3 99.7 99.3 99.4 98.1 99.5 98.2 99.4 98.0 diffusivity W 22.1 22.8 24.1 32.0 24.9 26.3 15.3 29.3 15.5 25.6 15.2 b value 0.3 1.0 1.1 0.6 0.2 0.2 0.4 0.6 0.5 0.5 0.5 Meta, f Light color difference ⁇ 0.4 0.6 0.7 0.5 0.4 1.0 0.5 0.6 0.5 0.5 0.5 0.5
  • Dimensional stability Water absorption warp (mm) 0.6 1.1 1.2
  • Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Middle layer Type Resin 40 Resin 40 Resin 40 Resin 40 Resin 40 Resin 40 Resin 40 Resin 40 Resin 40 Resin 40 Sheath b Thickness (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 ⁇ 1.8 1.8 1.8
  • Thickness (mm) 0.1 0.1 0. 1 0.1 0. 1 0.1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 Total thickness (mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 70.2 69.6 73.0 62.1 74.5 62.8 65.0 70.4 69.4 68.4 55.4
  • Optical characteristics Haze (3 ⁇ 4) 99.1 99.2 98.8 99.5 98.4 99.5 99.4 99.1 99.2 99.3 99.6 Sex diffusivity tt) 21.1 22.1 17.4 28.0 15.8 27.4 25.9 21.2 21.9 23.4 31.8 b value 0.3 1.4 0.5 0.6 0.2 0.2 0.2 0.3 1.0 1.
  • a first complete mixing tank with a volume of about 5 liters and a second complete mixing tank with a capacity of about 15 liters in series and further connect two first and second devolatilization tanks with a preheater in series.
  • This raw material solution was supplied to the first complete mixing tank controlled at 135 ° C at 6. Okg per hour.
  • the conversion rate at the outlet of the first complete mixing tank was 28%.
  • the turnover rate at the second complete mixing tank outlet was 63%.
  • a styrene copolymer (I 2) was prepared in the same manner as the styrene copolymer (I 1) except that a monomer solution composed of 80% styrene and 20% methyl methacrylate was used. Obtained.
  • a styrene copolymer (I 3) was obtained in the same manner as the styrene copolymer (I 1) except that a monomer solution composed of 10% styrene and 90% methyl methacrylate was used.
  • the composition of the obtained styrenic polymer is shown in Table V-1.
  • a styrene copolymer (III-1) was obtained in the same manner as the styrene copolymer (I) except that a monomer solution composed of 20% styrene and 80% methyl methacrylate was used.
  • composition of the obtained styrene copolymer (III 1) is shown in Table V-2. 36% of the styrene copolymer (II-1) and 64% of the styrene copolymer (III 1) were mixed to obtain (II) ′ (II detailed composition 1).
  • Styrene copolymer (II-1) 0% and styrene copolymer (III 1) 100% were mixed to obtain (II) ′ (II detailed composition 2).
  • the styrene-based resin compositions 1 to 13 in Table V-4 correspond to the styrene-based resin composition (component (A)) in the surface layer a and the back layer c.
  • the styrene resin compositions in Table V-5 The system resin compositions 14 to 25 correspond to the resin composition (component (B)) of the intermediate layer b.
  • Resin 7 100 ⁇ ⁇ 0. 05 0. 05 D ⁇ 1 3.
  • Resin 8 100 ⁇ ⁇ 3 3 D-1 3.
  • Resin 9 100 ⁇ One 0. 3 0. 3 D ⁇ 1 0. 5
  • Resin 1 0 100 ⁇ ⁇ 0. 3 0. 3 D ⁇ 1 13.0
  • Resin 1 1 100 ⁇ ⁇ 0. 3 0. 3 D ⁇ 2 3.
  • Resin 1 2 100 ⁇ ⁇ 0. 3 0. 3 D ⁇ 4 3.
  • multilayer sheets of each constitution were prepared with a T-die type multilayer extruder having a feed block.
  • the multi-layer extruder is composed of one single-axis extruder with a main flight S65mm ⁇ full flight screw and one single 30mm ⁇ full-flight screw single-screw extruder for the surface layer.
  • a test extruder in which the fats were joined and multilayered at the feed block was used.
  • Each cylinder temperature in sheeting was operated and molded at 230 ° C.
  • Example V an example of a multilayer sheet with a high thermal deformation temperature
  • the haze is 99% or more and the total light transmittance is
  • the excess rate is 60% or more
  • the diffusion rate is 20% or more
  • the b value is less than 1
  • light resistance is excellent when the color difference is less than ⁇
  • dimensional stability is excellent when the water absorption warpage is 1 mm or less and the heat deformation is 1 mm or less.
  • Examples V ⁇ to ⁇ -10 and V-14 are particularly preferred examples that combine all these properties.
  • Examples ⁇ —11 to ⁇ —16, ⁇ —18 to ⁇ —23, ⁇ —26 and ⁇ —27 are other examples.
  • Examples V-14 to V-16 and V-24 are comparative examples.
  • Sheet layer structure b 1. 8 1. 8 and 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 Thickness (mm)
  • Type Resin 12 Resin 13 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Back layer
  • the measuring method of each physical property value is as follows.
  • L, a, b are hues before light resistance evaluation
  • L ′, a ′, b ′ are hues after light resistance evaluation (after 400 Hr irradiation).
  • Hygroscopicity The obtained light diffusion sheet was cut into dimensions of 300 mm x 300 mm, and the deformation after standing for 7 days in an atmosphere of 50 ° C and 80% humidity was measured on a scale. Hygroscopicity was good when the deformation was 1 mm or less.
  • Resin composition of styrene copolymer Dissolve styrene copolymer in heavy chloroform to prepare 2% solution, and use FT-NMR (FX-90Q model, manufactured by JEOL Ltd.) as measurement data. ) was used to measure c 13 and calculated from the peak areas of styrene and methyl methacrylate.
  • Antistatic property The surface resistivity value of the material conditioned at a temperature of 23 and a humidity of 50% 13 ⁇ 41 for 24 hours in accordance with JIS 1: 6911 was measured using a surface resistivity measuring machine (R50 3) manufactured by KAWAGUCHI. This value was used as a measure of antistatic properties.
  • Methacrylic acid content (%) [ ⁇ (A-B) X M ⁇ / (S X 1000)] X 100
  • the multilayer sheet of the present invention is a transmissive screen or a liquid crystal screen for a projection television or the like. It can be suitably used in a wide range of fields as a TV fullnel lens, a lenticular lens, a light diffusion plate, and the like.
  • Japanese patent application 2004-341624 filed on November 26, 2004, Japanese patent application 2005-109374 filed on April 6, 2005, Japan filed April 7, 2005 Patent application 2005-110800, Japanese patent application filed on April 11, 2005, Japanese patent application 2005-113155, and Japanese patent application 2005-127367 filed on April 26, 2005 , And the entire contents of the abstract are hereby incorporated by reference as a disclosure of the specification of the present invention.

Abstract

Disclosed is a multilayer sheet which is excellent in dimensional stability, light resistance and light diffusion. Specifically disclosed is a sheet having a multilayer structure wherein a front layer (a) and a back layer (c) are mainly composed of the component (A) below, and an intermediate layer (b) is mainly composed of the component (B) below. Component (A): A styrene resin composition containing 100 parts by mass of a styrene copolymer composed of 20-50% by mass of a styrene monomer unit and 80-50% by mass of a (meth)acrylate monomer unit, 1-10 parts by mass of an unmelted compound having a refractive index difference with the styrene copolymer of not more than 0.005 and an average particle diameter of 5-15 μm, 0.1-2 parts by mass of a hindered amine compound, and 0.1-2 parts by mass of a benzotriazole compound. Component (B): A resin composition containing 100 parts by mass of a styrene copolymer and 1-10 parts by mass of an unmelted compound having a refractive index difference with the styrene copolymer of 0.05-0.14 and an average particle diameter of 2-10 μm.

Description

明 細 書  Specification
多層シート及び光拡散シート  Multilayer sheet and light diffusion sheet
技術分野  Technical field
[0001] 本発明は、光拡散性、寸法安定性、耐光性に優れた多層シートに関する。特に、プ ロジェクシヨンテレビ等の画面の透過型スクリーンや液晶 TVの光拡散板として使用さ れる光拡散シートに関するものである。  The present invention relates to a multilayer sheet excellent in light diffusibility, dimensional stability, and light resistance. In particular, the present invention relates to a light diffusing sheet used as a light diffusing plate for a transmissive screen of a screen such as a projection television or a liquid crystal TV.
背景技術  Background art
[0002] 透過型スクリーン等のスクリーンレンズは、プロジェクシヨンテレビの画像を投影し、 目的とする画像を表示するものであり、広く用いられている。このスクリーンレンズは、 観察者が観察する際に明るぐ視野角が広いことが望まれるため、一般的にレンチキ ユラ一レンズやフレネルレンズ等のレンズ成形体を組み合わせて構成されて 、る。こ れらスクリーンレンズに使用されるレンズ成形体は、透明性、耐光性、耐傷付き性等 に優れ、かつ成形カ卩ェ性に優れたメタクリル樹脂が広く使用され、スクリーンレンズの 加工方法もプレス成形、押出し成形、キャスト成形や射出成形等により行われている  A screen lens such as a transmissive screen projects an image of a projection television and displays a target image, and is widely used. Since this screen lens is desired to have a bright and wide viewing angle when observed by an observer, the screen lens is generally configured by combining lens moldings such as a lenticular lens and a Fresnel lens. The lens moldings used for these screen lenses are widely used methacrylic resins with excellent transparency, light resistance, scratch resistance, etc., and excellent moldability. It is performed by molding, extrusion molding, cast molding, injection molding, etc.
[0003] このようなスクリーンレンズ用成形体の基材として使用されるメタクリル榭脂は、吸水 率が高いため、スクリーンレンズ用成形体の寸法変化が生じ、スクリーンの反りや浮き が生じ、光学特性が損なわれたり、枠体からのスクリーンレンズの脱落が生じるという 問題を有していた。また、スクリーンレンズの輸送時の温度や使用環境温度が高くな ると変形する問題も有して 、た。 [0003] Since the methacrylic resin used as the base material of such a molded body for screen lenses has a high water absorption rate, the dimensional change of the molded body for screen lenses occurs, causing warping and floating of the screen, resulting in optical characteristics. Or damage of the screen lens from the frame. In addition, there was a problem that the screen lens was deformed when the temperature during transportation and the ambient temperature were high.
[0004] これらの問題を解決するために、特許文献 1には、芳香族ビニル単量体、（メタ)ァク リル酸エステル系単量体、及び多官能性不飽和単量体の混合物にスチレンージェ ン系共重合体を溶存させて重合し、フレネルレンズを得る方法が開示されている。し 力しながらこの技術では、光拡散性の優れたスクリーンレンズ用成形体を得るには不 充分であった。  In order to solve these problems, Patent Document 1 describes a mixture of an aromatic vinyl monomer, a (meth) acrylic acid ester monomer, and a polyfunctional unsaturated monomer. A method for obtaining a Fresnel lens by dissolving and polymerizing a styrene-gen copolymer is disclosed. However, this technique is insufficient to obtain a molded article for a screen lens having an excellent light diffusibility.
また、液晶 TVの光拡散板の基材として使用されるメタクリル樹脂にっ 、ても吸水率 が高いため、光拡散板成形体の寸法変化が生じ、光拡散板の反りが生じ、光学特性 が損なわれる問題を有していた。また、映像やランプの光を長時間投射するとスクリ ーンレンズや光拡散板に使用される榭脂の劣化による変色が起こり、画像が変色す るという問題を有していた。 In addition, even the methacrylic resin used as the base material for the light diffusing plate of liquid crystal TVs has a high water absorption rate, which causes a change in the dimensions of the light diffusing plate molding, causing warping of the light diffusing plate, and optical characteristics Had the problem of being damaged. In addition, when the image or lamp light is projected for a long time, there is a problem that discoloration occurs due to deterioration of the resin used in the screen lens and the light diffusion plate, and the image is discolored.
[0005] 特許文献 1 :特開平 5— 341101号公報  Patent Document 1: Japanese Patent Laid-Open No. 5-341101
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] 本発明の課題は、寸法安定性、耐光性、及び光拡散性に優れた多層シート、特に 、スクリーンレンズ用成形体や光拡散板用成形体等の光拡散シートとして使用される 多層シートを提供することである。 [0006] An object of the present invention is to provide a multilayer sheet excellent in dimensional stability, light resistance and light diffusibility, particularly as a light diffusion sheet such as a molded article for a screen lens and a molded article for a light diffusion plate. Is to provide a sheet.
課題を解決するための手段  Means for solving the problem
[0007] 本発明者らは、前記課題を解決すべく鋭意検討をした結果、スチレン系単量体単 位を主成分とする特定のスチレン系共重合体と特定の未溶融化合物を含有する榭 脂組成物を多層シートの中間層とし、スチレン系単量体単位及び (メタ）アクリル酸ェ ステル系単量体単位を主成分とする共重合体と、特定の未溶融化合物と特定の耐 光剤とを含有するスチレン系榭脂組成物を表層、裏層とすることにより、寸法安定性 に優れ、耐光性に優れ、かつ光拡散性の優れた多層シートが得られることを見出し、 本発明に到達したものである。  [0007] As a result of intensive studies to solve the above problems, the inventors of the present invention contain a specific styrene copolymer mainly composed of a styrene monomer unit and a specific unmelted compound. Copolymers mainly composed of styrene monomer units and (meth) acrylic acid ester monomer units, specific unmelted compounds and specific light resistance The present invention has found that a multilayer sheet having excellent dimensional stability, excellent light resistance, and excellent light diffusibility can be obtained by using a styrene-based resin composition containing an agent as a surface layer and a back layer. Has reached
[0008] すなわち、本発明は以下の要旨を有する。  That is, the present invention has the following gist.
(1)多層構成のシートであって、表層 a及び裏層 cが下記 (A)成分を主成分とし、中 間層 bが下記 (B)成分を主成分とすることを特徴とする多層シート。  (1) A multilayer sheet characterized in that the surface layer a and the back layer c are composed mainly of the following component (A) and the intermediate layer b is composed mainly of the following component (B). .
(A)成分:スチレン系単量体単位 20〜50質量％及び (メタ）アクリル酸エステル系単 量体単位 80〜50質量0 /0力もなるスチレン系共重合体 100質量部と、該スチレン系 共重合体との屈折率差が 0. 005以内であり、平均粒子径が 5〜 15 mの未溶融化 合物を 1〜10質量部と、ヒンダードアミン系化合物を 0. 1〜2質量部と、ベンゾトリア ゾール系化合物を 0. 1〜2質量部と、を含有してなるスチレン系榭脂組成物。 Component (A): styrene-based monomer unit 20 to 50% by weight, and (meth) and styrene copolymer 100 parts by weight is also an acrylic acid ester-based monomer unit 80 to 50 weight 0/0 force, the styrene-based 1 to 10 parts by mass of an unmelted compound having a refractive index difference with the copolymer within 0.005 and an average particle diameter of 5 to 15 m, and 0.1 to 2 parts by mass of a hindered amine compound And a styrene-based resin composition comprising 0.1 to 2 parts by mass of a benzotriazole-based compound.
(B)成分:スチレン系共重合体 100質量部と、該スチレン系共重合体との屈折率差 が 0. 05〜0. 14であり、平均粒子径が 2〜10 /ζ πιの未溶融化合物 1〜10質量部と を、含有してなる榭脂組成物。 (2) (B)成分のスチレン系共重合体力 スチレン系単量体単位 50〜90質量0 /0、及 び (メタ）アクリル酸エステル系単量体単位 50〜10質量％からなるスチレン系共重合 体である、上記（1)に記載の多層シート。 Component (B): 100 parts by mass of a styrene copolymer and an unmelted material having a refractive index difference of 0.05 to 0.14 and an average particle diameter of 2 to 10 / ζ πι A resin composition comprising 1 to 10 parts by mass of a compound. (2) (B) styrene copolymer fitness styrenic monomer units of component 50 to 90 mass 0/0, 及Beauty (meth) styrenic consisting 50 to 10% by weight acrylic acid ester monomer units The multilayer sheet according to (1) above, which is a polymer.
(3) (B)成分のスチレン系共重合体力 スチレン系単量体単位 50〜90質量0 /0、（メ タ）アクリル酸エステル系単量体単位 50〜10質量％、及び共重合可能なビニル化合 物単量体単位 0〜： LO質量％からなるスチレン系共重合体である、上記（1)に記載の 多層シート。 (3) (B) styrene copolymer fitness styrenic monomer units of component 50 to 90 mass 0/0, (meth) acrylic acid ester monomer units 50-10 wt%, and copolymerizable Vinyl compound monomer unit 0-: The multilayer sheet according to the above (1), which is a styrene copolymer comprising LO mass%.
(4) (B)成分のスチレン系共重合体力 スチレン系単量体単位 80〜99質量0 /0とメタ クリル酸単量体単位 20〜1質量％及び共重合可能なビニル化合物単量体単位 0〜 10質量0 /0力もなるスチレン系共重合体 (II) 30〜70質量部と、スチレン系単量体単 位 20〜60質量％、（メタ）アクリル酸エステル系単量体単位 80〜40質量％力 なる スチレン系共重合体 (III) 70〜30質量部力もなる榭脂混合物である、上記（1)に記 載の多層シート。 (4) (B) component of the styrene copolymer fitness styrenic monomer units from 80 to 99 weight 0/0 and methacrylic acid monomer units 20 to 1% by weight and copolymerizable vinyl compound monomer unit 0 and 10 weight 0/0 force becomes styrene copolymer (II) 30 to 70 parts by weight of a styrene monomer unit of 20 to 60 wt%, (meth) acrylic acid ester monomer units 80 Styrene copolymer having a force of 40% by mass (III) The multilayer sheet according to (1) above, which is a resin mixture having a force of 70 to 30 parts by mass.
(5) (A)成分に含有される未溶融化合物は、その一部を表層 a及び裏層 cの表面に 突出させ、表層 a及び裏層 cの表面に凹凸を形成してなる、上記（1)〜(4)のいずれ かに記載の多層シート。  (5) A part of the unmelted compound contained in the component (A) protrudes from the surface of the surface layer a and the back layer c, and forms irregularities on the surface of the surface layer a and the back layer c. The multilayer sheet according to any one of 1) to (4).
(6)未溶融化合物は、 1気圧の雰囲気下で、 200°C以上の融点又は軟ィ匕点を有する 化合物である、上記（1)〜（5)の 、ずれかに記載の多層シート。  (6) The multilayer sheet according to any one of the above (1) to (5), wherein the unmelted compound is a compound having a melting point or soft spot of 200 ° C or higher under an atmosphere of 1 atm.
(7) (A)成分に含有される未溶融化合物が、単量体としてスチレン及びメタクリル酸メ チルを含む架橋共重合体である上記（1)〜（6)の 、ずれかに記載の多層シート。 (7) The multilayer according to any one of (1) to (6) above, wherein the unmelted compound contained in component (A) is a cross-linked copolymer containing styrene and methyl methacrylate as monomers. Sheet.
(8) (B)成分に含有される未溶融化合物が、単量体としてメタクリル酸メチルを含む 架橋重合体である上記（1)〜（7)の 、ずれかに記載の多層シート。 (8) The multilayer sheet according to any one of (1) to (7) above, wherein the unmelted compound contained in the component (B) is a crosslinked polymer containing methyl methacrylate as a monomer.
(9)ヒンダードアミン系化合物力 ビス（2, 2, 6, 6—テトラメチルー 4ーピペリジル）セ バケートである上記（1)〜（8)の 、ずれかに記載の多層シート。  (9) The multilayer sheet according to any one of the above (1) to (8), which is a hindered amine compound strength bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.
(10)ベンゾトリアゾール系化合物力 2- (2H ベンゾトリアゾール 2—ィル） 4 一（1, 1, 3, 3—テトラメチルブチル）フエノールである上記（1)〜（9)のいずれかに 記載の多層シート。  (10) Benzotriazole-based compound power 2- (2H benzotriazole 2-yl) 4 Described in any one of (1) to (9) above, which is one (1, 1, 3, 3-tetramethylbutyl) phenol Multilayer sheet.
(11) (A)成分と（B)成分の少なくとも一方に、ベンゾキサゾール系化合物を 0. 000 5〜0. 5質量部含有する、上記（1)〜（10)のいずれかに記載の多層シート。 (11) A benzoxazole compound is added to at least one of the component (A) and the component (B) The multilayer sheet according to any one of (1) to (10) above, containing 5 to 0.5 parts by mass.
(12)ベンゾキサゾール系化合物が、 2, 5—チォフェンジィル（5— tーブチルー 1, 3 一べンゾキサゾール)である、上記（11)に記載の多層シート。  (12) The multilayer sheet according to (11), wherein the benzoxazole-based compound is 2,5-thiophenzyl (5-tert-butyl-1,3 monobenzoxazole).
(13) (A)成分のスチレン系榭脂組成物力 さらに、スチレン系共重合体 100質量部 に対して、スチレン系共重合体との屈折率差が 0. 02以下のポリエーテルエステルァ ミドブロック共重合体を 7〜20質量部、ァ-オン系界面活性剤及び Z又は非アミンノ ユオン系界面活性剤を 0〜2質量部含有する、上記（1)〜（12)の 、ずれかに記載の 多層シート。  (13) Composition power of styrene-based resin of component (A) Furthermore, a polyether ester amide block having a refractive index difference of 0.02 or less with respect to 100 parts by mass of the styrene-based copolymer. 7 to 20 parts by mass of a copolymer, 0 to 2 parts by mass of a Zeon-based surfactant and Z or a non-amine surfactant, or any one of (1) to (12) above Multi-layer sheet.
(14)ポリエーテルエステルアミドブロック共重合体力 単量体として次の（F— A)、 (F -B)、及び (F— C)からなるポリエーテルエステルアミドブロック共重合体である上記 (13)に記載の多層シート。  (14) Polyether ester amide block copolymer strength The polyether ester amide block copolymer comprising the following (F—A), (F 2 -B), and (F—C) as monomers: ).
(F-A)：炭素数 6以上のアミノカルボン酸若しくはラタタム、又は炭素原子数 6以上 のジァミンとジカルボン酸の塩。  (F-A): An aminocarboxylic acid or ratatam having 6 or more carbon atoms, or a salt of diamine and dicarboxylic acid having 6 or more carbon atoms.
(F-B) :一般式 (化 1)〜（化 3)の少なくとも 1種のジオールィ匕合物。  (F-B): At least one diol compound of the general formulas (Chemical Formula 1) to (Chemical Formula 3).
[化 1] [Chemical 1]
(化 1 ) (Chemical 1)
Figure imgf000005_0001
Figure imgf000005_0001
(式中、 R1はエチレンォキシド基、 R2はエチレンォキシド基又はプロピレンォキシド 基、 Xはハロゲン、アルキル基 (炭素数： 1〜6)又はスルホン酸基若しくはその金属塩 、 Lは 0〜4の整数、 m及び nは 16以上の整数を表す。 ) (Wherein R1 is an ethylene oxide group, R2 is an ethylene oxide group or propylene oxide group, X is a halogen, an alkyl group (carbon number: 1 to 6) or a sulfonic acid group or a metal salt thereof, L is 0 to Integer of 4, m and n represent an integer of 16 or more.
[化 2] (化 2 )
Figure imgf000006_0001
[Chemical 2] (Chemical 2)
Figure imgf000006_0001
(式中、 Rlはエチレンォキシド基、 R2はエチレンォキシド基又はプロピレンォキシド 基、 Xはハロゲン、アルキル基 (炭素数： 1〜6)又はスルホン基若しくはその金属塩、 Yはアルキレン基 (炭素数： 1〜6)、アルキリデン基 (炭素数： 1〜6)、シクロアルキリ デン基 (炭素数： 7〜 17)、ァリールアルキリデン基 (炭素数： 7〜 17)、 0、 SO、 SO、(Wherein Rl is an ethylene oxide group, R2 is an ethylene oxide group or propylene oxide group, X is a halogen, an alkyl group (carbon number: 1 to 6) or a sulfone group or a metal salt thereof, Y is an alkylene group ( Carbon number: 1-6), alkylidene group (carbon number: 1-6), cycloalkylidene group (carbon number: 7-17), arylealkylidene group (carbon number: 7-17), 0, SO, SO,
22
CO、 S、 CF、 C (CF ) 又は NH、 Lは 0〜4の整数、 m及び nは 16以上の整数を表CO, S, CF, C (CF) or NH, L is an integer of 0 to 4, m and n are integers of 16 or more
2 3 2 2 3 2
す。） The )
[化 3] [Chemical 3]
(化 3 )
Figure imgf000006_0002
(Chemical 3)
Figure imgf000006_0002
(式中、 R1はエチレンォキシド基、 R2はエチレンォキシド基又はプロピレンォキシド 基、 m及び nは 16以上の整数を表す。 ) (In the formula, R1 represents an ethylene oxide group, R2 represents an ethylene oxide group or a propylene oxide group, and m and n represent an integer of 16 or more.)
(F-C)：炭素数 4〜20のジカルボン酸。 (F-C): a dicarboxylic acid having 4 to 20 carbon atoms.
(15) (A)成分中のァニオン系界面活性剤及び非アミンノニオン系界面活性剤の配 合比が、ァ-オン系界面活性剤 Z非アミンノ-オン系界面活性剤 =0. 5/99. 5〜 15Z85 (質量比）であることを特徴とする上記（13)又は（14)に記載の多層シート。 (15) The combination ratio of the anionic surfactant and the non-amine nonionic surfactant in the component (A) is the same as that of the cationic surfactant Z non-amine-non surfactant = 0.5 / 99. The multilayer sheet as described in (13) or (14) above, which is 5 to 15Z85 (mass ratio).
(16) (A)成分中のァ-オン系界面活性剤力 炭素数 10〜 14の有機スルホン酸金 属塩であり、非アミンノニオン系界面活性剤が、グリセリン脂肪酸エステルである上記 (13)〜（15)のいずれかに記載の多層シート。 (16) The cation surfactant power in component (A) is an organic sulfonic acid metal salt having 10 to 14 carbon atoms, and the non-amine nonionic surfactant is a glycerin fatty acid ester (13) -The multilayer sheet in any one of (15).
(17)表層 a及び裏層 cが 0. 005〜0. 5mm、中間層 bが l〜7mmである上記（1)〜 (16)のいずれかに記載の多層シート。 (17) The above (1) to (1), wherein the surface layer a and the back layer c are 0.005 to 0.5 mm, and the intermediate layer b is 1 to 7 mm. The multilayer sheet according to any one of (16).
(18)表層 a、中間層 b及び裏層 cが、押出し加工して得られた層である上記（1)〜（1 (18) The above layers (1) to (1), wherein the surface layer a, the intermediate layer b, and the back layer c are layers obtained by extrusion processing.
7)の 、ずれかに記載の多層シート。 The multilayer sheet according to 7).
(19)表層 a、中間層 b及び裏層 cが、同時に押出し加工して得られた層である上記（1 (19) Surface layer a, intermediate layer b, and back layer c are layers obtained by extrusion at the same time (1
8)に記載の多層シート。 The multilayer sheet as described in 8).
(20)上記（1)〜（19)のいずれかに記載の多層シートを用いた光拡散シート。  (20) A light diffusion sheet using the multilayer sheet according to any one of (1) to (19).
発明の効果  The invention's effect
[0009] 本発明により、従来にない光拡散性に優れた多層シートを工業上極めて有利に提 供することができる。本発明の多層シートは、光拡散性、寸法安定性、耐光性に優れ ているため、特にフレネルレンズやレンチキュラーレンズ、光拡散板等の光学的表示 用途に好適に用いることができる。  [0009] According to the present invention, an unprecedented multilayer sheet having excellent light diffusibility can be provided extremely advantageously in the industry. Since the multilayer sheet of the present invention is excellent in light diffusibility, dimensional stability and light resistance, it can be suitably used particularly for optical display applications such as Fresnel lenses, lenticular lenses and light diffusion plates.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0010] 以下、本発明を詳細に説明する。  Hereinafter, the present invention will be described in detail.
本発明に用いられるスチレン系単量体としては、例えばスチレン、 aーメチルスチレ ン、 p—メチルスチレン、 p—t—ブチルスチレン等が挙げられる力 好ましくはスチレ ンである。  Examples of the styrenic monomer used in the present invention include styrene, a-methylstyrene, p-methylstyrene, p-t-butylstyrene and the like, and preferably styrene.
[0011] 本発明における、（メタ）アクリル酸エステル系単量体としては、例えばメチルメタタリ レート、ェチルメタタリレート、メチルアタリレート、ェチルアタリレート、 n—ブチルアタリ レート、 2—メチルへキシルアタリレート、 2—ェチルへキシルアタリレート、ォクチルァ タリレート等が挙げられる。これらは、単独で使用するかあるいは 2種類以上を併用し てもよい。好ましくは、メチルメタタリレート、ェチルアタリレート、 n—ブチルアタリレート 又はこれらの混合物である。  [0011] Examples of the (meth) acrylic acid ester monomer in the present invention include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methyl hexyl acrylate. Rate, 2-ethylhexyl acrylate, octyl acrylate and the like. These may be used alone or in combination of two or more. Preferred is methyl metatalylate, ethyl acrylate, n-butyl acrylate, or a mixture thereof.
[0012] 本発明の表層 a、裏層 cに使用される (A)成分中のスチレン系共重合体は、スチレ ン系単量体単位 20〜50質量％、好ましくは 22〜48質量％、及び (メタ）アクリル酸 エステル系単量体単位 80〜50質量0 /0、好ましくは 78〜52質量0 /0である。スチレン 系単量体単位が 20質量％未満では、吸湿により多層シートが変形する場合があり、 50質量％を超えると、耐光性が低下し、光照射により多層シートが変色する場合が ある。 [0013] (B)成分中のスチレン系共重合体としては、スチレン系単量体単位を主成分とする 共重合体であり、なかでも、スチレン系単量体単位が 38〜90質量％、好ましくは 50 〜 90質量％及び (メタ）アクリル酸エステル系単量体単位が 62〜 10質量％、好ましく は 50〜10質量％カもなる共重合体 (I)が好適である。スチレン系単量体単位が 90 質量％を越えると耐光性が低下し、光照射により光拡散シートが変色する場合がある 。また 50質量％未満では吸湿により光拡散シートが変形する場合がある。 [0012] The styrene copolymer in the component (A) used for the surface layer a and the back layer c of the present invention is 20 to 50% by mass, preferably 22 to 48% by mass, of a styrene monomer unit. and (meth) acrylic acid ester monomer units 80-50 mass 0/0, preferably from 78 to 52 weight 0/0. If the styrene monomer unit is less than 20% by mass, the multilayer sheet may be deformed due to moisture absorption, and if it exceeds 50% by mass, the light resistance is lowered, and the multilayer sheet may be discolored by light irradiation. [0013] The styrene copolymer in the component (B) is a copolymer having a styrene monomer unit as a main component, and among them, the styrene monomer unit is 38 to 90% by mass, The copolymer (I) having 50 to 90% by mass and 62 to 10% by mass, preferably 50 to 10% by mass of (meth) acrylic acid ester monomer units is preferred. When the styrene monomer unit exceeds 90% by mass, the light resistance is lowered, and the light diffusion sheet may be discolored by light irradiation. If it is less than 50% by mass, the light diffusion sheet may be deformed by moisture absorption.
[0014] (B)成分中のスチレン系共重合体は、スチレン系単量体及び (メタ）アクリル酸エス テル単量体の他に、これらと共重合可能なビニル系単量体が共重合していてもよぐ その量はスチレン系単量体と (メタ）アクリル酸エステル単量体の合計量 100質量部 に対して、およそ 10質量部以下程度が好ましい。具体的には、スチレン系単量体単 位 50〜90質量％、好ましくは 52〜88質量％、（メタ）アクリル酸エステル系単量体単 位 50〜10質量％、好ましくは 48〜12質量％、及び共重合可能なビニル化合物単 量体単位 0〜10質量％、好ましくは 0〜8質量％である。  [0014] The styrene copolymer in component (B) is a copolymer of a styrene monomer and a (meth) acrylic acid ester monomer, as well as a vinyl monomer copolymerizable therewith. The amount is preferably about 10 parts by mass or less with respect to 100 parts by mass of the total amount of the styrene monomer and the (meth) acrylate monomer. Specifically, the styrene monomer unit is 50 to 90% by mass, preferably 52 to 88% by mass, the (meth) acrylic acid ester monomer unit is 50 to 10% by mass, preferably 48 to 12% by mass. %, And copolymerizable vinyl compound monomer units of 0 to 10% by mass, preferably 0 to 8% by mass.
この共重合可能なビュル系単量体としては、例えば、アクリロニトリルゃメタクリロ-ト リル等のシアン化ビュル単量体;メタクリル酸、アクリル酸、無水マレイン酸、マレイン 酸、ィタコン酸、無水ィタコン酸等の不飽和カルボン酸単量体；マレイミド、 N—メチル マレイミド、 N—フエ-ルマレイミド等のマレイミド単量体等が挙げられる。これらは、単 独で使用してもよぐ又は 2種類以上を併用してもよい。  Examples of this copolymerizable bur monomer include cyanide butyl monomers such as acrylonitrile methacrylo-tril; methacrylic acid, acrylic acid, maleic anhydride, maleic acid, itaconic acid, itaconic anhydride, etc. And unsaturated carboxylic acid monomers; maleimide monomers such as maleimide, N-methylmaleimide, N-phenolmaleimide, and the like. These may be used alone or in combination of two or more.
[0015] さらに、（B)成分中のスチレン系共重合体としては、前記以外に、スチレン系単量 体単位 80〜99質量％とメタクリル酸単量体単位 20〜1質量％及び共重合可能なビ ニル化合物単量体単位 0〜10質量％からなるスチレン系共重合体（11) 30〜70質量 部と、スチレン系単量体単位 20〜60質量％、（メタ）アクリル酸エステル系単量体単 位 80〜40質量％からなるスチレン系共重合体 (III) 70〜30質量部とから構成される 榭脂混合物（(Π) ·0Π)榭脂混合物という）を使用することもできる。 (II) ·0Π)榭脂組成 物中のスチレン系単量体総量が 90質量％を越えると耐光性が低下し、光照射により 多層シートが変色する場合がある。また 40質量部未満では吸湿により多層シートが 変形する場合がある。 (Π) ·0Π)榭脂混合物を使用すると、熱変形温度が高い多層シ ートを得ることが可能となる。 [0016] 本発明の (A)成分中の未溶融化合物は、その一部を表層 a及び裏層 cの表面に突 出させ、表層 a及び裏層 cの表面に凹凸を形成していることが好ましい。かかる凹凸に より、多層シート表面の流動性や離型性を向上させることができる。 [0015] Further, as the styrene copolymer in the component (B), in addition to the above, 80 to 99% by mass of a styrene monomer unit and 20 to 1% by mass of a methacrylic acid monomer unit can be copolymerized. 30 to 70 parts by mass of a styrene copolymer (11) consisting of 0 to 10% by mass of a vinyl compound monomer unit, 20 to 60% by mass of a styrene monomer unit, a (meth) acrylic acid ester unit A styrene-based copolymer composed of 80 to 40% by mass of a monomer unit (III) A resin mixture composed of 70 to 30 parts by mass (referred to as (Π) · 0Π) a resin mixture) can also be used. . (II) · 0Π) Resin composition If the total amount of styrene monomer in the composition exceeds 90% by mass, the light resistance is lowered and the multilayer sheet may be discolored by light irradiation. If it is less than 40 parts by mass, the multilayer sheet may be deformed by moisture absorption. (Ii) · 0Π) Using a resin mixture makes it possible to obtain a multilayer sheet having a high heat distortion temperature. [0016] The unmelted compound in the component (A) of the present invention partially protrudes from the surface of the surface layer a and the back layer c, and forms irregularities on the surface of the surface layer a and the back layer c. Is preferred. Such irregularities can improve the fluidity and releasability of the multilayer sheet surface.
(A)成分中の未溶融化合物は、（A)成分のスチレン系共重合体の融点では溶融し ない化合物であり、 101. 3kPa (l気圧）の雰囲気下で、好ましくは 200°C以上、特に 好ましくは 220〜320°Cの融点又は軟ィ匕点を有する化合物が好ましい。融点、軟ィ匕 点が 200°C未満では、スチレン系重合体との溶融混練時、又はスチレン系榭脂組成 物のシート化時や射出成形時に該化合物が溶融しやすぐ優れた光学特性を保持 することができな！/、場合がある。  The unmelted compound in component (A) is a compound that does not melt at the melting point of the styrene copolymer of component (A), and is preferably 200 ° C or higher in an atmosphere of 101.3 kPa (l atm). Particularly preferred are compounds having a melting point or soft spot of 220-320 ° C. When the melting point and softening point are less than 200 ° C, the compound melts immediately when melt kneaded with a styrene polymer, or when a styrene resin composition is formed into a sheet or during injection molding, so that excellent optical properties are obtained. I ca n’t hold it! / There may be cases.
[0017] (A)成分中の未溶融化合物は、（A)成分中のスチレン系共重合体との屈折率差が 0. 005以内、好ましくは 0. 003以内である。屈折率差が 0. 005を超えると、得られ る多層シートの全光線透過率及び光拡散性が低下する。また、（A)成分中の未溶融 化合物は、平均粒子径が 5〜 15 mであり、 7〜14 mが好ましい。平均粒子径が 5 μ m未満では、拡散率が大きくなり光拡散性が上昇し、 15 μ mを超えると全光線透 過率及び光拡散性が低下する。なお、未溶融化合物の平均粒子径は、コールター' マルチサイザ一（ベックマン'コールター社製）を用いて測定して得られる値である。  [0017] The unmelted compound in the component (A) has a refractive index difference with respect to the styrene copolymer in the component (A) within 0.005, preferably within 0.003. When the refractive index difference exceeds 0.005, the total light transmittance and light diffusibility of the resulting multilayer sheet are lowered. The unmelted compound in component (A) has an average particle size of 5 to 15 m, preferably 7 to 14 m. When the average particle size is less than 5 μm, the diffusivity increases and the light diffusivity increases, and when it exceeds 15 μm, the total light transmittance and the light diffusivity decrease. The average particle size of the unmelted compound is a value obtained by measurement using a Coulter Multisizer (manufactured by Beckman Coulter).
[0018] また、（A)成分中の未溶融化合物の含有量は、（A)成分中のスチレン系共重合体 100質量部に対して 1〜10質量部であり、好ましくは 2〜8質量部である。未溶融化 合物の含有量が 1質量部未満では、曇り度や拡散率が小さくなり光拡散性が低下し 、 10質量部を超えると全光線透過率及び拡散率が低下し、光拡散性が低下する傾 I口」にある。  [0018] The content of the unmelted compound in the component (A) is 1 to 10 parts by weight, preferably 2 to 8 parts by weight, based on 100 parts by weight of the styrene copolymer in the component (A). Part. When the content of the unmelted compound is less than 1 part by mass, the haze and diffusivity are reduced and the light diffusibility is reduced.When the content exceeds 10 parts by mass, the total light transmittance and the diffusivity are reduced, and the light diffusibility is reduced. "I'm going down".
(A)成分中の未溶融化合物の組成は、特に限定されるものではないが、単量体と してスチレンとメタクリル酸メチルを含む架橋共重合体が好ましい。  The composition of the unmelted compound in component (A) is not particularly limited, but a crosslinked copolymer containing styrene and methyl methacrylate as monomers is preferred.
[0019] (B)成分に用いられる未溶融化合物は、（B)成分のスチレン系共重合体の融点で は溶融しない化合物であり、 101. 3kPa (l気圧）の雰囲気下で、好ましくは 200°C以 上、特に好ましくは 220〜500°Cの融点又は軟ィ匕点を有する化合物が好ましい。融 点、軟ィ匕点が 200°C未満では、スチレン系共重合体との溶融混練時、又はスチレン 系榭脂組成物のシート化時に未溶融化合物が溶融しやすぐ優れた光学特性を保 持することができない場合がある。また、（B)成分中のスチレン系共重合体と未溶融 ィ匕合物との屈折率差は、 0. 05〜0. 14であり、好ましくは 0. 06〜0. 13である。屈 折率差が 0. 05未満では、得られる多層シートの曇り度や拡散率が小さくなり光拡散 性が低下し、 0. 14を超えると全光線透過率及び拡散率が低下する。 [0019] The unmelted compound used for component (B) is a compound that does not melt at the melting point of the styrene copolymer of component (B), and is preferably 200 200 kPa (l atm) in an atmosphere. A compound having a melting point or soft point of not lower than ° C and particularly preferably from 220 to 500 ° C is preferable. When the melting point and soft melting point are less than 200 ° C, the unmelted compound melts at the time of melt-kneading with a styrene copolymer or when a styrene-based resin composition is formed into a sheet, and excellent optical characteristics are maintained immediately. You may not be able to hold it. Further, the difference in refractive index between the styrene copolymer and the unmelted compound in component (B) is 0.05 to 0.14, preferably 0.06 to 0.13. If the refractive index difference is less than 0.05, the haze and diffusivity of the resulting multilayer sheet will be small and the light diffusivity will be reduced, and if it exceeds 0.14, the total light transmittance and diffusivity will be reduced.
[0020] (B)成分中の未溶融化合物の平均粒子径は 2〜： LO mであり、好ましくは 3〜8 mである。未溶融化合物の平均粒子径が 2 m未満では、得られる多層シートの曇り 度が小さくなるとともに光拡散性が低下し、 10 mを超えると全光線透過率及び拡散 率が低下する。なお、未溶融化合物の平均粒子径は、コールター'マルチサイザ一（ ベックマン'コールター社製）を用いて測定して得られる値である。  [0020] The average particle size of the unmelted compound in component (B) is 2 to: LO m, preferably 3 to 8 m. If the average particle size of the unmelted compound is less than 2 m, the resulting multilayer sheet has a low haze and light diffusibility, and if it exceeds 10 m, the total light transmittance and diffusivity are reduced. The average particle size of the unmelted compound is a value obtained by measurement using a Coulter Multisizer (Beckman Coalter).
(B)成分中の未溶融化合物の含有量は、（B)成分中のスチレン系共重合体 100質 量部に対して 1〜10質量部であり、好ましくは 2〜8質量部である。未溶融化合物の 含有量が 1質量部未満では、得られる多層シートの曇り度が小さくなるとともに光拡散 性が低下し、 10質量部を超えると全光線透過率及び拡散率が低下する。  The content of the unmelted compound in the component (B) is 1 to 10 parts by mass, preferably 2 to 8 parts by mass with respect to 100 parts by mass of the styrene copolymer in the component (B). When the content of the unmelted compound is less than 1 part by mass, the haze of the resulting multilayer sheet decreases and the light diffusibility decreases, and when it exceeds 10 parts by mass, the total light transmittance and the diffusivity decrease.
(B)成分中の未溶融化合物の組成は、特に限定されるものでは無いが、単量体と してメタクリル酸メチルを含む架橋共重合体が好ましい。例えば、ポリメチルメタクリレ ート架橋ビーズ (以下、「PMMA架橋ビーズ」という）等が挙げられる。  The composition of the unmelted compound in component (B) is not particularly limited, but a cross-linked copolymer containing methyl methacrylate as a monomer is preferred. Examples thereof include polymethyl methacrylate crosslinked beads (hereinafter referred to as “PMMA crosslinked beads”).
[0021] (A)成分中には、スチレン系共重合体 100質量部に対して、ヒンダードアミン系化 合物を 0. 1〜2質量部、好ましくは 0. 2〜1. 8質量部、及びべンゾトリアゾール系化 合物を 0. 1〜2質量部、好ましくは 0. 2〜1. 8質量部含有する必要がある。  [0021] In the component (A), 0.1 to 2 parts by mass of a hindered amine compound, preferably 0.2 to 1.8 parts by mass, and 100 parts by mass of a styrene copolymer. It is necessary to contain 0.1 to 2 parts by mass, preferably 0.2 to 1.8 parts by mass of the benzotriazole compound.
ヒンダードアミン系化合物及びべンゾトリアゾール系化合物力 それぞれ 0. 1質量 部未満では得られる多層シートの耐光性が低下し、 2質量部を超えると得られる多層 シートの黄色度が強くなる傾向があり、好ましくない。  The hindered amine compound and the benzotriazole compound strength are each less than 0.1 parts by mass, the light resistance of the resulting multilayer sheet is lowered, and when it exceeds 2 parts by mass, the yellowness of the obtained multilayer sheet tends to be strong, It is not preferable.
ヒンダードアミン系化合物は、ァミン系の光安定性向上剤であって、例えば、デカン 二酸ビス（2, 2, 6, 6—テトラメチルー 1 (ォクチルォキシ）ー4ーピベリジ-ル）エステ ル、 1, 1ージメチルェチルヒドロペルォキシド、ビス（1, 2, 2, 6, 6—ペンタメチルー 4—ピペリジル） [ [3, 5—ビス（1, 1—ジメチルェチル）— 4—ヒドリ（口）キシフヱ-ル] メチル]ブチルマロネート、ビス（1, 2, 2, 6, 6—ペンタメチルー 4ーピペリジル）セバ ケート、メチル 1, 2, 2, 6, 6—ペンタメチル一 4—ピベリジルセノ ケート、ビス（2, 2, 6, 6—テトラメチル一 4—ピペリジル)セバケート等がある。これらを単独で使用しても よぐまた 2種類以上を混合して使用してもよい。 Hindered amine compounds are amamine-based photostabilizers such as bis (2, 2, 6, 6-tetramethyl-1- (octyloxy) -4-piveridyl) ester, decanodioic acid, 1, 1- Dimethylethyl hydroperoxide, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl)-4-hydrido (methyl)] Methyl] butyl malonate, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, methyl 1, 2, 2, 6, 6-pentamethyl 4-piberidyl cenocate, bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate. These may be used alone or in combination of two or more.
また、ベンゾトリアゾール系化合物は、紫外線吸収剤であって、例えば、 2- (2H- ベンゾトリアゾール 2—ィル） p クレゾール、 2- (2H—ベンゾトリアゾール 2 —ィル） 4— 6 ビス（ 1 メチル 1 フエ-ルェチル）フエノール、 2— [5 クロ口 (2H)—ベンゾトリアゾール—2—ィル]—4—メチル ]—6— (t—ブチル）フエノール、 2, 4ージ—tーブチルー 6—（5 クロ口べンゾトリァゾールー 2 ィル）フエノール、 2 - (2H ベンゾトリアゾール—2—ィル） -4, 6 ジ— t—ペンチルフエノール等であ る。これらを単独で使用してもよぐまた 2種類以上を混合して使用してもよい。  Benzotriazole compounds are ultraviolet absorbers such as 2- (2H-benzotriazole 2-yl) p cresol, 2- (2H-benzotriazole 2-yl) 4-6 bis (1 Methyl 1-phenyl) phenol, 2- [5 Black mouth (2H) -benzotriazole-2-yl] —4-methyl] -6- (t-butyl) phenol, 2,4-di-tert-butyl-6 — (5 black-mouthed benzotriazole-2-yl) phenol, 2- (2H benzotriazole-2-yl) -4,6 di-t-pentylphenol. These may be used alone or in combination of two or more.
なお、表層 a、裏層 cに用いられるスチレン系榭脂組成物は、同一である必要はなく 、異なっていてもかまわない。  The styrenic resin composition used for the surface layer a and the back layer c does not need to be the same and may be different.
[0022] 本発明においては、（A)成分と (B)成分の少なくとも一方に、着色剤であっていわ ゆる蛍光増白剤であるベンゾキサゾール系化合物を好ましくは 0. 0005-0. 5質量 部、特に好ましくは 0. 005〜0. 05質量部含有することが望ましい。少なくとも一方の 成分中のベンゾキサゾール系化合物含有量が 0. 0005質量部以上であると、 0. 00 05質量部未満と比べて、得られるシートの黄色度が低減され、外観がより改善される とともに、結果として得られる多層シートの全光線透過率の値が上がる傾向があり好 ましい。 0. 5質量部以下では、 0. 5質量部を超える場合と比較して、得られる多層シ 一トの耐光性がより向上するため、好ましい。 In the present invention, at least one of component (A) and component (B) is preferably a benzoxazole-based compound that is a so-called fluorescent whitening agent as a colorant. It is desirable to contain parts by mass, particularly preferably 0.005 to 0.05 parts by mass. When the content of the benzoxazole-based compound in at least one of the components is 0.0005 part by mass or more, the yellowness of the obtained sheet is reduced and the appearance is further improved as compared with less than 0.005 part by mass. In addition, the total light transmittance of the resulting multilayer sheet tends to increase, which is preferable. The amount of 0.5 parts by mass or less is preferable because the light resistance of the resulting multilayer sheet is further improved as compared with the case of exceeding 0.5 parts by mass.
ベンゾキサゾール系化合物としては、例えば、 2, 5 チォフェンジィル（5 tーブ チルー 1, 3 べンゾキサゾール、 2, 5 チォフェンジィル（5— t—ブチルー 1, 3— ベンゾキサゾール 10%とジシクロへキシルフタレート 90%の混合物、 4, 4 '—ビス（ベ ンゾォキサゾ一ルー 2—ィル)スチルベン等が挙げられ、これらを単独で用いてもよく 、又はこれらを併用してもよい。  Examples of benzoxazole compounds include 2,5 thiopheneyl (5 tert-butyl-1,3 benzoxazole, 2,5 thiopheneyl (5-t-butyl-1,3-benzoxazole 10% and dicyclohexyl phthalate). 90% mixture, 4,4′-bis (benzoxazol 2-yl) stilbene and the like may be mentioned, and these may be used alone or in combination.
[0023] 本発明の多層シートに耐傷付き性及び防塵のために帯電防止性能を付与したい 場合は、（A)成分中に、スチレン系共重合体との屈折率差が 0. 02以下のポリエー テルエステルアミドブロック共重合体を、スチレン系共重合体 100質量部に対して 7 〜20質量部、ァ-オン系界面活性剤及び Z又は非アミンノ-オン系界面活性剤を 0 〜2質量部含有することが好ま ヽ。 [0023] In the case where it is desired to impart antistatic performance to the multilayer sheet of the present invention for scratch resistance and dust prevention, the component (A) has a refractive index difference of 0.02 or less with respect to the styrene copolymer. Tellester amide block copolymer, 7 to 20 parts by mass with respect to 100 parts by mass of styrene-based copolymer, 0-on surfactant and Z or non-amine non-one surfactant. It is preferable to contain ~ 2 parts by mass.
ポリエーテルエステルアミドブロック共重合体の含有量が 7質量部以上であると、 7 質量部未満の場合と比べて、得られる多層シートの耐傷付き性がより向上し、充分な 帯電防止効果が得られるため、好ましい。ポリエーテルエステルアミドブロック共重合 体の含有量が 20質量部以下であると、 20質量部を超える場合と比較して、得られる 多層シートの黄色度がさらに低減されるため好ましい。また屈折率差が 0. 02以下で あれば、 0. 02を超える場合と比べて、光透過性が向上するため好ましい。  When the content of the polyetheresteramide block copolymer is 7 parts by mass or more, the scratch resistance of the resulting multilayer sheet is further improved compared to the case of less than 7 parts by mass, and a sufficient antistatic effect is obtained. Therefore, it is preferable. When the content of the polyether ester amide block copolymer is 20 parts by mass or less, the yellowness of the resulting multilayer sheet is further reduced as compared with the case where the content exceeds 20 parts by mass. Further, it is preferable that the difference in refractive index is 0.02 or less because the light transmittance is improved as compared with the case where the refractive index difference exceeds 0.02.
[0024] ポリエーテルエステルアミドブロック共重合体中の単量体 (F— A)は、炭素原子数 6 以上のアミノカルボン酸若しくはラタタム、又は炭素原子数 6以上のジァミンとジカル ボン酸の塩である。炭素原子数 6以上のアミノカルボン酸としては、例えば、 ω アミ ノカブロル酸、 ω—ァミノ力プリル酸、 ω—アミノエナント酸、 1, 2アミノドデカン酸が挙 げられ、ラタタムとしては、例えば、力プロラタタム、ェナントラクタム、力プリルラタタム が挙げられる。炭素原子数 6以上のジァミンとジカルボン酸の塩としては、例えば、へ キサメチレンジァミン アジピン酸塩、へキサメチレンジァミンーセバシン酸塩、へキ サメチレンジァミン一イソフタル酸塩等が挙げられる。単量体 (F— Α)としては、力プロ ラタタム、 1, 2アミノドデカン酸あるいはへキサメチレンジァミン アジピン酸塩が特に 好ましい。 [0024] The monomer (FA) in the polyetheresteramide block copolymer is an aminocarboxylic acid or ratatam having 6 or more carbon atoms, or a salt of diamine and dicarboxylic acid having 6 or more carbon atoms. is there. Examples of aminocarboxylic acids having 6 or more carbon atoms include ω-aminocabrolic acid, ω -amino force prillic acid, ω- aminoenanthic acid, and 1,2-aminododecanoic acid. Prolatatam, Enantolactam, and Power Prillatatum. Examples of the salt of diamine and dicarboxylic acid having 6 or more carbon atoms include hexamethylene diamine adipate, hexamethylene diamine-sebacinate, hexamethylene diamine monoisophthalate, etc. Is mentioned. As the monomer (F—Α), force prolatatam, 1,2 aminododecanoic acid or hexamethylenediamine adipate is particularly preferable.
[0025] ポリエーテルエステルアミドブロック共重合体中の単量体（F— Β)は、ジオール化合 物であって、一般式 (化 1)〜(化 3)で示される。  [0025] The monomer (F-Β) in the polyetheresteramide block copolymer is a diol compound represented by general formulas (Chemical Formula 1) to (Chemical Formula 3).
[化 4]  [Chemical 4]
(化 1 ) (Chemical 1)
Figure imgf000012_0001
Figure imgf000012_0001
(式中、 R1はエチレンォキシド基、 R2はエチレンォキシド基又はプロピレンォキシド 基、 Xはハロゲン、アルキル基 (炭素数： 1〜6)又はスルホン酸基若しくはその金属塩 、 Lは 0〜4の整数、 m及び nは 16以上の整数を表す。） (Wherein R1 is an ethylene oxide group, R2 is an ethylene oxide group or propylene oxide group, X is a halogen, an alkyl group (carbon number: 1 to 6), a sulfonic acid group or a metal salt thereof. , L represents an integer of 0 to 4, and m and n represent an integer of 16 or more. )
[0026] [化 5] [0026] [Chemical 5]
(化 2 ) (Chemical 2)
H -(R
Figure imgf000013_0001
H-(R
Figure imgf000013_0001
(式中、 R1はエチレンォキシド基、 R2はエチレンォキシド基又はプロピレンォキシド 基、 Xはハロゲン、アルキル基 (炭素数： 1〜6)又はスルホン基若しくはその金属塩、 Yはアルキレン基 (炭素数： 1〜6)、アルキリデン基 (炭素数： 1〜6)、シクロアルキリ デン基 (炭素数： 7〜 17)、ァリールアルキリデン基 (炭素数： 7〜 17)、 0、 SO、 SO、(Wherein R1 is an ethylene oxide group, R2 is an ethylene oxide group or propylene oxide group, X is a halogen, an alkyl group (carbon number: 1 to 6) or a sulfone group or a metal salt thereof, Y is an alkylene group ( Carbon number: 1-6), alkylidene group (carbon number: 1-6), cycloalkylidene group (carbon number: 7-17), arylealkylidene group (carbon number: 7-17), 0, SO, SO,
22
CO、 S、 CF、 C (CF ) 又は NH、 Lは 0〜4の整数、 m及び nは 16以上の整数を表 す。） CO, S, CF, C (CF) or NH, L represents an integer of 0 to 4, and m and n represent an integer of 16 or more. )
[0027] [ィ匕 6] [0027] [6]
(化 3 ) (Chemical 3)
Figure imgf000013_0002
Figure imgf000013_0002
(式中、 R1はエチレンォキシド基、 R2はエチレンォキシド基又はプロピレンォキシド 基、 m及び nは 16以上の整数を表す。 ) (In the formula, R1 represents an ethylene oxide group, R2 represents an ethylene oxide group or a propylene oxide group, and m and n represent an integer of 16 or more.)
[0028] これらのジオール化合物としては、例えば、ビスフエノール Aのエチレンォキシド及 び Z又はプロピオンォキシド付カ卩物、 2, 2—ビス（4, 4'ーヒドロキシシクロへキシル） [0028] Examples of these diol compounds include ethylene oxide of bisphenol A and Z or propionoxide-containing products, 2,2-bis (4,4'-hydroxycyclohexyl).
4, 4，ーヒドロキシフエ-ルー 3, 3，ースルホン酸ナトリウム）プロパンのエチレンォキ シド及び Z又はプロピレンォキシド付カ卩物、ビスフエノール sのエチレンォキシド及び4, 4, Hydroxyphenol 3, 3, Sodium sulfonate) Propane ethylene oxide Carbide with Sid and Z or Propylene Oxide, Ethylene Oxide of Bisphenol and
Z又はプロピレンォキシド付カ卩物、 4, 4' （ヒドロキシ）ビフエ-ルのエチレンォキシ ド及び Z又はプロピレンォキシド付カ卩物、ビス（4ーヒドロキシフエ-ル)スルフイドのェ チレンォキシド及び Z又はプロピレンォキシド付カ卩物、ビス（4ーヒドロキシフエ-ル)メ タンのエチレンォキシド及び Z又はプロピレンォキシド付カ卩物、ビス（4ーヒドロキシフ Carboxy with Z or propylene oxide, Ethylene oxide with 4, 4 '(hydroxy) biphenyl and Carboxy with Z or propylene oxide, Ethylene oxide with bis (4-hydroxyphenol) sulfide and Z or propylene oxide Carbide with oxide, Bis (4-hydroxyphenol) methane ethylene oxide and Z or Propylene oxide, Bis (4-hydroxyphenol)
、 1, 1 ビス（4ーヒドロキシフエ-ル）シタリへキサンのエチレンォキシド及び/又は プロピレンォキシド付カ卩物、 1, 4ージヒドロキシシクロへキサンのエチレンォキシド及 び Z又はプロピレンォキシド付加物、ハイドロキノンのエチレンォキシド及び Z又はプ ロピレンォキシド付カ卩物、ジヒドロキシナフタレンのエチレンォキシド及び Z又はプロ ピレンォキシド付加物が挙げられ、あるいはこれらのブロック共重合体でもよ!/、。 1, 1 Bis (4-hydroxyphenol) Citaryhexane Ethylene Oxide and / or Propylene Oxide Carbide, 1,4-Dihydroxycyclohexane Ethylene Oxide and Z or Propylene Oxide Adduct And hydroquinone ethylene oxide and Z or propylene oxide adduct, dihydroxynaphthalene ethylene oxide and Z or propylene oxide adduct, or a block copolymer thereof.
[0029] 好まし!/、単量体（F— B)のジオール化合物は、ハイドロキノンのエチレンォキシド付 加物や、ビスフエノール Aのエチレンォキシド付カ卩物、ビスフエノーノレ Sのエチレンォ キシド付力!]物、ジヒドロキシナフタレンのエチレンォキシド付力!]物であり、あるいはその ブロック重合体でもよい。特に好ましいのは、ビスフエノール Aのエチレンォキシド付 加物である。 [0029] Preferable! / The monomer (F-B) diol compound includes hydroquinone ethylene oxide adducts, bisphenol A ethylene oxide adducts, and bisphenolore S ethylene oxide adducts. !], Dihydroxynaphthalene with ethylene oxide!] Or a block polymer thereof. Particularly preferred is an ethylene oxide adduct of bisphenol A.
[0030] ポリエーテルエステルアミドブロック共重合体中の単量体（F— C)は、ジカルボン酸 であって、炭素数 4〜20のジカルボン酸が好ましぐ例えば、テレフタル酸、イソフタ ル酸、フタル酸、ナフタレン一 2, 6 ジカルボン酸、ナフタレン一 2, 7 ジカルボン 酸等の芳香族ジカルボン酸、 1, 4ーシクロへキサンジカルボン酸、 1, 2 シクロへキ サンジカルボン酸等の脂環族ジカルボン酸及びコハク酸、シユウ酸、アジピン酸、セ バシン酸などが挙げられる。  [0030] The monomer (F—C) in the polyetheresteramide block copolymer is a dicarboxylic acid, and a dicarboxylic acid having 4 to 20 carbon atoms is preferred. For example, terephthalic acid, isophthalic acid, Aromatic dicarboxylic acids such as phthalic acid, naphthalene-1,6 dicarboxylic acid, naphthalene-1,2,7 dicarboxylic acid, etc., 1,4-cyclohexanedicarboxylic acid, 1,2 cyclohexane dicarboxylic acid, etc. And succinic acid, oxalic acid, adipic acid, sebacic acid and the like.
(F—A)、（F— B)及び (F— C)の使用割合は、（F—A)が 25〜85質量部、（F— B )が 15〜70質量部、（F— C)が 5〜60質量部の割合が好ましい。  (F—A), (F—B) and (F—C) are used in proportions of (F—A) of 25 to 85 parts by mass, (F—B) of 15 to 70 parts by mass, (F—C). ) Is preferably 5 to 60 parts by mass.
[0031] ポリエーテルエステルアミドブロック共重合体の重合方法は、例えば (F— A)である アミノカルボン酸又はラタタムと (F— C)であるジカルボン酸を反応させて、両末端が カルボン酸基のポリアミドプレポリマーをつくり、これに（F— B)ジオール化合物を真 空下に反応させる方法や前記 (F— A)、 （F— B)及び (F— C)の各化合物を反応槽 に仕込み、高温で反応させ、ジカルボン酸末端のポリアミドプレボリマーを生成させ、 その後常圧又は減圧下で重合を進める方法がある。 [0031] The method of polymerizing the polyetheresteramide block copolymer is, for example, by reacting an aminocarboxylic acid or ratatam (F—A) with a dicarboxylic acid (F—C), and both ends are carboxylic acid groups. A polyamide prepolymer of (F—B) diol compound The reaction in the air and the compounds (F-A), (F-B) and (F-C) are charged into a reaction vessel and reacted at a high temperature to produce a dicarboxylic acid-terminated polyamide prepolymer. Thereafter, there is a method of proceeding polymerization under normal pressure or reduced pressure.
[0032] 上述の通り、（A)成分中には、スチレン系共重合体 100質量部に対してァ-オン系 界面活性剤及び Z又は非アミンノ-オン系界面活性剤を 0〜2質量部含有すること が望ま 、。ァ-オン系界面活性剤及び Z又は非アミンノ-オン系界面活性剤が 2 質量部以下であれば、 2質量部より多い場合と比べ、得られる多層シートの黄色味が より低減されるため好ましい。また、一級ァミン、二級ァミン、三級ァミンの各構造を有 するアミンノ-オン系界面活性剤が含有されると、（A)成分が黄色の色相を呈する。  [0032] As described above, in component (A), 0 to 2 parts by mass of an ionic surfactant and Z or a non-amine-based surfactant are added to 100 parts by mass of the styrene copolymer. It is desirable to contain it. It is preferable that the amount of the cation-based surfactant and the Z or non-amine-one-based surfactant is 2 parts by mass or less because the yellowishness of the resulting multilayer sheet is further reduced as compared with the case of more than 2 parts by mass. . In addition, when an amine-on-type surfactant having each of primary, secondary and tertiary amine structures is contained, the component (A) exhibits a yellow hue.
[0033] ァ-オン系界面活性剤としては、有機スルホン酸金属塩が挙げられる。具体的には 、例えば、アルキルスルホン酸ナトリウム、アルキルスルホン酸リチウム、アルキルベン ゼンスルホン酸ナトリウム、アルキルベンゼンスルホン酸リチウム等がある。この中でも アルキルスルホン酸ナトリウムが好適に使用される。更に好ましくは、炭素数 10〜14 のアルキルスルホン酸ナトリウムである。これらは単独で使用してもよぐまた 2種類以 上を併用してもよい。  [0033] As the ionic surfactant, an organic sulfonic acid metal salt may be mentioned. Specific examples include sodium alkyl sulfonate, lithium alkyl sulfonate, sodium alkylbenzene sulfonate, and lithium alkylbenzene sulfonate. Among these, sodium alkyl sulfonate is preferably used. More preferred is sodium alkyl sulfonate having 10 to 14 carbon atoms. These may be used alone or in combination of two or more.
[0034] 非アミンノニオン系界面活'性剤としては、例えば、ポリオキシエチレンァノレキルエー テル、ポリオキシエチレン脂肪酸エステル、グリセリン脂肪酸エステルが挙げられる。 その中でもグリセリン脂肪酸エステルが好適に用いられる。これらは単独で使用して もよぐまた 2種類以上を併用してもよい。  [0034] Examples of the non-amine nonionic surfactant include polyoxyethylene anolalkyl ether, polyoxyethylene fatty acid ester, and glycerin fatty acid ester. Of these, glycerin fatty acid esters are preferably used. These may be used alone or in combination of two or more.
[0035] 以上に示したァニオン系界面活性剤と非アミンノニオン系界面活性剤を併用する 場合は、ァ-オン系界面活性剤 Z非アミンノ-オン系界面活性剤 =0. 5/99. 5〜 15Z85 (質量比)の割合で用いると、より優れた帯電防止性能が得られる。  [0035] When the anionic surfactant and the non-amine nonionic surfactant shown above are used in combination, the cationic surfactant Z non-amine non-ionic surfactant = 0.5 / 99. 5 When used at a ratio of ˜15Z85 (mass ratio), better antistatic performance can be obtained.
[0036] (A)成分中のスチレン系共重合体及び（B)成分中のスチレン系共重合体の製造 方法に特に制限はないが、塊状重合法、懸濁重合法、溶液重合法、乳化重合法を 好適に採用できる。  [0036] The production method of the styrene copolymer in the component (A) and the styrene copolymer in the component (B) is not particularly limited, but is a bulk polymerization method, suspension polymerization method, solution polymerization method, emulsification A polymerization method can be suitably employed.
[0037] (A)成分及び (B)成分の各素材の配合方法に特に制限はなぐそれぞれのスチレ ン系共重合体の重合前、重合途中、重合直後に配合する方法、分離したスチレン系 共重合体と溶融混合により配合する方法等が挙げられる。 [0038] それぞれのスチレン系共重合体をペレツトイ匕した後に、それと未溶融化合物を溶融 混合する場合も、その混合方法に特に制限はなぐ例えば、ヘンシェルミキサーゃタ ンブラーミキサー等の公知の混合装置にて予備混合した後、単軸押出機又は二軸 押出機等の押出機を用いて溶融混練を行うことにより、均一に混合することができる。 また、スチレン系共重合体に未溶融化合物を高濃度に混合した高濃度混合物を作 製しておき、シートの製造時に、この高濃度混合物とスチレン系共重合体をドライブレ ンドし、未溶融化合物の含有量が規定の濃度となるようにしたものを原料に用いても よい。 [0037] There are no particular restrictions on the blending method of each material of component (A) and component (B), a method of blending before, during or immediately after the polymerization of each styrene copolymer, and a separated styrene copolymer. Examples include a method of blending with a polymer by melt mixing. [0038] Even when each styrene copolymer is pelletized and then melted and mixed with an unmelted compound, the mixing method is not particularly limited. For example, a known mixing apparatus such as a Henschel mixer or a tumbler mixer may be used. After the preliminary mixing, the mixture can be uniformly mixed by melt kneading using an extruder such as a single screw extruder or a twin screw extruder. In addition, a high-concentration mixture in which an unmelted compound is mixed at a high concentration with a styrene-based copolymer is prepared, and when the sheet is manufactured, the high-concentration mixture and the styrene-based copolymer are driven and unmelted. A material in which the content of the compound becomes a specified concentration may be used as a raw material.
[0039] (A)成分中のスチレン系共重合体及び（B)成分中のスチレン系共重合体には、必 要に応じて添加剤を配合することができる。例えば、流動性や離型性を向上させるた めに、可塑剤、滑剤、シリコンオイル等を配合することができる。また、多層シートの防 塵のために帯電防止剤を配合することもできる。さらに、耐熱性や熱安定性を付与す るため、熱安定剤を配合することができる。その他、着色剤を配合することもできる。  [0039] Additives may be blended with the styrene copolymer in the component (A) and the styrene copolymer in the component (B), if necessary. For example, plasticizers, lubricants, silicone oils and the like can be blended to improve fluidity and releasability. In addition, an antistatic agent can be added to prevent dust from the multilayer sheet. Furthermore, a heat stabilizer can be blended in order to impart heat resistance and heat stability. In addition, a coloring agent can also be mix | blended.
[0040] 本発明のシートは多層構成を有しており、各層の厚みは、（A)成分力もなる表層 a 及び裏層 c力^). 005〜0. 5mm、好ましくは 0. 01〜0. 4mmであり、（B)成分力らな る中間層 bが、 l〜7mm、好ましくは 1. 2〜6. 8mmである。表層 a及び裏層 cが 0. 0 05mm未満では、得られる多層シートが光照射により変色する場合があり、 0. 5mm を超えると吸湿により変形する場合がある。また、中間層 bが lmm未満や 7mmを超 えると、優れた光学特性 (光拡散性)が得られない場合がある。  [0040] The sheet of the present invention has a multilayer structure, and the thickness of each layer is (A) the surface layer a and the back layer c force which also has component force ^). 005 to 0.5 mm, preferably 0.01 to 0 The intermediate layer b, which is 4 mm and (B) component strength, is 1 to 7 mm, preferably 1.2 to 6.8 mm. If the surface layer a and the back layer c are less than 0.05 mm, the resulting multilayer sheet may be discolored by light irradiation, and if it exceeds 0.5 mm, it may be deformed by moisture absorption. If the intermediate layer b is less than 1 mm or more than 7 mm, excellent optical properties (light diffusibility) may not be obtained.
尚、表層 a及び裏層 cの厚みは同一である必要はなぐ異なっても力まわない。  It should be noted that the thicknesses of the surface layer a and the back layer c need not be the same and can be different.
[0041] 多層シートは、表層 a、中間層 b及び裏層 cを別々に押出し加工して得られたシート を熱融着等により貼り合せてもよぐまたフィードブロックを用いた Tダイやマルチマ- ホールドダイを用いて同時に押出し加工してもよい。後者による手法の方が、経済的 に有利である他、貼り合せ時のシート表面への傷や異物の混入等を防ぎやす 、と ヽ う品質面にぉ 、ても有利である。  [0041] The multilayer sheet may be a sheet obtained by extruding the surface layer a, the intermediate layer b, and the back layer c separately by heat fusion or the like. -You may extrude at the same time using a hold die. The latter method is not only economically advantageous, but also advantageous in terms of quality, which is easy to prevent damage to the surface of the sheet and mixing of foreign matters during lamination.
実施例  Example
[0042] 以下、実施例によって本発明を具体的に説明する力 本発明はこれらの実施例に よって限定されるものではない。尚、実施例中の部、％はいずれも質量基準である。 [0043] [例 I] [0042] Hereinafter, the power to specifically describe the present invention by way of examples. The present invention is not limited to these examples. In the examples, parts and% are based on mass. [0043] [Example I]
スチレン系共重合体 A— 1〜Α—4の製造  Production of styrenic copolymers A— 1 to IV-4
容積約 5リットルの第 1完全混合槽と約 15リットルの第 2完全混合槽を直列に接続し 、さらに予熱器を付した第 1脱揮槽と第 2脱揮槽を 2基直列に接続して構成した。 スチレン 40%、メチルメタタリレート（以下、「MMA」という。）60%で構成する単量 体溶液 100部に対し、ェチルベンゼン 15部、 t ブチルパーォキシイソプロピルモノ カーボネート 0. 01部、 2, 4 ジフエ-ルー 4—メチル—1—ペンテン 0. 2部を混合し 原料溶液とした。  Connect a first complete mixing tank with a volume of about 5 liters and a second complete mixing tank with a capacity of about 15 liters in series, and further connect two first and second devolatilization tanks with a preheater in series. Configured. To 100 parts of a monomer solution composed of 40% styrene and 60% methyl methacrylate (hereinafter referred to as “MMA”), 15 parts ethylbenzene, 0.01 parts t-butylperoxyisopropyl monocarbonate, 2, 4 Diphenol-ru 4-Methyl-1-pentene 0.2 part was mixed to make a raw material solution.
この原料溶液を毎時 6. Okgで 135°Cに制御した第 1完全混合槽に供給した。第 1 完全混合槽出口での転ィ匕率は 28%であった。次に第 1完全混合槽より連続的に抜 き出し、 135°Cに制御した第 2完全混合槽に供給した。第 2完全混合槽出口での転 化率は 63%であった。次に第 2完全混合槽より連続的に抜き出し、予熱器で加温し 、 67kPa、 160°Cに制御した第 1脱揮槽に導入した。さらに第 1脱揮槽より連続的に 抜き出し、予熱器で加温し、 1. 3kPa、 230°Cに制御した第 2脱揮槽に導入し単量体 を除去した。これをストランド状に押出し切断することによりペレット形状のスチレン系 共重合体 A— 1を得た。  This raw material solution was supplied to the first complete mixing tank controlled at 135 ° C at 6. Okg per hour. The turnover rate at the outlet of the first complete mixing tank was 28%. Next, it was continuously extracted from the first complete mixing tank and supplied to the second complete mixing tank controlled at 135 ° C. The conversion rate at the outlet of the second complete mixing tank was 63%. Next, it was continuously extracted from the second complete mixing tank, heated by a preheater, and introduced into the first devolatilization tank controlled at 67 kPa and 160 ° C. Furthermore, it was continuously extracted from the first devolatilization tank, heated with a preheater, and introduced into the second devolatilization tank controlled at 1.3 kPa and 230 ° C to remove the monomer. This was extruded and cut into strands to obtain pellet-shaped styrenic copolymer A-1.
[0044] スチレン 80%、 MMA20%で構成する単量体溶液を用いた以外は、スチレン系共 重合体 A— 1と同様に実施しスチレン系共重合体 A— 2を得た。  [0044] A styrene copolymer A-2 was obtained in the same manner as the styrene copolymer A-1, except that a monomer solution composed of 80% styrene and 20% MMA was used.
スチレン 10%、 MMA90%で構成する単量体溶液を用いた以外は、スチレン系共 重合体 A—1と同様に実施しスチレン系共重合体 A— 3を得た。  Styrene copolymer A-3 was obtained in the same manner as styrene copolymer A-1, except that a monomer solution composed of 10% styrene and 90% MMA was used.
スチレン 95%、 MMA5%で構成する単量体溶液を用いた以外は、スチレン系共 重合体 A— 1と同様に実施しスチレン系共重合体 A— 4を得た。  Styrene copolymer A-4 was obtained in the same manner as styrene copolymer A-1, except that a monomer solution composed of 95% styrene and 5% MMA was used.
得られたスチレン系共重合体の組成及び屈折率を表 I 1に示す。  The composition and refractive index of the resulting styrene copolymer are shown in Table I1.
[0045] [表 1] 表 I — 1 [0045] [Table 1] Table I — 1
Figure imgf000018_0001
Figure imgf000018_0001
[0046] ポリオルガノシロキサン架橋ビーズ（B) [0046] Polyorganosiloxane cross-linked beads (B)
ポリオルガノシロキサン架橋ビーズとして、東芝シリコーン社製トスパール 2000Bを 使用した。平均粒子径、屈折率を表 1— 2に示す。  Toshiba Silicone Tospearl 2000B was used as the polyorganosiloxane crosslinked beads. The average particle diameter and refractive index are shown in Table 1-2.
[0047] MMA— nBA共重合架橋ビーズ（C)  [0047] MMA—nBA copolymer crosslinked beads (C)
攪拌機付きオートクレープにメタクリル酸メチル 20部、 n—ブチルアタリレート 80部、 架橋剤としてジビュルベンゼン 5部、重合開始剤として、ベンゾィルパーオキサイド 0 . 2部、懸濁安定剤としてドデシルベンゼンスルホン酸ナトリウム 0. 001部及び第三リ ン酸カルシウム 0. 5部、純水 200部を仕込み、温度 95°Cにて 6時間、さらに温度 130 °Cにて 2時間重合した。反応終了後、洗浄、脱水、乾燥を行い、ビーズ状の架橋ビー ズ (C)を得た。平均粒子径、屈折率を表 I 2に示す。  In an autoclave with a stirrer, 20 parts of methyl methacrylate, 80 parts of n-butyl acrylate, 5 parts of dibutylbenzene as a crosslinking agent, 0.2 part of benzoyl peroxide as a polymerization initiator, and dodecylbenzenesulfone as a suspension stabilizer Sodium oxalate (0.001 part), tribasic calcium phosphate (0.5 part) and pure water (200 parts) were charged and polymerized at a temperature of 95 ° C for 6 hours and further at a temperature of 130 ° C for 2 hours. After completion of the reaction, washing, dehydration and drying were carried out to obtain a bead-shaped crosslinked bead (C). The average particle diameter and refractive index are shown in Table I2.
[0048] スチレン一 MMA架橋ビーズ（D)  [0048] Styrene-MMA cross-linked beads (D)
攪拌機付きオートクレープにスチレン 40部、メタクリル酸メチル 60部、架橋剤として ジビュルベンゼン 5部、重合開始剤として、ベンゾィルパーオキサイド 0. 2部、懸濁安 定剤としてドデシルベンゼンスルホン酸ナトリウム 0. 001部及び第三リン酸カルシゥ ム 0. 5部、純水 200部を仕込み、温度 95°Cにて 6時間、さらに温度 130°Cにて 2時 間重合した。反応終了後、洗浄、脱水、乾燥を行い、ビーズ状の架橋ビーズ D— 1を 得た。第三リン酸カルシウム 1. 0部を用いた以外は D—1と同様な製法により D— 2を 得た。また、第三リン酸カルシウム 0. 2部を用いた以外は D—1と同様な製法によりビ ーズ状の架橋ビーズ D— 3を得た。更に第三リン酸カルシウム 0. 1部を用いた以外は D— 1と同様な製法によりビーズ状の架橋ビーズ D— 4を得た。これらの平均粒子径、 屈折率を表 I 2に示す。 In an autoclave with a stirrer, 40 parts of styrene, 60 parts of methyl methacrylate, 5 parts of dibutylbenzene as a crosslinking agent, 0.2 part of benzoyl peroxide as a polymerization initiator, sodium dodecylbenzenesulfonate as a suspension stabilizer 0 001 parts and 0.5 part of tribasic calcium phosphate and 200 parts of pure water were charged and polymerized at a temperature of 95 ° C for 6 hours and further at a temperature of 130 ° C for 2 hours. After completion of the reaction, washing, dehydration and drying were carried out to obtain bead-like crosslinked beads D-1. D-2 was obtained by the same production method as D-1, except that 1.0 part of tricalcium phosphate was used. In addition, using the same production method as D-1, except that 0.2 part of tribasic calcium phosphate was used. A cross-linked bead D-3 was obtained. Further, bead-like crosslinked beads D-4 were obtained by the same production method as D-1, except that 0.1 part of tricalcium phosphate was used. These average particle diameters and refractive indexes are shown in Table I2.
[0049] ポリメチルメタタリレート架橋ビーズ (E)  [0049] Polymethylmetatalylate cross-linked beads (E)
攪拌機付きオートクレープにメタクリル酸メチル 100部、架橋剤としてジビュルベン ゼン 5部、重合開始剤として、ベンゾィルパーオキサイド 0. 2部、懸濁安定剤としてド デシルベンゼンスルホン酸ナトリウム 0. 001部及び第三リン酸カルシウム 0. 5部、純 水 200部を仕込み、温度 95°Cにて 6時間、さらに温度 130°Cにて 2時間重合した。反 応終了後、洗浄、脱水、乾燥を行い、ビーズ状のポリメチルメタタリレート架橋ビーズ（ 以下、「PMMA架橋ビーズ」という。） E—1を得た。第三リン酸カルシウム 1. 5部を用 V、た以外は PMMA架橋ビーズ E— 1と同様な製法によりビーズ状の PMMA架橋ビ ーズ E— 2を得た。また、第三リン酸カルシウム 1. 0部を用いた以外は E—1と同様な 製法によりビーズ状の PMMA架橋ビーズ E— 3を得た。更に、第三リン酸カルシウム 0. 2部を用いた以外は E— 1と同様な製法によりビーズ状の PMMA架橋ビーズ E— 4を得た。これらの平均粒子径、屈折率を表 I 2に示す。  In an autoclave with a stirrer, 100 parts of methyl methacrylate, 5 parts of dibutene benzene as a crosslinking agent, 0.2 part of benzoyl peroxide as a polymerization initiator, 0.001 part of sodium dodecylbenzenesulfonate as a suspension stabilizer and 0.5 parts of calcium triphosphate and 200 parts of pure water were charged and polymerized at a temperature of 95 ° C for 6 hours and further at a temperature of 130 ° C for 2 hours. After completion of the reaction, washing, dehydration and drying were carried out to obtain bead-like polymethylmetatalate crosslinked beads (hereinafter referred to as “PMMA crosslinked beads”) E-1. A beaded PMMA crosslinked bead E-2 was obtained by the same production method as PMMA crosslinked bead E-1, except that 1.5 parts of tribasic calcium phosphate was used. Further, bead-like PMMA cross-linked beads E-3 were obtained by the same production method as E-1, except that 1.0 part of tricalcium phosphate was used. Further, bead-like PMMA cross-linked beads E-4 were obtained by the same production method as E-1, except that 0.2 part of tricalcium phosphate was used. These average particle diameters and refractive indexes are shown in Table I2.
[0050] [表 2] [0050] [Table 2]
表 I— 2 Table I— 2
Figure imgf000020_0001
Figure imgf000020_0001
[0051] スチレン系共重合体 A— 1〜Α—4、未溶融化合物として架橋ビーズ B、 C、 D— 1 〜D—4、 Ε—1〜Ε—4、ヒンダードアミン系化合物としてビス（2, 2, 6, 6—テトラメチ ルー 4ーピペリジル）セバケート、ベンゾトリアゾール系化合物として 2—（2H べンゾ トリァゾールー 2 ィル）—4, 6 ジ tert ペンチルフエノールを表 1— 3、表 1—4 に示す配合比にて混合した。得られた混合物を 40mm径の単軸押出し機にて、温度 240°C、スクリュー回転数 lOOrpmにて混練し、ペレット化を行い、スチレン系榭脂組 成物 1〜25のペレットを得た。 [0051] Styrene-based copolymers A-1 to Α-4, crosslinked beads B, C, D-1 to D-4, Ε-1 to Ε-4 as unmelted compounds, bis (2, 2, 6, 6-Tetramethyl 4-piperidyl) sebacate and 2- (2H benzotriazole-2-yl) -4, 6 di tert pentylphenol as benzotriazole compounds are shown in Table 1-3 and Table 1-4. It mixed with the compounding ratio. The obtained mixture was kneaded with a 40 mm diameter single screw extruder at a temperature of 240 ° C. and a screw rotation speed of lOO rpm, and pelletized to obtain pellets of styrene-based resin compositions 1 to 25.
尚、表 1— 3のスチレン系榭脂組成物 1〜13は、表層 a、裏層 cのスチレン系榭脂組 成物（(A)成分）に対応しており、表 1—4のスチレン系榭脂組成物 14〜25は、中間 層 bの榭脂組成物（ (B)成分）に対応して 、る。  The styrene-based resin compositions 1 to 13 in Table 1-3 correspond to the styrene-based resin composition (component (A)) in the surface layer a and the back layer c, and the styrene resin compositions in Table 1-4. The system resin compositions 14 to 25 correspond to the resin composition (component (B)) of the intermediate layer b.
[0052] [表 3] 表 [0052] [Table 3] table
配合 （質量部）  Formulation (parts by mass)
スチレン系 スチレン系 ヒンダード ベンゾ卜リ  Styrene Styrene Hindered Benzyl
共重合体 共重合体 共重合体 アミン系化 ァゾール系 未溶融化合 未溶融化合0053 A - 1 A- 2 A- 3 合物 化合物 物種 物配合量 スチレン系樹脂組成物 1 100 - - 0. 3 0. 3 D— 1 3 スチレン系樹脂組成物 2 100 - 1. 5 1. 5 D- 1 3 スチレン系樹脂組成物 3 100 - - 0. 3 0. 3 D— 1 8 スチレン系樹脂組成物 4 100 - 一 0. 3 0. 3 D— 3 3 スチレン系樹脂組成物 5 ― 100 - 0. 3 0. 3 D- 1 3 スチレン系樹脂組成物 6 ― 100 0. 3 0. 3 D— 1 3 スチレン系樹脂組成物 7 100 - 0. 05 0. 05 D- 1 3 スチレン系樹脂組成物 8 100 - 一 3 3 D— 1 3 スチレン系榭脂組成物 9 100 - 0. 3 0. 3 D— 1 0. 5 スチレン系樹脂組成物 10 100 ― - 0. 3 0. 3 D - 1 13 スチレン系樹脂組成物 1 1 100 - - 0. 3 0. 3 D— 2 3 スチレン系樹脂組成物 12 100 - - 0. 3 0. 3 D-4 3 スチレン系樹脂組成物 13 100 - - 0. 3 0. 3 E— 1 3 Copolymer Copolymer Copolymer Amine-based Azol-based Unmelted compound Not-melted compound 0053 A-1 A-2 A-3 Compound Compound Compound type Compound content Styrenic resin composition 1 100--0.30 3 D— 1 3 Styrenic resin composition 2 100-1. 5 1. 5 D- 1 3 Styrenic resin composition 3 100--0. 3 0. 3 D— 1 8 Styrenic resin composition 4 100 -1 0.3 3 0.3 D-3 3 Styrenic resin composition 5 ― 100-0. 3 0. 3 D-1 3 Styrene resin composition 6 ― 100 0. 3 0. 3 D— 1 3 Styrene 7 100-0. 05 0. 05 D- 1 3 Styrenic resin composition 8 100-1 3 3 D— 1 3 Styrene resin composition 9 100-0. 3 0. 3 D— 1 0.5 Styrenic resin composition 10 100 ―-0. 3 0. 3 D-1 13 Styrenic resin composition 1 1 100--0. 3 0. 3 D― 2 3 Styrenic resin composition 12 100- -0. 3 0. 3 D-4 3 Styrenic resin composition 13 100--0. 3 0. 3 E— 1 3
m m
合（質量部）  Combined (parts by mass)
ダゾ系系系トドチチレリヒチレベレンスンンンススンー  Dazo-based Todochichiririhichiberensunsunsu
重ゾ重合体重合共合体未溶共体未溶合融化合系化共融化ァル系アミンー i  Bi-polymer Polymerized copolymer Undissolved copolymer Undissolved melt-fused coalesced eutectic alloy Amine i
物種化合物合物物配合量 4 A A 1 A 2-—— 1 1 1 1 1 1 1 1 1 CO CJ  Compound compound mix 4 A A 1 A 2 -—— 1 1 1 1 1 1 1 1 1 CO CJ
ω W ω W ω ω ω Q  ω W ω W ω ω ω Q
樹脂成物系組チレン]ス  Resin composite group
1 樹チ系脂組成物レンス] 1 1 I 1 1 1 1 1 1 1 1 Tree fat composition lens] 1 1 I 1 1 1 1 1 1 1 1
系樹脂組成物チレン]ス  -Based resin composition Tylene]
樹脂組成物チ系レスン]  Resin composition
1 1 1 1 1 1 1 1 1 1 1  1 1 1 1 1 1 1 1 1 1 1
系樹脂組成物チレスン]  -Based resin composition Chilesun]
樹脂組成物系チレスン]  Resin composition system Chilesun]
1 1 1 1 樹系脂組成物チレンス 1 1 1 1 1 1  1 1 1 1 Tree fat composition chillence 1 1 1 1 1 1
樹脂組成物系チレスン  Resin composition system Chilesun
ο ο o o ο ο 系樹脂組成物チレ οスン o o o ο ο o 1 1 o ο ο σ o o o  ο ο o o ο ο-based resin composition Chile ο Sun o o o ο ο o 1 1 o ο ο σ o o o
i  i
樹脂成物系組チレスン  Resin composition group Chilesun
樹系脂組成物チレスン 2  Tree fat composition Chilesun 2
1 1 1 o 1 1 1 1 I 1 1 1  1 1 1 o 1 1 1 1 I 1 1 1
樹系脂組成物チスレン 2 σ> ο  Tree fat composition Tislen 2 σ> ο
例 I 1〜ト 30 Example I 1 to G 30
スチレン系榭脂組成物 1 25を用いて、フィードブロックを有する Tダイ方式の多層 押出機にて表 I 5 8に示した 3層構成のシートを作製した。尚、多層押出機は、中 間層用が 65mm φのフルフライトスクリューの単軸押出機 1台、表裏層用に 30mm φ のフルフライトスクリューの単軸押出機各 1台からなり、各々の溶融榭脂がフィードブ ロックで合流多層化される試験押出機を使用した。シートィ匕の各シリンダー温度は 23Using the styrene-based resin composition 125, a three-layered sheet shown in Table I 58 was produced using a T-die type multilayer extruder having a feed block. The multi-layer extruder consists of a single 65mmφ full flight screw single screw extruder for the middle layer and one 30mmφ full flight screw single screw extruder for the front and back layers. Oil is the feed A test extruder that was joined in layers with a lock was used. The temperature of each cylinder of the sheet is 23
0°Cにて運転、成形した。 Operation and molding at 0 ° C.
得られた多層シートの光学特性、耐光性、吸湿性データを表 1— 5〜！ー 8に示す。 尚、表 I— 5〜1— 8の榭脂 1とは、スチレン系榭脂組成物 1のことをいう。以下、同様 に榭脂 2〜榭脂 25とは、スチレン系榭脂組成物 2〜スチレン系榭脂組成物 25のこと をいう。  The optical properties, light resistance, and moisture absorption data of the obtained multilayer sheet are shown in Table 1-5! -Shown in 8. In Tables I-5 to 1-8, the resin 1 refers to the styrene-based resin composition 1. Hereinafter, similarly, the resin 2 to the resin 25 refers to the styrene resin composition 2 to the styrene resin composition 25.
[0055] また、光学特性については、曇り度 99%以上、全光線透過率 60%以上、拡散率 2 0%以上、 b値は 1以下である場合、優れた光拡散性を発現し、光学特性が良好と判 断できる。耐光性は色差 ΔΕ値が 1未満、吸湿性は変形量 lmm以下である場合、各 特性が優れて 、ると判断できる。  [0055] As for the optical characteristics, when the haze is 99% or more, the total light transmittance is 60% or more, the diffusivity is 20% or more, and the b value is 1 or less, excellent light diffusibility is exhibited, It can be judged that the characteristics are good. When the light resistance has a color difference ΔΕ value of less than 1 and the hygroscopicity has a deformation of 1 mm or less, it can be judged that each characteristic is excellent.
なお、得られた多層シートの表層 a及び裏層 cの表面には、未溶融化合物からなる 凹凸が形成されていた。これは、下記する例 II〜例 Vの多層シートの場合も同じであ る。  Note that the surface of the surface layer a and the back layer c of the obtained multilayer sheet had irregularities made of an unmelted compound. The same applies to the multilayer sheets of Examples II to V below.
例 I 1〜卜 9は、これらの特性を全て併せ持つ特に好ましい実施例である。  Examples I 1 to 卜 9 are particularly preferred embodiments that combine all of these properties.
例 1—10, 1— 11、 1— 27、 1— 28、 1— 30はその他の実施例である。  Examples 1-10, 1-11, 1-27, 1-28, 1-30 are other examples.
例1 12〜1 26、 1— 29は比較例である。  Examples 1 12 to 1 26, 1-29 are comparative examples.
[0056] [表 5] [0056] [Table 5]
表 I— 5 Table I—5
例 例 例 例 例 例 例 例 例 1 2 3 4 5 6 7 8 9 種類 樹脂 1 樹脂 2 樹脂 3 樹脂 1 樹脂 4 樹脂 1 樹脂 1 樹脂 1 樹脂 1 a 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.01 0.1 肉厚 (mm)  Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8 9 Types Resin 1 Resin 2 Resin 3 Resin 1 Resin 4 Resin 1 Resin 1 Resin 1 Resin 1 a 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.01 0.1 Wall thickness ( mm)
種類 樹脂 14 榭脂 14 樹脂 14 樹脂 15 樹脂 14 榭脂 25 榭脂 16 樹脂 14 樹脂 14 b 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 5 肉厚 (mm)  Type Resin 14 Resin 14 Resin 14 Resin 15 Resin 14 Resin 25 Resin 16 Resin 14 Resin 14 b 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 5 Thickness (mm)
シート層構成  Sheet layer configuration
種類 樹脂 1 樹脂 2 樹脂 3 樹脂 1 樹脂 4 樹脂 1 樹脂 1 樹脂 1 樹脂 1 c 0.1 0.1 0.1 0.1 0-1 0.1 0.1 0-01 0.1 肉厚 (mm)  Type Resin 1 Resin 2 Resin 3 Resin 1 Resin 4 Resin 1 Resin 1 Resin 1 Resin 1 c 0.1 0.1 0.1 0.1 0-1 0.1 0.1 0-01 0.1 Wall thickness (mm)
2 2 2 2 2 2 2 1.82 5.2 総肉厚 （mm)  2 2 2 2 2 2 2 1.82 5.2 Total wall thickness (mm)
67.4 67.3 65.2 65.4 65.4 65.2 69.6 68.1 63.3 シート光学特性 全光線透過率 ）  67.4 67.3 65.2 65.4 65.4 65.2 69.6 68.1 63.3 Sheet optical characteristics Total light transmittance)
99.2 99.2 99.3 99.3 99.3 99.3 99.0 99.1 99.4 曇り度 W  99.2 99.2 99.3 99.3 99.3 99.3 99.0 99.1 99.4 Cloudiness W
23.5 23.4 23.8 23.8 23.8 23.7 21.8 22.8 24.8 拡散率 (¾)  23.5 23.4 23.8 23.8 23.8 23.7 21.8 22.8 24.8 Diffusivity (¾)
0.3 0.5 0.3 0.3 0.3 0.3 0.3 0.3 0.3 b値  0.3 0.5 0.3 0.3 0.3 0.3 0.3 0.3 0.3 b value
耐光性 色差 ΔΕ 0.4 0.3 0.4 0.4 0.4 0.4 0.4 0. 6 0.4 吸湿性 （mm) 0.32 . 0.32 0.32 0.32 0.32 0.32 0.32 0.31 0.31 Light resistance Color difference ΔΕ 0.4 0.3 0.4 0.4 0.4 0.4 0.4 0. 6 0.4 Hygroscopicity (mm) 0.32. 0.32 0.32 0.32 0.32 0.32 0.32 0.31 0.31
表 I— 6 Table I—6
例 例 例 例 例 例 例 例 例 Example Example Example Example Example Example Example Example Example
10 1 1 12 13 14 15 16 17 18 種類 樹脂 1 樹脂 1 樹脂 5 樹脂 6 樹脂 7 樹脂 8 樹脂 9 樹脂 10 樹脂 11 a 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 肉厚 （mm) 10 1 1 12 13 14 15 16 17 18 Types Resin 1 Resin 1 Resin 5 Resin 6 Resin 7 Resin 8 Resin 9 Resin 10 Resin 11 a 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Thickness (mm)
種類 樹脂 17 樹脂 18 樹脂 14 樹脂 14 樹脂 14 樹脂 14 樹脂 14 樹脂 14 樹脂 14 b 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 肉厚 (mm)  Type Resin 17 Resin 18 Resin 14 Resin 14 Resin 14 Resin 14 Resin 14 Resin 14 Resin 14 b 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Thickness (mm)
シート層構成  Sheet layer configuration
種類 樹脂 1 樹脂 1 樹脂 5 樹脂 6 樹脂 7 樹脂 8 樹脂 9 樹脂 10 樹脂 11 c 0.1 0.1 0.1 0.1 0-1 0.1 0.1 0-1 0.1 肉厚 （mm)  Type Resin 1 Resin 1 Resin 5 Resin 6 Resin 7 Resin 8 Resin 9 Resin 10 Resin 11 c 0.1 0.1 0.1 0.1 0-1 0.1 0.1 0-1 0.1 Thickness (mm)
2 2 2 2 2 2 2 2 2 総肉厚 （mm)  2 2 2 2 2 2 2 2 2 Total wall thickness (mm)
67.4 67.3 67.4 67.3 67.4 67.4 70.1 59.6 70.2 シート光学特性 全光線透過率は）  67.4 67.3 67.4 67.3 67.4 67.4 70.1 59.6 70.2 Sheet optical characteristics Total light transmittance is
99.2 99.2 99.2 99.2 99.2 99.2 98.3 99.5 98.2 曇り度は）  99.2 99.2 99.2 99.2 99.2 99.2 98.3 99.5 98.2 Cloudiness)
23.5 23.4 23.4 23.3 23.5 23.5 19.5 25.3 19.3 拡散率 tt)  23.5 23.4 23.4 23.3 23.5 23.5 19.5 25.3 19.3 Diffusion rate tt)
0.3 0.3 0.3 0.3 0.3 1.2 0.3 0.3 0.3 b値  0.3 0.3 0.3 0.3 0.3 1.2 0.3 0.3 0.3 b value
耐光性 色差 ΔΕ 0.4 1.2 1.1 0.4 1. 0.2 0.4 0.4 0.4 吸湿性 （mm) 1.21 0.32 0.32 1.14 0.32 0.33 0.32 0.33 0.33 Light resistance Color difference ΔΕ 0.4 1.2 1.1 0.4 1. 0.2 0.4 0.4 0.4 Hygroscopicity (mm) 1.21 0.32 0.32 1.14 0.32 0.33 0.32 0.33 0.33
Figure imgf000026_0001
表
Figure imgf000026_0001
table
例 例 例 例 例 例 例 例 例 Example Example Example Example Example Example Example Example Example
19 20 21 22 23 24 25 26 27 種類 樹脂 12 樹脂 13 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 榭脂 1 樹脂 1 a 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.003 肉厚 （mm) 19 20 21 22 23 24 25 26 27 Types Resin 12 Resin 13 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 a 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.003 Thickness (mm)
種類 樹脂 14 樹脂 14 樹脂 19 樹脂 20 樹脂 21 樹脂 22 樹脂 23 樹脂 24 樹脂 14 b 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 肉厚 （mm)  Type Resin 14 Resin 14 Resin 19 Resin 20 Resin 21 Resin 22 Resin 23 Resin 24 Resin 14 b 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Thickness (mm)
シート層構成  Sheet layer configuration
種類 樹脂 12 樹脂 13 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 c 0.1 0.1 0.1 0.1 0-1 0.1 0.1 0-1 0.003 肉厚 (mm)  Type Resin 12 Resin 13 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 c 0.1 0.1 0.1 0.1 0-1 0.1 0.1 0-1 0.003 Thickness (mm)
2 2 2 2 2 2 2 2  2 2 2 2 2 2 2 2
総肉厚 （mm) 1.806  Total wall thickness (mm) 1.806
59.7 58.8 70.5 58.8 70.4 58.7 71.5 56.4 67.4 シート光学特性 全光線透過率 (¾)  59.7 58.8 70.5 58.8 70.4 58.7 71.5 56.4 67.4 Sheet optical properties Total light transmittance (¾)
99.5 99.5 98.1 99.5 98.2 99.5 98.0 99.6 99.2 曇り度は）  99.5 99.5 98.1 99.5 98.2 99.5 98.0 99.6 99.2 Haze is)
25.3 25.5 19.1 25.4 19.2 25.5 18.8 25.7 23.5 拡散率 (¾)  25.3 25.5 19.1 25.4 19.2 25.5 18.8 25.7 23.5 Diffusion rate (¾)
0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 b値  0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 b value
耐光性 色差 ΔΕ 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 1.6 吸湿性 （mm) 0.33 ' 0.33 0.32 0.33 0.33 0.33 0.32 0.33 0.33 Light resistance Color difference ΔΕ 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 1.6 Hygroscopicity (mm) 0.33 '0.33 0.32 0.33 0.33 0.33 0.32 0.33 0.33
Figure imgf000027_0001
Figure imgf000027_0001
[例 II] (着色剤 (蛍光増白剤)を含有する多層シートの例） [Example II] (Example of multilayer sheet containing colorant (fluorescent brightener))
スチレン系共重合体の製造 Production of styrenic copolymers
スチレン 10%、メチルメタタリレート 90%で構成する単量体溶液を用いた以外は、 例 I (A— 1)と同様に実施し、スチレン系共重合体 II (A- 1)を得た。  Except that a monomer solution composed of 10% styrene and 90% methyl methacrylate was used, the same procedure as in Example I (A-1) was performed to obtain a styrene copolymer II (A-1). .
スチレン 40%、メチルメタタリレート 60%で構成する単量体溶液を用いた以外は、 例 I (A— 1)と同様に実施し、スチレン系共重合体 II (A- 2)を得た。  Except for using a monomer solution composed of 40% styrene and 60% methyl methacrylate, the same procedure as in Example I (A-1) was carried out to obtain a styrene copolymer II (A-2). .
スチレン 80%、メチルメタタリレート 20%で構成する単量体溶液を用いた以外は、 例 I (A— 1)と同様に実施し、スチレン系共重合体 II (A- 3)を得た。  Except that a monomer solution composed of 80% styrene and 20% methyl methacrylate was used, the same procedure as in Example I (A-1) was performed to obtain a styrene copolymer II (A-3). .
スチレン 95%、メチルメタタリレート 5%で構成する単量体溶液を用いた以外は、（A - 1)と同様に実施し、スチレン系共重合体 II (A-4)を得た。  Styrene copolymer II (A-4) was obtained in the same manner as in (A-1) except that a monomer solution composed of 95% styrene and 5% methyl methacrylate was used.
以上のように得られたスチレン系共重合体 II (A— 1 4)の榭脂組成及び屈折率を 表 II 1に示す。 [0061] 未溶融化合物として、例 1 (表 I 2)の架橋ビーズ B、 C、 D— 1〜D— 4、 E— 1〜E 4を使用した。 Table II 1 shows the resin composition and refractive index of the styrene copolymer II (A-14) obtained as described above. [0061] As the unmelted compound, the crosslinked beads B, C, D-1 to D-4 and E-1 to E4 of Example 1 (Table I2) were used.
着色剤 (F)は、いわゆる蛍光増白剤である 2, 5 チォフェンジィル（5— t ブチル — 1, 3 ベンゾキサゾール）（チバスペシャルティケミカルズ社製ュビテックス OB)を（ F— 1)、無機顔料である DAYGRO社製 ZQ— 19を (F— 2)、有機染料である三菱 化学社製ダイァレジン BLUE Jを (F— 3)として用 、た。  Colorant (F) is a so-called fluorescent whitening agent, 2,5-thiopheneyl (5-t-butyl-1,3 benzoxazole) (Ubitex OB manufactured by Ciba Specialty Chemicals) (F-1), an inorganic pigment. One DAYGRO ZQ-19 was used as (F-2), and the organic dye Dairesin BLUE J made by Mitsubishi Chemical was used as (F-3).
[0062] スチレン系共重合体 (A— 1)〜 (A— 4)、未溶融化合物として B、 C、（D— 1)〜（D —4)、（Ε—1)〜（Ε—4)、ヒンダードアミン系化合物としてビス（2, 2, 6, 6—テトラメ チル— 4 ピペリジル）セバケート、ベンゾトリアゾール系化合物として 2— (2H ベン ゾトリァゾールー 2 ィル） -4, 6 ジ t—ペンチルフエノール、着色剤として（F—1 ；)〜 (F— 3)を、表 II - 2〜11 - 5に示す配合比にて混合した。得られた混合物を 40m m径の単軸押出し機にて、温度 240°C、スクリュー回転数 lOOrpmにて混練し、ペレ ット化を行い、表 11 2〜11 5に示したスチレン系榭脂組成物 1〜54のペレットを得 た。 [0062] Styrene copolymers (A-1) to (A-4), B, C, (D-1) to (D-4), (Ε-1) to (Ε-4) as unmelted compounds ), Bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate as a hindered amine compound, 2- (2H benzotriazole-2-yl) as a benzotriazole compound, -4, 6 di-t-pentylphenol, colored As agents, (F-1;) to (F-3) were mixed at the blending ratios shown in Tables II-2 to 11-5. The resulting mixture was kneaded with a 40 mm single-screw extruder at a temperature of 240 ° C and a screw rotation speed of lOOrpm, pelletized, and styrene-based resins shown in Tables 11 2 to 115. Pellets of compositions 1-54 were obtained.
[0063] 尚、表 11 2〜11 3のスチレン系榭脂組成物 1〜27は、表層 a、裏層 cのスチレン系 榭脂組成物（(A)成分）に対応しており、表 Π—4〜Π 5のスチレン系榭脂組成物 28 〜54は、中間層 bの榭脂組成物（（B)成分）に対応している。  [0063] The styrene-based resin compositions 1-27 in Tables 11 2-11 3 correspond to the styrene-based resin compositions (component (A)) of the surface layer a and the back layer c. The styrene-based resin compositions 28 to 54 of −4 to 5 correspond to the resin composition (component (B)) of the intermediate layer b.
[0064] [例 II 1〜Π— 70]  [0064] [Example II 1 to Π-70]
スチレン系榭脂糸且成物 1〜54を用いて、フィードブロックを有する Τダイ方式の多層 押出機にて表 II— 6〜11— 12に示した 3層構成のシートを作製した。尚、多層押出機 は、中間層用が 65mm φのフルフライトスクリューの単軸押出機 1台、表裏層用に 30 mm φのフルフライトスクリューの単軸押出機各 1台からなり各々の溶融榭脂がフィー ドブロックで合流多層化される試験押出機を使用した。シートィ匕の各シリンダー温度 は 230°Cにて運転、成形した。  Using the styrene-based cocoon yarn composites 1 to 54, a sheet having a three-layer structure shown in Tables II-6 to 11-12 was prepared using a Τ die type multilayer extruder having a feed block. The multi-layer extruder consists of a single 65mm φ full flight screw single screw extruder for the intermediate layer and a single 30mm φ full flight screw single screw extruder for the front and back layers. A test extruder was used in which the fats were joined and multilayered at the feed block. Each cylinder temperature of sheety was operated and molded at 230 ° C.
得られたシートの光学特性、耐光性、吸水反りを評価し、そのデータを表 II 6〜11 12に示した。  The optical properties, light resistance and water absorption warpage of the obtained sheet were evaluated, and the data are shown in Tables II 6-1112.
[0065] 例 IIにおいては、曇り度 99%以上、全光線透過率 68%以上、拡散率 18%以上、 b 値は 1以下である場合、光学特性が特に優れていると判断できる。また、耐光性は色 差 Δ Ε値が 1未満、寸法安定性は吸水反りが lmm以下であれば、優れていると判断 できる。例 II— 1〜11— 18は、これらの特性を全て併せ持つ特に好ましい実施例であ る。例 Π—19、 Π— 20、 Π— 30、 Π— 31、 Π— 38〜Π— 45、 Π— 61〜Π— 70はその他 の実施例である。例 Π— 21〜Π— 29、 Π— 32〜Π— 37、 Π— 46〜Π— 60は比較例で ある。 In Example II, when the haze is 99% or more, the total light transmittance is 68% or more, the diffusivity is 18% or more, and the b value is 1 or less, it can be determined that the optical characteristics are particularly excellent. Also, light resistance is color If the difference ΔΕ value is less than 1 and the dimensional stability is less than 1 mm, the dimensional stability can be judged as excellent. Examples II-1 to 11-18 are particularly preferred examples having all these characteristics. Examples Π-19, Π-20, Π-30, Π-31, Π-38 to Π-45, Π-61 to Π-70 are other examples. Examples Π—21 to Π—29, Π—32 to Π—37, Π—46 to Π—60 are comparative examples.
[0066] [表 9] 表 Π— 1 [0066] [Table 9] Table Π— 1
Figure imgf000029_0001
Figure imgf000029_0001
[0067] [表 10] [0067] [Table 10]
表 table
配合  Formulation
スチレン スチレン スチレン ヒンダ一  Styrene Styrene Styrene Hinder
リアゾ一  Riazo
系共重合 系共重合 系共重合 ドアミン 未溶融化合物 着色剤¾006 ル系化合  Copolymer Copolymer Copolymer Doamine Unmelted compound Colorant ¾006
体 A— 1 体 A - 2 体 A - 3 系化合物  Body A— 1 body A-2 body A-3 series compounds
物  object
スチレン系樹脂組成物名 質量部 質量部 質量部 質量部 質量部 種類 質量部 種類 質量部 樹脂 1 ― 100 - 0. 3 0. 3 D - 1 3 F— 1 0. 01 樹脂 2 ― 100 - 0. 05 0. 05 D— 1 3 F - 1 0. 01 樹脂 3 ― 100 ― 3 3 D— 1 3 F— 1 0. 01 樹脂 4 - 100 - 0. 3 0. 3 D— 1 0. 5 F— 1 0. 01 樹脂 5 - 100 - 0. 3 0. 3 D - 1 13 F— 1 0. 01 樹脂 6 - 100 - 0. 3 0. 3 D - 2 3 F— 1 0. 01 樹脂 7 一 100 - 0. 3 0. 3 D - 3 3 F— 1 0. 01 樹脂 8 - 100 - 0. 3 0. 3 D— 4 3 F - 1 0. 01 樹脂 9 - 100 ― 0. 3 0. 3 E - 1 3 F— 1 0. 01 樹脂 1 0 100 - - 0. 3 0. 3 D - 1 3 F - 1 0. 0 1 樹脂 1 1 - - 100 0. 3 0. 3 D - 1 3 F - 1 0. 01 樹脂 1 2 - 100 - 0. 3 0. 3 D— 1 3 F— 1 0. 0001 樹脂 1 3 - 100 ― 0. 3 0. 3 D - 1 3 F— 1 0. 1 樹脂 1 4 ― 1 00 ― 0. 3 0. 3 D— 1 3 F— 1 1 Styrene resin composition name Mass part Mass part Mass part Mass part Mass part Type Mass part Type Mass part Resin 1 ― 100-0. 3 0. 3 D-1 3 F― 1 0. 01 Resin 2 ― 100-0. 05 0. 05 D— 1 3 F-1 0. 01 Resin 3 ― 100 ― 3 3 D— 1 3 F— 1 0. 01 Resin 4-100-0. 3 0. 3 D— 1 0. 5 F— 1 0. 01 Resin 5-100-0. 3 0. 3 D-1 13 F— 1 0. 01 Resin 6-100-0. 3 0. 3 D-2 3 F— 1 0. 01 Resin 7 1 100 -0. 3 0. 3 D-3 3 F— 1 0. 01 Resin 8-100-0. 3 0. 3 D— 4 3 F-1 0. 01 Resin 9-100 ― 0. 3 0. 3 E -1 3 F— 1 0. 01 Resin 1 0 100--0. 3 0. 3 D-1 3 F-1 0. 0 1 Resin 1 1--100 0. 3 0. 3 D-1 3 F- 1 0. 01 Resin 1 2-100-0. 3 0. 3 D— 1 3 F— 1 0. 0001 Resin 1 3-100 ― 0. 3 0. 3 D-1 3 F— 1 0. 1 Resin 1 4 ― 1 00 ― 0. 3 0. 3 D— 1 3 F— 1 1
表 table
配合  Formulation
ベンゾ卜  Benzo
スチレン スチレン スチレン ヒンダ一  Styrene Styrene Styrene Hinder
リアゾー  Riazo
系共重合 系共重合 系共重合 ドアミン 未溶融化合物 着色剤 体 A— 1 体 A— 2 体 A— 3 ル系化合  Copolymer Copolymer Copolymer Copolymer Doamine Unmelted compound Colorant Body A— 1 body A— 2 body A— 3
系化合物  Compounds
物  object
スチレン系樹脂組成物名 質量部 質量部 質量部 質量部 質量部 種類 質量部 種類 質量部 樹脂 1 5 ― 100 ― 0. 3 0. 3 D— 1 3 F - 2 0. 01 樹脂 1 6 一 100 ― 0. 3 0. 3 D - 1 3 F - 3 0. 01 樹脂 1 7 ― 100 0. 3 0. 3 D 1 3 ― ― 樹脂 1 8 ― 100 0. 05 0. 05 D - 1 3 ― ― 樹脂 1 9 ― 100 ― 3 3 D— 1 3 ― ― 樹脂 2 0 ― 100 ― 0. 3 0. 3 D— 1 0. 5 ― ― 樹脂 2 1 ― 100 ― 0. 3 0. 3 D— 1 13 ― ― 樹脂 2 2 ― 100 一 0. 3 0. 3 D - 2 3 ― ― 樹脂 2 3 ― 100 ― 0. 3 0. 3 D— 3 3 ― ― 樹脂 2 4 ― 100 ― 0. 3 0. 3 D - 4 3 一 ― 樹脂 2 5 ― 100 0. 3 0. 3 E - 1 3 ― ― 樹脂 2 6 100 一 0. 3 0. 3 D - 1 3 一 ― 樹脂 2 7 100 0. 3 0. 3 D— 1 3 ― - Styrene resin composition name Mass part Mass part Mass part Mass part Mass part Type Mass part Type Mass part Resin 1 5 ― 100 ― 0. 3 0. 3 D― 1 3 F-2 0. 01 Resin 1 6 1 100 ― 0. 3 0. 3 D-1 3 F-3 0. 01 Resin 1 7 ― 100 0. 3 0. 3 D 1 3 ― ― Resin 1 8 ― 100 0. 05 0. 05 D-1 3 ― ― Resin 1 9 ― 100 ― 3 3 D― 1 3 ― ― Resin 2 0 ― 100 ― 0. 3 0. 3 D― 1 0. 5 ― ― Resin 2 1 ― 100 ― 0. 3 0. 3 D― 1 13 ― ― Resin 2 2 ― 100 1 0. 3 0. 3 D-2 3 ― ― Resin 2 3 ― 100 ― 0. 3 0. 3 D ― 3 3 ― ― Resin 2 4 ― 100 ― 0. 3 0. 3 D -4 3 1-Resin 2 5-100 0. 3 0. 3 E-1 3--Resin 2 6 100 1 0. 3 0. 3 D-1 3 1-Resin 2 7 100 0. 3 0. 3 D - 13 - -
表 I I— 4 Table I I — 4
配合  Formulation
ベンゾ卜  Benzo
スチレン スチレン スチレン ヒンダ一  Styrene Styrene Styrene Hinder
リアゾー  Riazo
S 系共重合 系共重合 系共重合 ドアミン 未溶融化合物 着色剤s007 ル系化合 S-based copolymerization-based copolymerization-based copolymerization Doamine Unmelted compound Colorant s007
体 A— 1 体 A— 3 体 A— 4 系化合物  Body A— 1 body A— 3 bodies A— 4 compounds
物  object
スチレン系樹脂組成物名 質量部 質量部 質量部 質量部 質量部 種類 質量部 種類 質量部 樹脂 2 8 100 - ― ― E— 1 3 F— 1 0. 01 樹脂 2 9 100 一 ― ― E— 1 0. 5 F— 1 0. 01 樹脂 3 0 - 100 ― ― E— 1 13 F— 1 0. 01 樹脂 3 1 ― 100 一 一 ― E - 2 3 F— 1 0. 01 樹脂 3 2 - 100 一 ― E - 3 3 F— 1 0. 01 樹脂 3 3 - 100 一 - E - 4 3 F— 1 0. 01 樹脂 3 4 ― 100 - - 一 B 3 F - 1 0. 01 樹脂 3 5 - 100 一 - - C 3 F - 1 0. 01 樹脂 3 6 ― 100 ― 一 一 D - 1 3 F— 1 0. 01 樹脂 3 7 100 ― ― - ― E - 1 3 F— 1 0. 01 樹脂 3 8 100 - E— 1 3 F— 1 0. 01 樹脂 3 9 - ■ ― E - 1 3 F— 1 0. 0001 樹脂 4 0 - 100 ― E - 1 3 F— 1 0. 1 樹脂 4 1 ― 100 - ― E— 1 3 F— 1 1 Styrenic resin composition name Mass part Mass part Mass part Mass part Mass part Type Mass part Type Mass part Resin 2 8 100---E-1 3 F-1 0. 01 Resin 2 9 100 1--E-1 0 5 F— 1 0. 01 Resin 3 0-100 ― ― E— 1 13 F— 1 0. 01 Resin 3 1 ― 100 1 ― E-2 3 F― 1 0. 01 Resin 3 2-100 1 ― E-3 3 F— 1 0. 01 Resin 3 3-100 1-E-4 3 F— 1 0. 01 Resin 3 4 ― 100--1 B 3 F-1 0. 01 Resin 3 5-100 1- -C 3 F-1 0. 01 Resin 3 6 ― 100 ― One D-1 3 F― 1 0. 01 Resin 3 7 100 ― ―-― E-1 3 F― 1 0. 01 Resin 3 8 100- E— 1 3 F— 1 0. 01 Resin 3 9-■ ― E-1 3 F— 1 0. 0001 Resin 4 0-100 ― E-1 3 F— 1 0. 1 Resin 4 1 ― 100-― E — 1 3 F— 1 1
表 I I— 5 Table I I— 5
配合  Formulation
ベンゾ卜  Benzo
スチレン スチレン スチレン ヒンダ一  Styrene Styrene Styrene Hinder
リアゾー  Riazo
系共重合 系共重合 系共重合 ドアミン 未溶融化合物 着色剤 体 A - 3 体 A— 4 ル系化合  Copolymer Copolymer Copolymer Copolymer Doamine Unmelted Compound Colorant Body A-3 Body A-4
体 A - 1 系化合物  Body A-1 series compounds
物  object
スチレン系樹脂組成物名 質量部 質量部 質量部 質量部 質量部 種類 質量部 種類 質量部 樹脂 4 2 - 100 - - - E - 1 3 F - 2 0. 01 樹脂 4 3 - 100 - - - E - 1 3 F— 3 0. 01 樹脂 4 4 - 100 - - 一 E - 1 3 ― - 樹脂 4 5 - 100 - ― - E - 1 0. 5 - - 樹脂 4 6 - 100 - - - E 1 13 - - 樹脂 4 7 一 100 一 - 一 E— 2 3 一 - 樹脂 4 8 ― 100 一 - 一 E— 3 3 - - 樹脂 4 9 - 100 - —― ― E - 4 3 ― - 樹脂 5 0 - 100 - ― ― B 3 ― ― 樹脂 5 1 - 100 - ― - C 3 一 - 樹脂 5 2 - 100 - - 一 D— 1 3 ― 一 樹脂 5 3 100 - 一 - 一 E 1 3 - 一 樹脂 5 4 ― - 100 - - E— 1 3 - 一 Styrene resin composition name Mass part Mass part Mass part Mass part Mass part Type Mass part Type Mass part Resin 4 2-100---E-1 3 F-2 0. 01 Resin 4 3-100---E- 1 3 F— 3 0. 01 Resin 4 4-100--One E-1 3--Resin 4 5-100---E-1 0. 5--Resin 4 6-100---E 1 13- -Resin 4 7 1 100 1-1 E- 2 3 1-Resin 4 8-100 1-1 E-3 3--Resin 4 9-100----E-4 3--Resin 5 0-100- ― ― B 3 ― ― Resin 5 1-100-―-C 3 One-Resin 5 2-100--One D ― 1 3 ― One Resin 5 3 100-One-One E 1 3-One Resin 5 4 ―- 100--E— 1 3-One
Figure imgf000034_0001
Figure imgf000034_0001
表 I I— 7 Table I I— 7
例 例 例 例 例 例 例 12 13 14 15 16 17 18 類 樹脂 脂  Example Example Example Example Example Example Example 12 13 14 15 16 17 18 Class Resin Fat
表層 a 使用樹脂の種 17 樹脂 17 樹脂 17 樹 1 樹脂 1 樹脂 13 樹脂 13 肉厚 （mm) 0. 01 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 使用樹脂の種類 樹脂 28 樹脂 28 樹脂 40 樹脂 28 樹脂 40 樹脂 28 樹脂 40 Surface layer a Resin type 17 Resin 17 Resin 17 Tree 1 Resin 1 Resin 13 Resin 13 Thickness (mm) 0. 01 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 Resin type Resin 28 Resin 28 Resin 40 Resin 28 Resin 40 Resin 28 Resin 40
〔〕 sffi0073- シート 中間層 b [] Sffi0073- sheet intermediate layer b
肉厚 (mm) 1. 8 5 1. 8 1. 8 1. 8 1. 8 層構成 1. 8 使用樹脂の種類 樹脂 17 樹脂 17 樹脂 17 樹脂 1 樹脂 1 樹脂 13 樹脂 13 裏層 c  Thickness (mm) 1. 8 5 1. 8 1. 8 1. 8 1. 8 Layer structure 1. 8 Resin type Resin 17 Resin 17 Resin 17 Resin 1 Resin 1 Resin 13 Resin 13 Resin 13 Back layer c
肉厚 （mm) 0. 01 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 総肉厚 （mm) 1. 81 5. 2 2 2 2 2 2 全光線透過率は） 71. 2 69. 1 71. 7 71. 1 72. 1 71. 6 72. 9 光学特 曇り度 ft) 99. 1 99. 3 99. 1 99. 1 99 99. 1 99 性 拡散率は） 20. 6 23. 2 19. 8 20. 7 19. 1 20 18. 7 b値 0. 1 0 0 0. 1 0 0 -0. 1 耐光性 色差 Δ Ε 0. 6 0. 7 0. 8 0. 7 0. 9 0. 8 0. 9 寸法安定性 吸水反り （mm) 0. 32 0. 32 0. 32 0. 32 0. 32 0. 32 0. 32 Thickness (mm) 0. 01 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 Total thickness (mm) 1. 81 5. 2 2 2 2 2 2 Total light transmittance is 71) 2 69. 1 71. 7 71. 1 72. 1 71. 6 72.9 Optical Haze ft) 99. 1 99. 3 99. 1 99. 1 99 99. 1 99 6 23. 2 19. 8 20. 7 19. 1 20 18. 7 b Value 0. 1 0 0 0. 1 0 0 -0. 1 Light resistance Color difference Δ Ε 0. 6 0. 7 0. 8 0. 7 0. 9 0. 8 0. 9 Dimensional stability Water absorption warp (mm) 0. 32 0. 32 0. 32 0. 32 0. 32 0. 32 0. 32
表 Π— 8 Table Π— 8
例 例 例 例 例 例 例 例 例 例 例 Example Example Example Example Example Example Example Example Example Example Example
19 20 21 22 23 24 25 26 27 28 29 使用樹脂の種類 樹脂 1 樹脂 1 樹脂 11 樹脂 10 樹脂 2 樹脂 3 樹脂 4 樹脂 5 樹脂 6 樹脂 8 樹脂 9 肉厚 （mm) 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 使用樹脂の種類 樹脂 53 榭脂 54 樹脂 44 樹脂 44 樹脂 44 樹脂 44 樹脂 44 樹脂 44 樹脂 44 樹脂 44 樹脂 44 シ一卜 中間層 b 19 20 21 22 23 24 25 26 27 28 29 Resin type Resin 1 Resin 1 Resin 11 Resin 10 Resin 2 Resin 3 Resin 4 Resin 5 Resin 6 Resin 8 Resin 9 Thickness (mm) 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 Type of resin used Resin 53 Oil 54 Resin 44 Resin 44 Resin 44 Resin 44 Resin 44 Resin 44 Resin 44 Resin 44 Resin 44 Resin 44 Single layer b
肉厚 （mm) 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8  Thickness (mm) 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8
層構成 1. 8 1. 8 使用樹脂の種類 樹脂 1 樹脂 1 樹脂 11 樹脂 10 樹脂 2 樹脂 3 樹脂 4 樹脂 5 樹脂 6 樹脂 8 樹脂 9 裏層 c Layer structure 1. 8 1. 8 Resin type Resin 1 Resin 1 Resin 11 Resin 10 Resin 2 Resin 3 Resin 4 Resin 5 Resin 6 Resin 8 Resin 9 Resin c
肉厚 （mm) 0. 1 0. 1 0. 1 0. 1 0 - 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 総肉厚 （mm) 2 2 2 2 2 2 2 1 2 2 2 全光線透過率は） 68. 7 74. 2 69. 3 69. 5 70. 3 69. 9 73. 2 62. 4 74. 6 63. 3 65. 2 光学特 曇り度は） 99. 4 98. 8 99. 3 99. 3 99. 2 99. 2 98. 9 99. 5 98. 7 99. 5 99. 4 性 拡散率は） 23. 6 16. 5 23 22. 8 21. 9 22. 4 18. 4 28 16. 3 27. 1 26. 3 b値 0. 3 0. 3 0. 3 0. 2 0. 1 1 0. 3 0. 4 0. 3 0. 3 0. 3 耐光性 色差 Δ Ε 0. 5 1. 3 1. 2 0. 5 1. 3 0. 2 0. 5 0. 5 0. 5 0. 5 0. 5 寸法安定性 吸水反り （mm) 1. 26 0. 23 0. 29 1. 02 0. 32 0. 32 0. 32 0. 31 0. 31 0. 32 0. 32 Thickness (mm) 0. 1 0. 1 0. 1 0. 1 0-1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 Total thickness (mm) 2 2 2 2 2 2 2 1 2 2 2 Total light transmittance is 68. 7 74. 2 69. 3 69. 5 70. 3 69. 9 73. 2 62. 4 74. 6 63. 3 65. 2 Optical haze is) 99. 4 98. 8 99. 3 99. 3 99. 2 99. 2 98. 9 99. 5 98. 7 99. 5 99. 4 Sex Diffusion rate) 23. 6 16. 5 23 22. 8 21. 9 22. 4 18. 4 28 16. 3 27. 1 26. 3 b Value 0. 3 0. 3 0. 3 0. 2 0. 1 1 0. 3 0. 4 0. 3 0. 3 0. 3 Light resistance Color difference Δ Ε 0. 5 1. 3 1. 2 0. 5 1. 3 0. 2 0. 5 0. 5 0. 5 0. 5 0. 5 Dimensional stability Water absorption warpage (mm) 1. 26 0 23 0. 29 1. 02 0. 32 0. 32 0. 32 0. 31 0. 31 0. 32 0. 32
表 Π— 9Table Π— 9
Figure imgf000037_0001
Figure imgf000037_0001
例 例 例 例 例 例 例 例 例 例 例 30 31 32 33 34 35 36 37 38 39 40 使用樹脂の種類 樹脂 15 樹脂 16 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂  Example Example Example Example Example Example Example Example Example Example 30 31 32 33 34 35 36 37 38 39 40 Type of resin used Resin 15 Resin 16 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin
表層 a 1 樹脂 1 樹脂 1 肉厚 （mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.003 0.8 0.1 脂 44 樹脂 45 樹脂 46 樹脂 47 樹脂 49 樹脂 52 樹脂 50 樹脂 44 樹脂 44 樹脂 44 シート 中間層 b 使用樹脂の種類 樹脂 44 樹  Surface layer a 1 Resin 1 Resin 1 Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.003 0.8 0.1 Grease 44 Resin 45 Resin 46 Resin 47 Resin 49 Resin 52 Resin 50 Resin 44 Resin 44 Resin 44 Resin 44 Sheet Intermediate layer b Type Resin 44 Tree
肉厚 （mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 層構成 0.8 脂 15 樹脂 16  Thickness (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Layer structure 0.8 Fat 15 Resin 16
裏層 c 使用樹脂の種類 樹 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 肉厚 （mm) 0.1 0.1 0.1 0.1 0.1 0.1 0-1 0.1 0.003 0.8 0.1 総肉厚 （mm) 2 2 2 2 2 2 2 2 1.806 3.4 1 全光線透過率は） 67.2 65.4 76.1 61.1 75.9 66.3 76.5 58.8 70.9 69.8 77.3 光学特 曇り度 (¾) 99.3 99.4 98.1 99.5 98.2 99.4 98 99.5 99.1 99.2 97.8 性 拡散率は） 24.3 25.9 14.9 28.9 15 25.1 14.7 29.9 21.1 22.6 13.3 b値 - 0.1 - 0.1 0.1 0.3 0.2 0.2 0.2 0.3 0.1 0.2 0.2 耐光性 色差 ΔΕ 0.4 1 0.5 0.6 0.5 0.5 0.5 0.5 1.5 0.5 0.5 寸法安定性 吸水反り （mm) 0.32 0.34 0.32 0.32 0.32 0.32 0.32 0.32 0.32 1.09 0.31 Back layer c Type of resin Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0-1 0.1 0.003 0.8 0.1 Total thickness (mm) 2 2 2 2 2 2 2 2 1.806 3.4 1 Total light transmittance is 67.2 65.4 76.1 61.1 75.9 66.3 76.5 58.8 70.9 69.8 77.3 Optical haze (¾) 99.3 99.4 98.1 99.5 98.2 99.4 98 99.5 99.1 99.2 97.8 ) 24.3 25.9 14.9 28.9 15 25.1 14.7 29.9 21.1 22.6 13.3 b value-0.1-0.1 0.1 0.3 0.2 0.2 0.2 0.3 0.1 0.2 0.2 Light resistance Color difference ΔΕ 0.4 1 0.5 0.6 0.5 0.5 0.5 0.5 1.5 0.5 0.5 Dimensional stability Water absorption warpage (mm) 0.32 0.34 0.32 0.32 0.32 0.32 0.32 0.32 0.32 1.09 0.31
表 I I一 1 0Table I I 1 0
Figure imgf000038_0001
Figure imgf000038_0001
例 例 例 例 例 例 例 例 例 例 例 Example Example Example Example Example Example Example Example Example Example Example
41 42 43 44 45 46 47 48 49 50 51 使用樹脂の種類 樹脂 1 樹脂 12 樹脂 14 樹脂 17 樹脂 17 樹脂 27 樹脂 26 樹脂 18 樹脂 19 樹脂 20 樹脂 表層 a 21 肉厚 (mm) 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 使用樹脂の種類 樹脂 44 樹脂 44 樹脂 44 樹脂 37 樹脂 38 樹脂 28 樹脂 28 樹脂 28 樹脂 41 42 43 44 45 46 47 48 49 50 51 Resin type Resin 1 Resin 12 Resin 14 Resin 17 Resin 17 Resin 27 Resin 26 Resin 18 Resin 19 Resin 20 Resin Surface a 21 Thickness (mm) 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 Resin type Resin 44 Resin 44 Resin 44 Resin 37 Resin 38 Resin 28 Resin 28 Resin 28 Resin
間層 b 28 樹脂 28 樹脂 28 シー卜 中  Interlayer b 28 Resin 28 Resin 28 Seed Medium
肉厚 （mm) 10 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8  Thickness (mm) 10 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8
層構成 1. 8 1. 8 使用樹脂の種類 樹脂 1 樹脂 12 樹脂 14 樹脂 17 樹脂 17 樹脂 27 樹脂 26 樹脂 18 樹脂 19 樹脂 20 樹脂 21 裏層 c  Layer structure 1. 8 1. 8 Resin type Resin 1 Resin 12 Resin 14 Resin 17 Resin 17 Resin 27 Resin 26 Resin 18 Resin 19 Resin 20 Resin 21 Resin c
肉厚 （mm) 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0- 1 0. 1 0. 1 0. 1 0. 1 総肉厚 （mm) 10. 2 2 2 2 2 2 2 2 2 2 2 全光線透過率は） 53. 8 67. 8 71. 8 69. 3 75. 8 70. 2 70. 3 71. 1 70. 6 73. 9 63 光学特 曇り度 W 96. 3 99. 4 99. 1 99. 1 98. 2 99. 2 99. 2 99. 1 99. 2 98. 8 99. 5 性 拡散率は） 30. 2 24. 6 19. 7 22. 8 15. 1 22 21. 9 20. 7 21. 6 17 27. 5 b値 0. 4 0. 3 - 0. 1 0. 2 0. 2 0. 2 0. 1 0 1 0. 2 0. 3 耐光性 色差 Δ Ε 0. 5 0. 4 1. 3 0. 6 1. 5 1. 4 0. 6 1. 4 0. 3 0. 6 0. 6 寸法安定性 吸水反り （mm) 0. 32 0. 32 0. 32 1. 38 0. 27 0. 28 1. 16 0. 32 0. 32 0. 31 0. 31 Thickness (mm) 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0- 1 0. 1 0. 1 0. 1 0. 1 Total thickness (mm) 10. 2 2 2 2 2 2 2 2 2 2 2 Total light transmittance) 53. 8 67. 8 71. 8 69. 3 75. 8 70. 2 70. 3 71. 1 70. 6 73. 9 63 Optical characteristics Haze W 96 3 99. 4 99. 1 99. 1 98. 2 99. 2 99. 2 99. 1 99. 2 98. 8 99. 5 Sex diffusion rate) 30. 2 24. 6 19. 7 22. 8 15 1 22 21. 9 20. 7 21. 6 17 27.5 b value 0. 4 0. 3-0. 1 0. 2 0. 2 0. 2 0. 1 0 1 0. 2 0. 3 Light resistance Color difference Δ Ε 0. 5 0. 4 1. 3 0. 6 1. 5 1. 4 0. 6 1. 4 0. 3 0. 6 0. 6 Dimensional stability Water absorption warpage (mm) 0. 32 0. 32 0. 32 1. 38 0. 27 0. 28 1. 16 0. 32 0. 32 0. 31 0. 31
Figure imgf000039_0001
表 II— 1 1
Figure imgf000039_0001
Table II— 1 1
例 例 例 例 例 例 例 例 例 例 例 52 53 54 55 56 57 58 59 60 61 62 使用樹脂の種類 樹脂 22 樹脂 24 樹脂 25 樹脂 17 樹脂 17 樹脂 17 樹脂 17 樹脂 17 樹脂 17 樹脂 17 a 樹脂 表層 17 肉厚 （mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 類 樹脂 28 樹脂 28 樹脂 44 樹脂 29 樹脂 30 樹脂 31 樹脂 33 樹脂 36 樹脂 34 樹脂 42 樹脂 43 シ一卜 中間層 b 使用樹脂の種  Example Example Example Example Example Example Example Example Example Example 52 53 54 55 56 57 58 59 60 61 62 Resin Type Resin 22 Resin 24 Resin 25 Resin 17 Resin 17 Resin 17 Resin 17 Resin 17 Resin 17 Resin 17 a Resin Surface 17 Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Type Resin 28 Resin 28 Resin 44 Resin 29 Resin 30 Resin 31 Resin 33 Resin 36 Resin 34 Resin 42 Resin 43 Resin 1 Intermediate layer b Type of resin used
肉厚 （mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 層構成  Thickness (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Layer structure
裏層 c 使用樹脂の種類 樹脂 22 樹脂 24 樹脂 25 樹脂 17 樹脂 17 樹脂 17 榭脂 17 樹脂 17 樹脂 17 樹脂 17 樹脂 17 肉厚 （mm) 0.1 0.1 0.1 0.1 0.1 0.1 0-1 0.1 0.1 0.1 0.1 総肉厚 （mm) 2 2 2 2 2 2 2 2 2 2 2 全光線透過率 (¾ 75.5 63.9 66 77.1 61.8 76.8 66.9 77.6 59.3 67.5 66.1 光学特 曇り度 ） 98.4 99.5 99.4 97.7 99.5 97.8 99.4 97.1 99.5 99.3 99.4 性 拡散率は） 15.2 26.9 25.4 14 28.3 14.4 24.4 13.1 29.4 23.8 25.3 b値 0.2 0.2 0.2 0 0.2 0.1 0.1 0.1 0.2 -0.4 - 0.3 耐光性 色差 ΔΕ 0.6 0.6 0.6 0.6 0.7 0.6 0.6 0.6 0.7 0.5 1.2 寸法安定性 吸水反り （mm) 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.31 0.3 Back layer c Resin type Resin 22 Resin 24 Resin 25 Resin 17 Resin 17 Resin 17 Resin 17 Resin 17 Resin 17 Resin 17 Resin 17 Resin 17 Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0-1 0.1 0.1 0.1 0.1 Total meat Thickness (mm) 2 2 2 2 2 2 2 2 2 2 2 Total light transmittance (¾ 75.5 63.9 66 77.1 61.8 76.8 66.9 77.6 59.3 67.5 66.1 Optical haze) 98.4 99.5 99.4 97.7 99.5 97.8 99.4 97.1 99.5 99.3 99.4 Sexual diffusion 15.2 26.9 25.4 14 28.3 14.4 24.4 13.1 29.4 23.8 25.3 b value 0.2 0.2 0.2 0 0.2 0.1 0.1 0.1 0.2 -0.4-0.3 Light resistance Color difference ΔΕ 0.6 0.6 0.6 0.6 0.7 0.6 0.6 0.6 0.7 0.5 1.2 Dimensional stability Water absorption warpage ( mm) 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.31 0.3
丄 丄
Figure imgf000040_0001
[例 III] (帯電防止剤を含有する多層シートの例）
Figure imgf000040_0001
[Example III] (Example of multilayer sheet containing antistatic agent)
スチレン系共重合体として、例 IIと同様にして製造した表 III— 1のスチレン系共重合 体 A— 1 A— 4を使用した。  As the styrene copolymer, the styrene copolymer A-1 A-4 shown in Table III-1 produced in the same manner as in Example II was used.
未溶融化合物として、例 1 (表 I 2)の架橋ビーズ B C D—:! D 4 E—：! E 4を使用した。 ポリエーテルエステルアミドブロック共重合体 (F)の製造は以下のように行った。 力プロラタタム 55部、ビスフエノール Aのエチレンォキシド付カ卩物 30部及びアジピン 酸 15部力もポリエーテルエステルアミド (F— 1)を得た。このポリエーテルエステルァ ミドの屈折率は 1. 530であった。また、力プロラタタム 40部、ビスフエノール Aのェチ レンォキシド付加物 45部及びアジピン酸 15部からポリエーテルエステルアミド (F— 2 )を得た。このポリエーテルエステルアミドの屈折率は 1. 490であった。 As an unmelted compound, the crosslinked beads BCD— :! D 4 E— :! E 4 of Example 1 (Table I 2) were used. Production of the polyetheresteramide block copolymer (F) was carried out as follows. A force of 55 parts of prolatatam, 30 parts of bisphenol A with ethylene oxide and 15 parts of adipic acid also gave polyether ester amide (F-1). This polyetheresteramide had a refractive index of 1.530. Further, polyether ester amide (F-2) was obtained from 40 parts of force prolatatam, 45 parts of ethylene oxide adduct of bisphenol A and 15 parts of adipic acid. The refractive index of this polyetheresteramide was 1.490.
[0079] ァ-オン系界面活性剤及び非アミンノ-オン系界面活性剤 (G)は、ァ-オン系界 面活性剤としてドデシルスルホン酸ナトリウムを、非アミン系ノ二オン系界面活性剤と してグリセリンステアリン酸ジエステルを用いた。  [0079] The ionic surfactant and the non-amine nonionic surfactant (G) include sodium dodecyl sulfonate as the ionic surfactant, non-amine nonionic surfactant, Then, glycerin stearic acid diester was used.
[0080] スチレン系共重合体 (A— 1)〜（A— 4)、未溶融化合物として B、 C、（D— 1)〜（D —4)、 （Ε—1)〜（Ε—4)、ヒンダードアミン系化合物としてビス（2, 2, 6, 6—テトラメ チル— 4 ピペリジル）セバケート、ベンゾトリアゾール系化合物として 2— (2H ベン ゾトリァゾールー 2 ィル） -4, 6 ジ t—ペンチルフエノール、ポリエーテルエステ ルアミドブロック共重合体として (F— 1)と (F— 2)、ァ-オン系界面活性剤にドデシル スルホン酸ナトリウムを、非アミンノ-オン系界面活性剤にグリセリンステアリン酸ジェ ステルを用いて事前にァ-オン系界面活性剤 Z非アミンノ-オン系界面活性剤 = 1 OZ90部の割合でブレンドしたものを複合界面活性剤として、表 III— 2〜4に示す配 合比にて混合した。得られた混合物を 40mm径の単軸押出し機にて、温度 240°C、 スクリュー回転数 lOOrpmにて混練し、ペレット化を行い、表 III— 2〜ΠΙ— 4に示した スチレン系榭脂組成物 1〜29のペレットを得た。  [0080] Styrenic copolymers (A-1) to (A-4), B, C, (D-1) to (D-4), (4-1) to (Ε-4) as unmelted compounds ), Bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate as a hindered amine compound, 2- (2H benzotriazole-2-yl) as a benzotriazole compound, -4, 6 di-t-pentylphenol, poly As ether ester amide block copolymers (F-1) and (F-2), doonyl sodium sulfonate is used as an ionic surfactant, and glyceryl stearate ester is used as a non-amine ionic surfactant. Used in advance as a ionic surfactant Z non-amine ionic surfactant = 1 OZ 90 parts blended as a composite surfactant with the mixing ratio shown in Table III-2-4 Mixed. The resulting mixture was kneaded with a 40 mm diameter single screw extruder at a temperature of 240 ° C and a screw rotation speed of lOOrpm, pelletized, and the styrene-based resin composition shown in Table III-2 to IV-4 1 to 29 pellets were obtained.
[0081] 尚、表 III 2〜ΠΙ— 3のスチレン系榭脂組成物 1〜18は、表層 a、裏層 cのスチレン 系榭脂組成物（(A)成分）に対応しており、表 III— 4のスチレン系榭脂組成物 19〜2 9は、中間層 bの榭脂組成物（（B)成分）に対応している。  [0081] The styrene-based resin compositions 1 to 18 in Table III 2 to 3 correspond to the styrene-based resin compositions (component (A)) of the surface layer a and the back layer c. The styrene-based resin compositions 19 to 29 of III-4 correspond to the resin composition (component (B)) of the intermediate layer b.
[0082] [例 III 1〜ΠΙ— 34]  [0082] [Example III 1 ~ ΠΙ- 34]
スチレン系榭脂糸且成物 1〜29を用いて、フィードブロックを有する Tダイ方式の多層 押出機にて表 III— 5〜ΠΙ— 8に示した 3層構成のシートを作製した。尚、多層押出機 は、中間層用が 65mm φのフルフライトスクリューの単軸押出機 1台、表裏層用に 30 mm φのフルフライトスクリューの単軸押出機各 1台からなり各々の溶融榭脂がフィー ドブロックで合流多層化される試験押出機を使用した。シートィ匕の各シリンダー温度 は 230°Cにて運転、成形した。 Three-layered sheets shown in Tables III-5 to VIII-8 were prepared by using T-die type multi-layer extruders having a feed block, using styrene-based cocoon yarn composites 1 to 29. The multi-layer extruder consists of a single 65mm φ full flight screw single screw extruder for the intermediate layer and a single 30mm φ full flight screw single screw extruder for the front and back layers. Fat is fee A test extruder that was joined and multilayered with a deblock was used. Each cylinder temperature of sheety was operated and molded at 230 ° C.
[0083] 得られたシートの光学特性、耐光性、吸水反り、帯電防止性、耐傷付き性を評価し 、そのデータを表 III 5〜ΠΙ— 8に示した。 [0083] The optical properties, light resistance, water absorption warpage, antistatic property and scratch resistance of the obtained sheet were evaluated, and the data are shown in Tables III-5 to IV-8.
例 III (帯電防止剤を含有する多層シートの例）においては、曇り度 99%以上、全光 線透過率 65%以上、拡散率 23%以上、 b値は 1以下である場合、光学特性が特に 優れていると判断できる。耐光性は色差 ΔΕ値が 1未満、寸法安定性は吸水反りが 1 mm以下、帯電防止性は表面固有抵抗値が 1012 Ω以下である場合、優れていると判 断できる。 In Example III (example of multilayer sheet containing antistatic agent), if the haze is 99% or more, the total light transmittance is 65% or more, the diffusivity is 23% or more, and the b value is 1 or less, the optical characteristics are It can be judged that it is particularly excellent. It can be judged that light resistance is excellent when the color difference ΔΕ value is less than 1, dimensional stability is water absorption warpage of 1 mm or less, and antistatic property is surface resistivity of 10 12 Ω or less.
例111 1〜111 8、 III— 22は、これらの特性を全て併せ持つ特に好ましい実施例で ある。  Examples 111 1 to 111 8, III-22 are particularly preferred embodiments having all these properties.
例 III— 9、 111— 10、 111— 20、 111— 21、 111— 23、 111— 24、 III— 31〜ΠΙ— 34はその他 の実施例である。  Examples III-9, 111-10, 111-20, 111-21, 111-23, 111-24, III-31 to ΠΙ-34 are other examples.
例 m - 11〜m - 19, in- 25〜m - 30は比較例である。  Examples m-11 to m-19, in-25 to m-30 are comparative examples.
ポリエーテルエステルアミドブロック共重合体を使用することで、得られた成形品の 耐傷つき性が向上し、更に複合界面活性剤を併用した場合は、耐傷付き性が著しく 向上していることがわ力る。  By using the polyether ester amide block copolymer, the scratch resistance of the obtained molded product is improved, and when the composite surfactant is used in combination, the scratch resistance is remarkably improved. Power.
[0084] [表 21] 表 m— 1  [0084] [Table 21] Table m— 1
Figure imgf000042_0001
Figure imgf000042_0001
[0085] [表 22] 2 [0085] [Table 22] 2
S¾86200 配合 Contains S¾86200
ベンゾ卜  Benzo
スチレン スチレン スチレン ヒンダ一 ポリエーテルエステ  Styrene Styrene Styrene Hinder One Polyether Este
リアゾー  Riazo
表 系共重合 系共重合 系共重合 ドアミン 未溶融化合物 ルアミドブロック共 複合界面 体 A— 1 体 A - 2 体 A— 3 ル系化合  Surface copolymerization Copolymerization system copolymerization Doamine Unmelted compound Luamide block copolymer Composite interface A— 1 body A-2 body A— 3
系化合物 重合体 活性剤 物  Compound polymer activator
スチレン系樹脂組成物名 質量部 質量部 質量部 質量部 質量部 質量部 種類 質量部 質量部 樹脂 1 ― 100 ― 0.3 0.3 D- 1 3.0 F— 1 15 1 樹脂 2 ― 100 ― 0.05 0.05 D— 1 3.0 F— 1 15 1 樹脂 3 ― 100 ― 3.0 3.0 D— 1 3.0 F - 1 15 1 樹脂 4 ― 100 ― 0.3 0.3 D- 1 0.5 F- 1 15 1 樹脂 5 ― 100 一 0.3 0.3 D- 1 13.0 F- 1 15 1 樹脂 6 ― 100 ― 0.3 0.3 D— 2 3.0 F— 1 15 1 樹脂 7 ― 100 一 0.3 0.3 D- 3 3.0 F- 1 15 1 樹脂 8 ― 100 ― 0.3 0.3 D-4 3.0 F- 1 15 1 樹脂 9 ― 100 ― 0.3 0.3 E— 1 3.0 F— 1 15 1 樹脂 10 100 ― ― 0.3 0.3 D- 1 3.0 F- 1 15 1 樹脂 1 1 ― 一 100 0.3 0.3 D- 1 3.0 F- 1 15 1 樹脂 12 ― 100 一 0.3 0.3 D- 1 3.0 F 1 3 1 樹脂 1 3 ― 100 ― 0.3 0.3 D - 1 3.0 F- 1 6 1 樹脂 14 一 100 ― 0.3 0.3 D— 1 3.0 F- 1 10 1 Styrenic resin composition name Mass part Mass part Mass part Mass part Mass part Mass part Type Mass part Mass part Resin 1-100-0.3 0.3 D- 1 3.0 F-1 15 1 Resin 2-100-0.05 0.05 D-1 3.0 F- 1 15 1 Resin 3-100-3.0 3.0 D-1 3.0 F-1 15 1 Resin 4-100-0.3 0.3 D- 1 0.5 F- 1 15 1 Resin 5-100 1 0.3 0.3 D- 1 13.0 F- 1 15 1 Resin 6 ― 100 ― 0.3 0.3 D― 2 3.0 F― 1 15 1 Resin 7 ― 100 1 0.3 0.3 D- 3 3.0 F- 1 15 1 Resin 8 ― 100 ― 0.3 0.3 D-4 3.0 F- 1 15 1 Resin 9 ― 100 ― 0.3 0.3 E ― 1 3.0 F ― 1 15 1 Resin 10 100 ― ― 0.3 0.3 D- 1 3.0 F- 1 15 1 Resin 1 1 ― 1 100 0.3 0.3 D- 1 3.0 F- 1 15 1 Resin 12-100 1 0.3 0.3 D- 1 3.0 F 1 3 1 Resin 1 3-100-0.3 0.3 D-1 3.0 F- 1 6 1 Resin 14 1 100-0.3 0.3 D-1 3.0 F- 1 10 1
表 III— 3Table III-3
0087 配合 0087 Formulation
一 ベンゾ卜  1 Benzo
スチレン スチレン スチレン ヒンダ ポリエーテルエステ  Styrene Styrene Styrene Hinder Polyether Este
リアゾー  Riazo
系共重合 系共重合 系共重合 ドアミン 未溶融化合物 ルアミドブロック共 複合界面 体 A— 1 体 A— 2 体 A— 3 ル系化合  Copolymer Copolymer Copolymer Copolymer Doamine Unmelted compound Luamide block copolymer Composite interface A— 1 body A— 2 body A— 3
系化合物 重合体 活性剤 物  Compound polymer activator
スチレン系樹脂組成物名 質量部 質量部 質 S部 質量部 質量部 種類 質: ki ιί 種類 質暈部 質量咅 β 樹脂 15 ― 100 ― 0.3 0.3 D - 1 3.0 F - 1 25 1 樹脂 16 ― 100 ― 0.3 0.3 D - 1 3.0 F 1 15 ― 樹脂 17 ― 100 ― 0.3 0.3 D— 1 3.0 F - 1 15 5 樹脂 18 ― 100 ― 0.3 0.3 D— 1 3.0 F— 2 15 1 Styrenic resin composition name Mass part Mass part S Part Mass part Mass part Type Quality: ki ιί Type Material part Mass 咅 β Resin 15 ― 100 ― 0.3 0.3 D-1 3.0 F-1 25 1 Resin 16 ― 100 ― 0.3 0.3 D-1 3.0 F 1 15-Resin 17-100-0.3 0.3 D-1 3.0 F-1 15 5 Resin 18-100-0.3 0.3 D-1 3.0 F-2 15 1
4 Four
S¾S0082 配合 Formulation S¾S0082
スチレン スチレン スチレン ヒンダ一 ベンゾ卜 ポリエーテルエステ 系共重合 系共重合 系共重合 ドアミン リアゾ一 未溶融化合物 ルアミドブロック共 複合界面 表 体 A— 1 体 A— 3 体 A— 4 活性剤 系化合物 ル系化合 重合体  Styrene Styrene Styrene Hinder Benzene Polyether Este Copolymer Copolymer Copolymer Copolymer Doamine Reazo One Unmelted Compound Luamide Block Co Composite Interface Surface A— 1 Compound A— 3 Compound A— 4 Activator Compound Compound polymer
スチレン系樹脂組成物名 質量部 質量部 質量部 質量部 質量部 種類 質量部 種類 質量部 質量部 樹脂 1 9 100 ― ― ― E— 1 3 ― ― 樹脂 2 0 100 ― ― E— 1 0. 5 ― ― 樹脂 2 1 100 ― ― ― E - 1 13 ― ― ― 樹脂 2 2 ― 100 ― ― ― E - 2 3 ― 樹脂 2 3 ― 100 ― ― ― E— 3 3 ― ― ― 樹脂 2 4 ― 100 ― ― ― E - 4 3 ― ― ― 樹脂 2 5 ― 100 ― ― ― B 3 ― ― 樹脂 2 6 ― 100 ― ― ― C 3 ― ― ― 樹脂 2 7 ― 100 ― ― D— 1 3 ― ― ― 樹脂 2 8 100 ― ― ― ― E— 1 3 ― ― ― 樹脂 2 9 100 ― ― E— 1 3 ― ― ― Styrene resin composition name Mass part Mass part Mass part Mass part Mass part Type Mass part Type Mass part Mass part Resin 1 9 100---E-1 3--Resin 2 0 100--E-1 0.5- -Resin 2 1 100---E-1 13---Resin 2 2-100---E-2 3-Resin 2 3-100---E-3 3---Resin 2 4-100-- ― E-4 3 ― ― ― Resin 2 5 ― 100 ― ― ― B 3 ― ― Resin 2 6 ― 100 ― ― ― C 3 ― ― ― Resin 2 7 ― 100 ― ― D ― 1 3 ― ― ― Resin 2 8 100----E-1 3---Resin 2 9 100--E-1 3---
表 II卜 5 Table II-5
例 例 例 例 例 例 例 例 1 2 3 4 5 6 7 8 使用樹脂の種類 樹脂 1 樹脂  Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8 Resin Type Resin 1 Resin
表層 a 7 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 14 樹脂 16  Surface layer a 7 Resin 1 Resin 1 Resin 1 Resin 1 Resin 14 Resin 16
肉厚 （mm) 0.1 0.1 0.1 0.1 0.01 0.1 0.1 0.1 使用樹脂の種類 樹脂 19 樹脂 19 樹脂 26 樹脂 23 樹脂 19 樹脂 19 樹脂 19 榭脂 19 シー卜 中間層 b  Thickness (mm) 0.1 0.1 0.1 0.1 0.01 0.1 0.1 0.1 Resin type Resin 19 Resin 19 Resin 26 Resin 23 Resin 19 Resin 19 Resin 19 Grease 19 Seed 19 Middle layer b
肉厚 (mm) 1.8 1.8 1.8 1.8 1.8 5 1.8 1.8 層構成  Thickness (mm) 1.8 1.8 1.8 1.8 1.8 5 1.8 1.8 Layer structure
使用樹脂の種類 樹脂 1 樹脂 7 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 14 樹脂 16 S 〔¾S0082 肉厚 (mm) 0. 1 0.1 0.1 0. 1 0.01 0.1 0. 1 0.1 総肉 mm) 2 2 2 2 1.82 5.2 2 2 全光線透過率は） 67.2 65.3 66.7 68 67.3 65.1 67.3 68.2 光学特 曇り度 ) 99.3 99.5 99.4 99.2 99.3 99.5 99.3 99.2 性  Resin type Resin 1 Resin 7 Resin 1 Resin 1 Resin 1 Resin 1 Resin 14 Resin 16 S (¾S0082 Thickness (mm) 0. 1 0.1 0.1 0. 1 0.01 0.1 0. 1 0.1 Total thickness mm) 2 2 2 2 1.82 5.2 2 2 Total light transmittance is 67.2 65.3 66.7 68 67.3 65.1 67.3 68.2 Optical haze) 99.3 99.5 99.4 99.2 99.3 99.5 99.3 99.2
拡散率 ） 24.5 26.4 24.9 23.4 24.4 26.9 24.4 23.2 b値 0.7 0.8 0.6 0.7 0.8 0.8 0.6 0.5 ϋ ϊί光性 色差 ΔΕ 0.3 0.4 0.3 0.3 0.5 0.3 0.3 0.3 寸法安定性 吸水反り （mm) 0.46 0.46 0.45 0.45 0.46 0.45 0.39 0.45 帯電防止性 表面固有抵抗（Ω) 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 IX 1012 1X10" 耐傷付き性 優 優 優 優 優 優 優 良 Diffusivity) 24.5 26.4 24.9 23.4 24.4 26.9 24.4 23.2 b value 0.7 0.8 0.6 0.7 0.8 0.8 0.6 0.5 ϋ Fluorescent color difference ΔΕ 0.3 0.4 0.3 0.3 0.5 0.3 0.3 0.3 Dimensional stability Water absorption warpage (mm) 0.46 0.46 0.45 0.45 0.46 0.45 0.39 0.45 Antistatic surface specific resistance (Ω) 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 IX 10 12 1X10 "Scratch resistance excellent excellent excellent excellent excellent excellent excellent
表 III 6 Table III 6
例 例 例 例 例 例 例 例 例 例 例 Example Example Example Example Example Example Example Example Example Example Example
9 10 11 12 13 14 15 16 17 18 19 使用樹脂の種類 樹脂 1 樹脂 1 樹脂 11 樹脂 10 樹脂 2 樹脂 3 樹脂 4 樹脂 5 樹脂 6 樹脂 8 樹脂 9 表層 a 9 10 11 12 13 14 15 16 17 18 19 Type of resin used Resin 1 Resin 1 Resin 11 Resin 10 Resin 2 Resin 3 Resin 4 Resin 5 Resin 6 Resin 8 Resin 9 Resin a
肉厚 (mm) 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 使用樹脂の種類 樹脂 28 樹脂 29 樹脂 19 樹脂 19 樹脂 19 樹脂 19 樹脂 19 樹脂 19 樹脂 19 樹脂 19 樹脂 19 シート 中間層 b  Thickness (mm) 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 Type of resin used Resin 28 Resin 29 Resin 19 Resin 19 Resin 19 Resin 19 Resin 19 Resin 19 Resin 19 Resin 19 Resin 19 Sheet Intermediate layer b
肉厚 (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 層構成  Thickness (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Layer structure
使用樹脂の種類 樹脂 1 樹脂 1 樹脂 11 樹脂 10 樹脂 2 樹脂 3 樹脂 4 樹脂 5 樹脂 6 樹脂 8 樹脂 9 裏層 c  Resin type Resin 1 Resin 1 Resin 11 Resin 10 Resin 2 Resin 3 Resin 4 Resin 5 Resin 6 Resin 8 Resin 9 Back layer c
肉厚 （mm) 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 総肉厚 （mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 全光線透過率 W 65.6 71.3 66.5 66.7 67.4 67.0 70.2 59.5 71.8 60.2 62.3 光学特 曇り度 ( > 99.5 99.0 99.4 99.4 99.3 99.3 99. 1 99.6 98.8 99.6 99.5 性  Thickness (mm) 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 Total thickness (mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Total light transmittance W 65.6 71.3 66.5 66.7 67.4 67.0 70.2 59.5 71.8 60.2 62.3 Optical characteristics Haze (> 99.5 99.0 99.4 99.4 99.3 99.3 99. 1 99.6 98.8 99.6 99.5
拡散率は） 26.0 19.2 25.4 25.2 24.3 24.8 20.8 29.8 18.6 29.2 28.7 b値 0.8 0.8 0.8 0.7 0.6 1.5 0.8 0.9 0.8 0.8 0.8 26.0 19.2 25.4 25.2 24.3 24.8 20.8 29.8 18.6 29.2 28.7 b value 0.8 0.8 0.8 0.7 0.6 1.5 0.8 0.9 0.8 0.8 0.8
P 光性 色差 ΔΕ 0.3 1.1 1. 1 0.3 1. 1 0. 1 0.3 0.3 0.3 0.3 0.3 寸法安定性 吸水反り （mm) 1.45 0.36 0.42 1. 18 0.46 0.46 0.45 0.45 0.46 0.46 0.45 帯電防止性 表面固有抵抗（Ω) 1X 1010 1X 1010 1X 1010 1 X 1010 1X 1010 1X 1010 1X10'" 1X1010 1X 1010 1X1010 1X 1010 耐傷付き性 優 優 優 優 優 優 優 優 優 優 優 P Lightness Color difference ΔΕ 0.3 1.1 1. 1 0.3 1. 1 0. 1 0.3 0.3 0.3 0.3 0.3 Dimensional stability Water absorption warpage (mm) 1.45 0.36 0.42 1. 18 0.46 0.46 0.45 0.45 0.46 0.46 0.45 Antistatic property Surface resistivity ( 1X 10 10 1X 10 10 1X 10 10 1 X 10 10 1X 10 10 1X 10 10 1X10 '"1X10 10 1X 10 10 1X10 10 1X 10 10 Scratch resistance Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent Excellent
Figure imgf000048_0001
表 III 7
Figure imgf000048_0001
Table III 7
例 例 例 例 例 例 例 例 例 例 例 20 21 22 23 24 25 26 27 28 29 30 使用樹脂の種類 樹脂 12 樹脂 13 樹脂 15 樹脂 17 榭脂 18 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 表層 a  Example Example Example Example Example Example Example Example Example Example 20 21 22 23 24 25 26 27 28 29 30 Resin type Resin 12 Resin 13 Resin 15 Resin 17 Resin 18 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Surface layer a
肉厚 （mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0. 1 脂 19 樹脂 19 樹脂 19 樹脂 20 樹脂 21 樹脂 22 榭脂 24 樹脂 27 樹脂 25 シー卜 中間層 b 使用樹脂の種類 樹脂 19 樹脂 19 樹  Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Fat 19 Resin 19 Resin 19 Resin 20 Resin 21 Resin 22 Grease 24 Resin 27 Resin 25 Seed 卜 Middle layer b Type of resin used Resin 19 Resin 19 Tree
肉厚 （mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 層構成 1.8 使用樹脂の種類 樹脂 12 樹脂 13 樹脂 15 樹脂 17 樹脂 18 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 裏層 c 1 肉厚 (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 総肉厚 (mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 全光線透過率 tt) 67.5 67.4 67.1 66.9 56.0 73.1 58.0 73.0 63.4 73.5 55.8 光学特 曇り度は） 99.3 99.3 99.3 99.4 99.8 98.4 99.7. 98.4 99.5 98.3 99.8 性  Thickness (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Layer structure 1.8 Resin type Resin 12 Resin 13 Resin 15 Resin 17 Resin 18 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin Back layer c 1 Thickness ( mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Total thickness (mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Total light transmittance tt) 67.5 67.4 67.1 66.9 56.0 73.1 58.0 73.0 63.4 73.5 55.8 Optical cloudiness 99.3 99.3 99.3 99.4 99.8 98.4 99.7. 98.4 99.5 98.3 99.8
拡散率は） 24.4 24.4 24.6 24.7 31.9 17.2 31.0 17.4 27.6 16.9 32.1 b値 0.5 0.6 1.0 1.3 0.8 0.6 0.8 0.7 0.7 0.7 0.8 光性 色差 ΔΕ 0.3 0.3 0.3 0.3 0.4 0.3 0.4 0.3 0.3 0.3 0.3 寸法安定性 吸水反り （mm) 0.37 0.39 0.58 0.47 0.45 0.46 0.47 0.46 0.46 0.47 0.46 带電防止性 表面固有抵抗（Ω) ixio'b 1X1014 1X1010 1X109 1X1010 ιχιο,ϋ 1X1010 1X1010 1X1010 1X1010 1X101 耐傷付き性 不良 良 優 優 優 優 優 優 優 優 優 24.4 24.4 24.6 24.7 31.9 17.2 31.0 17.4 27.6 16.9 32.1 b value 0.5 0.6 1.0 1.3 0.8 0.6 0.8 0.7 0.7 0.7 0.8 Light color difference ΔΕ 0.3 0.3 0.3 0.3 0.4 0.3 0.4 0.3 0.3 0.3 0.3 Dimensional stability Water absorption warpage (mm ) 0.37 0.39 0.58 0.47 0.45 0.46 0.47 0.46 0.46 0.47 0.46带電anti-surface resistivity (Ω) ixio 'b 1X10 14 1X10 10 1X10 9 1X10 10 ιχιο, ϋ 1X10 10 1X10 10 1X10 10 1X10 10 1X10 1 scratch resistance poor Good Yu Yu Yu Yu Yu Yu Yu Yu Yu Yu
Figure imgf000049_0001
Figure imgf000049_0001
[0092] [例 IV] (蛍光増白剤及び帯電防止剤を含有する多層シートの例）  [Example IV] (Example of multilayer sheet containing fluorescent whitening agent and antistatic agent)
スチレン系共重合体として、例 IIと同様にして製造した表 IV— 1のスチレン系共重合 体 A— 1 A— 4を使用した。  As the styrene copolymer, the styrene copolymer A-1 A-4 of Table IV-1 produced in the same manner as in Example II was used.
未溶融化合物として、例 1 (表 I 2)の架橋ビーズ B C D— 1 D— 4 E— 1 E 4を使用した。  As an unmelted compound, the crosslinked beads B C D— 1 D— 4 E— 1 E 4 of Example 1 (Table I 2) were used.
[0093] ポリエーテルエステルアミドブロック共重合体 (F)として、例 IIIと同様にして、屈折率 1. 530のポリエーテルエステルアミド（F—l)、及び屈折率 1. 490のポリエーテルエ ステルアミド (F— 2)を得た。  [0093] As the polyether ester amide block copolymer (F), in the same manner as in Example III, a polyether ester amide (F-l) having a refractive index of 1.530 and a polyether ester amide having a refractive index of 1.490 (F — I got 2).
[0094] ァニオン系界面活性剤及び非アミンノニオン系界面活性剤 (G)は、ァニオン系界 面活性剤としてドデシルスルホン酸ナトリウムを、非アミン系ノ二オン系界面活性剤と してグリセリンステアリン酸ジエステルを用いた。  [0094] An anionic surfactant and a non-amine nonionic surfactant (G) are sodium dodecyl sulfonate as an anionic surfactant and glycerin stearic acid as a non-amine nonionic surfactant. Diester was used.
[0095] 着色剤（H)は、いわゆる蛍光増白剤である 2, 5 チォフェンジィル（5 t ブチル — 1, 3 ベンゾキサゾール）（チバスペシャルティケミカルズ社製ュビテックス OB)を ( H— 1)、無機顔料である DAYGRO社製 ZQ— 19を (H— 2)、有機染料である三菱 化学社製ダイァレジン BLUE Jを (H— 3)として用いた。 [0095] The colorant (H) is a so-called fluorescent whitening agent, 2, 5 thiofensyl (5 t butyl — 1, 3 benzoxazole) (Ubitex OB manufactured by Ciba Specialty Chemicals) (H-1), inorganic The pigment DAYGRO ZQ-19 (H-2) and the organic dye Mitsubishi Chemical resin Dairesin BLUE J was used as (H-3).
[0096] スチレン系共重合体 (A— 1)〜（A— 4)、未溶融化合物として B、 C、（D— 1)〜（D —4)、（Ε—1)〜（Ε—4)、ヒンダードアミン系化合物としてビス（2, 2, 6, 6—テトラメ チル— 4 ピペリジル）セバケート、ベンゾトリアゾール系化合物として 2— (2H ベン ゾトリァゾールー 2 ィル） -4, 6 ジ t—ペンチルフエノール、ポリエーテルエステ ルアミドブロック共重合体として (F— 1)と (F— 2)、ァ-オン系界面活性剤としてドデ シルスルホン酸ナトリウムを、非アミンノ-オン系界面活性剤にグリセリンステアリン酸 ジエステルを用いて事前にァ-オン系界面活性剤 Z非アミンノ-オン系界面活性剤 = 10Z90部の割合でブレンドしたものを複合界面活性剤として、着色剤として (H— 1)〜(Η 3)を、表 IV— 2〜IV- 5に示す配合比にて混合した。得られた混合物を 40 mm径の単軸押出し機にて、温度 240°C、スクリュー回転数 lOOrpmにて混練し、ぺ レット化を行い、表 IV— 2〜IV-5に示したスチレン系榭脂組成物 1〜66のペレットを 得た。 [0096] Styrene copolymers (A-1) to (A-4), unmelted compounds B, C, (D-1) to (D-4), (Ε-1) to (と し て -4) ), Bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate as a hindered amine compound, 2- (2H benzotriazole-2-yl) as a benzotriazole compound, -4, 6 di-t-pentylphenol, poly Ether ester amide block copolymers (F-1) and (F-2), sodium dodecyl sulfonate as an ionic surfactant, and glyceryl stearic acid diester as a non-amine ionic surfactant. Use as a colorant (H-1) to (Η3) as a composite surfactant, which is a pre-adhered Z-amino surfactant Z non-amine non-ionic surfactant = blended at a ratio of 10 Z90 parts. These were mixed at the blending ratios shown in Tables IV-2 to IV-5. The resulting mixture was kneaded with a 40 mm diameter single screw extruder at a temperature of 240 ° C and a screw rotation speed of lOOrpm, pelletized, and the styrenic resins shown in Tables IV-2-IV-5. Pellets of fat composition 1 to 66 were obtained.
[0097] 尚、表 IV— 2〜IV— 3のスチレン系榭脂組成物 1〜39は、表層 a、裏層 cのスチレン 系榭脂組成物（ (A)成分）に対応しており、表 IV— 4〜IV— 5のスチレン系榭脂組成 物 40〜66は、中間層 bの榭脂組成物（（B)成分）に対応している。  [0097] The styrene-based resin compositions 1 to 39 in Tables IV-2 to IV-3 correspond to the styrene-based resin compositions (component (A)) of the surface layer a and the back layer c. The styrene-based resin compositions 40 to 66 in Tables IV-4 to IV-5 correspond to the resin composition (component (B)) of the intermediate layer b.
[0098] [例1¥—1〜1¥—82]  [0098] [Example 1——1 to 1——82]
スチレン系榭脂組成物 1〜66を用いて、フィードブロックを有する Tダイ方式の多層 押出機にて表 IV— 6〜IV— 13に示した 3層構成のシートを作製した。尚、多層押出 機は、中間層用が 65mm φのフルフライトスクリューの単軸押出機 1台、表裏層用に 30mm φのフルフライトスクリューの単軸押出機各 1台からなり各々の溶融榭脂がフィ ードブロックで合流多層化される試験押出機を使用した。シートィ匕の各シリンダー温 度は 230°Cにて運転、成形した。  Sheets having a three-layer structure shown in Tables IV-6 to IV-13 were prepared by using T-die type multi-layer extruders having feed blocks using styrene-based resin compositions 1 to 66. The multi-layer extruder consists of a single 65mmφ full flight screw single screw extruder for the intermediate layer and one 30mmφ full flight screw single screw extruder for the front and back layers. A test extruder was used in which the feed blocks were joined and multilayered. Each cylinder temperature of sheety was operated and molded at 230 ° C.
[0099] 得られたシートの光学特性、耐光性、吸水反り、帯電防止性、耐傷付き性を評価し 、そのデータを表 IV— 6〜IV— 13に示した。 [0099] Optical properties, light resistance, water absorption warpage, antistatic properties, and scratch resistance of the obtained sheets were evaluated, and the data are shown in Tables IV-6 to IV-13.
例 IV (蛍光増白剤及び帯電防止剤を含有する多層シートの例）においては、曇り度 99%以上、全光線透過率 67%以上、拡散率 18%以上、 b値 1未満である場合、光 学特性が特に優れていると判断できる。耐光性は色差 Δ Ε値が 1未満、寸法安定性 は吸水反りが lmm以下、帯電防止性は表面固有抵抗値が 1012 Ω以下である場合、 優れていると判断できる。 In Example IV (example of multilayer sheet containing fluorescent whitening agent and antistatic agent), when haze is 99% or more, total light transmittance is 67% or more, diffusivity is 18% or more, and b value is less than 1, It can be judged that the optical characteristics are particularly excellent. Light resistance is color difference Δ 差 value less than 1, dimensional stability Can be judged to be excellent when the water absorption warpage is 1 mm or less and the antistatic property is 10 12 Ω or less.
例 IV— 1〜IV— 22は、これらの特性を全て併せ持つ特に好ま ヽ実施例である。 例 IV— 23〜IV— 26、 IV— 34〜IV— 39、 IV— 46〜IV— 52、 IV— 53、 IV— 63〜IV 66、 IV— 73〜IV— 82はその他の実施例である。  Examples IV-1 to IV-22 are particularly preferred embodiments having all these characteristics. Examples IV-23 to IV-26, IV-34 to IV-39, IV-46 to IV-52, IV-53, IV-63 to IV 66, IV-73 to IV-82 are other examples. .
例 IV— 27〜IV— 33、 IV— 40〜IV— 45、 IV— 54〜IV— 62、 IV— 67〜IV— 72は 比較例である。  Examples IV-27 to IV-33, IV-40 to IV-45, IV-54 to IV-62, and IV-67 to IV-72 are comparative examples.
[表 29] 表 IV— 1  [Table 29] Table IV— 1
Figure imgf000051_0001
[表 30]
Figure imgf000051_0001
[Table 30]
表 IV— 2 Table IV-2
配合  Formulation
スチレン スチレン スチレン ヒンダ一 ベンゾ卜 ホリエーテルエステ  Styrene Styrene Styrene Hinder I Benzot Polyether Este
系共重合 系共重合 系共重合 ドアミン リアゾ一 未溶融化合物 ルアミドブロック共 複合界面  Copolymer Copolymer Copolymer Copolymer Doamine Reazo One Unmelted Compound Luamide Block Co-Compound Interface
着色剤 体 A— 1 体 A— 2 体 A— 3 系化合物 ル系化合 重合体 活性剤  Colorant Body A— 1 body A— 2 body A— 3 system compound Lu compound compound activator
スチレン系樹脂組成物名 質量部 質量部 質量部 質量部 質量部 種類 質量部 ¾頹 質量部 質量部 種類 質量部 樹脂 1 ― 100 ― 0.3 0.3 D— 1 3.0 F- 1 15 1 H— 1 0.01 樹脂 2 ― 100 ― 0.05 0.05 D— 1 3.0 F- 1 15 1 H- 1 0.01 樹脂 3 ― 100 一 3.0 3.0 D— 1 3.0 F— 1 15 1 H- 1 0.01 樹脂 4 ― 100 ― 0.3 0.3 D— 1 0.5 F - 1 15 1 H- 1 0.01 樹脂 5 - 100 ― 0.3 0.3 D— 1 13.0 F - 1 15 1 H- 1 0.01 樹脂 6 ― 100 ― 0.3 0.3 D— 2 3.0 F- 1 15 1 H- 1 0.01 樹脂 7 ― 100 ― 0.3 0.3 D— 3 3.0 F— 1 15 1 H— 1 0.01 樹脂 8 ― 100 ― 0.3 0.3 D-4 3.0 F— 1 15 1 H- 1 0.01 樹脂 9 ― 100 ― 0.3 0.3 E- 1 3.0 F- 1 15 1 H— 1 0.01 樹脂 10 100 ― ― 0.3 0.3 D— 1 3.0 F— 1 15 1 H- 1 0.01 樹脂 1 1 - - 100 0.3 0.3 D— 1 3.0 F— 1 15 1 H- 1 0.01 樹脂 12 ― 100 ― 0.3 0.3 D - 1 3.0 F— 1 6 1 H - 1 0.01 樹脂 1 3 - 100 - 0.3 0.3 D - 1 3.0 F- 1 10 1 H- 1 0.01 樹脂 14 ― 100 ― 0.3 0.3 D - 1 3.0 F- 1 25 1 H— 1 0.01 樹脂 15 一 100 一 0.3 0.3 D— 1 3.0 F- 1 15 ― H- 1 0.01 樹脂 16 一 100 ― 0.3 0.3 D— 1 3.0 F— 1 15 H— 1 0.01 樹脂 17 - 100 - 0.3 0.3 D— 1 3.0 F- 2 15 1 H— 1 0.01 樹脂 18 ― 100 ― 0.3 0.3 D— 1 3.0 F— 1 15 1 H- 1 0.0001 樹脂 19 ― 100 ― 0.3 0.3 D— 1 3.0 F— 1 15 1 H- 1 0.1 樹脂 20 ― 100 - 0.3 0.3 D— 1 3.0 F— 1 15 1 H- 1 1 樹脂 2 1 ― 100 ― 0.3 0.3 D— 1 3.0 F- 1 15 1 H- 2 0.01 樹脂 22 ― 100 ― 0.3 0.3 D— 1 3.0 F— 1 15 1 H- 3 0.01 Styrenic resin composition name Mass part Mass part Mass part Mass part Mass part Type Mass part ¾ 頹 Mass part Mass part Type Mass part Resin 1 ― 100 ― 0.3 0.3 D― 1 3.0 F-1 15 1 H― 1 0.01 Resin 2 ― 100 ― 0.05 0.05 D— 1 3.0 F- 1 15 1 H- 1 0.01 Resin 3 ― 100 1 3.0 3.0 D— 1 3.0 F— 1 15 1 H- 1 0.01 Resin 4 ― 100 ― 0.3 0.3 D— 1 0.5 F -1 15 1 H- 1 0.01 Resin 5-100 ― 0.3 0.3 D— 1 13.0 F-1 15 1 H- 1 0.01 Resin 6 ― 100 ― 0.3 0.3 D— 2 3.0 F- 1 15 1 H- 1 0.01 Resin 7 -100-0.3 0.3 D-3 3.0 F-1 15 1 H-1 0.01 Resin 8-100-0.3 0.3 D-4 3.0 F-1 15 1 H-1 0.01 Resin 9-100-0.3 0.3 E-1 3.0 F -1 15 1 H— 1 0.01 Resin 10 100 ― ― 0.3 0.3 D— 1 3.0 F— 1 15 1 H- 1 0.01 Resin 1 1--100 0.3 0.3 D— 1 3.0 F— 1 15 1 H- 1 0.01 Resin 12 ― 100 ― 0.3 0.3 D-1 3.0 F ― 1 6 1 H-1 0.01 Resin 1 3-100-0.3 0.3 D-1 3.0 F- 1 10 1 H- 1 0.01 Resin 14 ― 100 ― 0.3 0.3 D-1 3.0 F- 1 25 1 H— 1 0.01 Fat 15 1 100 1 0.3 0.3 D— 1 3.0 F- 1 15 ― H- 1 0.01 Resin 16 1 100 ― 0.3 0.3 D— 1 3.0 F— 1 15 H— 1 0.01 Resin 17-100-0.3 0.3 D— 1 3.0 F- 2 15 1 H— 1 0.01 Resin 18 ― 100 ― 0.3 0.3 D— 1 3.0 F— 1 15 1 H- 1 0.0001 Resin 19 ― 100 ― 0.3 0.3 D— 1 3.0 F— 1 15 1 H- 1 0.1 Resin 20 ― 100-0.3 0.3 D— 1 3.0 F— 1 15 1 H- 1 1 Resin 2 1 ― 100 ― 0.3 0.3 D— 1 3.0 F- 1 15 1 H- 2 0.01 Resin 22 ― 100 ― 0.3 0.3 D— 1 3.0 F— 1 15 1 H- 3 0.01
Figure imgf000053_0001
表 IV— 3
Figure imgf000053_0001
Table IV-3
配合  Formulation
スチレン スチレン スチレン ヒンダ一 ベンゾ卜 ポリエーテルエステ  Styrene Styrene Styrene Hinder One Benzene Polyether Este
系共重合 系共重合 系共重合 ドアミン リアゾー 未溶融化合物 ルアミドプロック共 複合界面  Copolymer Copolymer Copolymer Doamine Riazo Unmelted Compound Luamide Block Co-Compound Interface
着色剤 体 A— 1 体 A 2 体 A— 3 活性剤  Colorant Body A— 1 body A 2 body A— 3 Activator
系化合物 ル系化合 重合体  Compounds Lu-based compounds Polymers
スチレン系樹脂組成物名 質量部 質量部 質量部 質量部 質量部 種類 質量部 種類 質量部 質量部 種類 質量部 樹脂 23 ― 100 ― 0.3 0.3 D— 1 3.0 F- 1 15 1 ― ― 樹脂 24 一 100 - 0.05 0.05 D— 1 3.0 F— 1 15 1 ― 一 樹脂 25 - 100 一 3.0 3.0 D— 1 3.0 F - 1 15 1 ― ― 樹脂 26 ― 100 一 0.3 0.3 D— 1 0.5 F- 1 15 1 - ― 樹脂 27 - 100 ― 0.3 0.3 D - 1 13.0 F— 1 15 1 - 一 樹脂 28 一 100 一 0.3 0.3 D - 2 3.0 F— 1 15 1 - ― 榭脂 29 一 100 - 0.3 0.3 D— 3 3.0 F— 1 15 1 ― ― 樹脂 30 一 100 ― 0.3 0.3 D— 4 3.0 F- 1 15 1 ― ― 樹脂 31 一 100 ― 0.3 0.3 E - 1 3.0 F— 1 15 1 一 ― 榭脂 32 100 - - 0.3 0.3 D— 1 3.0 F— 1 15 1 一 一 樹脂 33 ― 一 100 0.3 0.3 D- 1 3.0 F- 1 15 1 ― ― 樹脂 34 ― 100 一 0.3 0.3 D - 1 3.0 F- 1 6 1 ― ― 樹脂 35 一 100 - 0.3 0.3 D - 1 3.0 F- 1 10 1 ― - 樹脂 36 - 100 一 0.3 0.3 D— 1 3.0 F— 1 25 1 一 ― 樹脂 37 ― 100 一 0.3 0.3 D— 1 3.0 F- 1 15 ― ― 一 樹脂 38 一 100 - 0.3 0.3 D - 1 3.0 F— 1 15 5 - 樹脂 39 一 100 ― 0.3 0.3 D— 1 3.0 F— 2 15 1 ― ― Styrenic resin composition name Mass part Mass part Mass part Mass part Mass part Type Mass part Type Mass part Mass part Type Mass part Resin 23 ― 100 ― 0.3 0.3 D― 1 3.0 F- 1 15 1 ― ― Resin 24 1 100- 0.05 0.05 D— 1 3.0 F— 1 15 1-One resin 25-100 One 3.0 3.0 D-1 3.0 F-1 15 1--Resin 26-100 One 0.3 0.3 D-1 0.5 F- 1 15 1--Resin 27-100 ― 0.3 0.3 D-1 13.0 F— 1 15 1-One Resin 28 One 100 One 0.3 0.3 D-2 3.0 F— 1 15 1-― Grease 29 One 100-0.3 0.3 D— 3 3.0 F— 1 15 1--Resin 30 1 100-0.3 0.3 D-4 3.0 F- 1 15 1--Resin 31 1 100-0.3 0.3 E-1 3.0 F-1 15 1 1-Grease 32 100--0.3 0.3 D- 1 3.0 F— 1 15 1 1 Resin 33 ― 1 100 0.3 0.3 D- 1 3.0 F- 1 15 1 ― ― Resin 34 ― 100 1 0.3 0.3 D-1 3.0 F- 1 6 1 ― ― Resin 35 1 100- 0.3 0.3 D-1 3.0 F- 1 10 1 ―-Resin 36-100 1 0.3 0.3 D— 1 3.0 F— 1 25 1 One ― Resin 37 ― 100 1 0.3 0.3 D— 1 3.0 F- 1 15 ― ― 1 Resin 38 1 100-0.3 0.3 D-1 3.0 F ― 1 15 5-Resin 39 1 100 ― 0.3 0.3 D ― 1 3.0 F ― 2 15 1 ― ―
¾〔〕〔010433 ¾ [] [010433
表 IV— 4  Table IV— 4
配合  Formulation
ベンゾ卜  Benzo
スチレン スチレン スチレン ヒンダ一 ポリエーテルエステ  Styrene Styrene Styrene Hinder One Polyether Este
リアゾー  Riazo
系共重合 系共重合 系共重合 ドア Sン 未溶融化合物 ルアミドブロック共 複合界面  Copolymer Copolymer Copolymer Copolymer Door Sun Unmelted compound Luamide block Co Composite interface
着色剤 体 A - 1 体 A— 3 体 A— 4 ル系化合  Colorant Body A-1 body A-3 body A-4
系化合物 重合体 活性剤  Compound polymer activator
物  object
スチレン系樹脂組成物名 質量部 質量部 質量部 質量部 質量部 種類 質量部 種類 質量部 質量部 種類 質量部 樹脂 4 0 一 100 ― ― ― E— 1 3 ― ― ― H— 1 0. 01 樹脂 4 1 一 100 一 ― ― E— 1 0. 5 ― ― ― H - 1 0. 01 樹脂 4 2 ― 100 ― ― ― E— 1 13 ― ― ― H— 1 0. 01 樹脂 4 3 ― 100 ― ― 一 E— 2 3 ― ― 一 H— 1 0. 01 樹脂 4 4 ― 100 ― ― ― E - 3 3 ― ― ― H— 1 0. 01 樹脂 4 5 ― 100 ― ― ― E - 4 3 一 ― ― H— 1 0. 01 樹脂 4 6 ― 100 一 ― ― B 3 一 ― ― H— 1 0. 01 樹脂 4 7 ― 100 ― ― ― C 3 ― ― ― H - 1 0. 01 樹脂 4 8 ― 100 一 D— 1 3 ― ― ― H - 1 0. 01 樹脂 4 9 100 ― ― ― ― E— 1 3 ― ― ― H— 1 0. 01 樹脂 5 0 ― 一 100 ― ― E— 1 3 ― ― ― H - 1 0. 01 樹脂 5 1 ― 100 ― ― 一 E— 1 3 ― ― ― H— 1 0. 0001 榭脂 5 2 ― 100 ― ― ― E— 1 3 ― 一 ― H— 1 0. 1 樹脂 5 3 ― 100 ― ― ― E— 1 3 ― ― ― H— 1 1 樹脂 5 4 ― 100 ― ― ― E— 1 3 ― ― H - 2 0. 01 樹脂 5 5 ― 100 ― ― ― E— 1 3 ― ― ― H— 3 0. 01 Styrenic resin composition name Mass part Mass part Mass part Mass part Mass part Type Mass part Type Mass part Mass part Type Mass part Resin 4 0 1 100---E-1 3---H-1 0. 01 Resin 4 1 1 100 1--E-1 0.5---H-1 0. 01 Resin 4 2-100---E-1 13---H-1 0. 01 Resin 4 3-100--One E-2 3 ― ― One H― 1 0. 01 Resin 4 4 ― 100 ― ― ― E-3 3 ― ― ― H ― 1 0.01 Resin 4 5 ― 100 ― ― ― E-4 3 One ― ― H — 1 0. 01 Resin 4 6 ― 100 1 ― ― B 3 1 ― ― H ― 1 0.01 Resin 4 7 ― 100 ― ― ― C 3 ― ― ― H-1 0. 01 Resin 4 8 ― 100 1 D -1 3---H-1 0. 01 Resin 4 9 100----E-1 3---H-1 0. 01 Resin 5 0-One 100--E-1 3---H- 1 0. 01 Resin 5 1 ― 100 ― ― One E ― 1 3 ― ― ― H ― 1 0. 0001 Oil 5 2 ― 100 ― ― ― E ― 1 3 ― One ― H ― 1 0. 1 Resin 5 3 ― 100 ― ― E-1 3 3 ― ― ― H-1 1 Resin 5 4 ― 100 ― ― ― E― 1 3 ― ― H-2 0. 01 Resin 5 5 ― 100 ― ― ― E― 1 3 ― ― ― H― 3 0 . 01
表 IV— 5 Table IV— 5
配合  Formulation
スチレン スチレン スチレン ヒンダ一 ベンゾ卜 ポリエーテルエステ  Styrene Styrene Styrene Hinder One Benzene Polyether Este
リアゾ一 アミドブロック共 複合界面  Riazo-amide block co-composite interface
系共重合 系共重合 系共重合 ドアミン 未溶融化合物 ル 着色剤 ル系化合  Copolymer Copolymer Copolymer Doamine Unmelted compound Lu Colorant Lu Compound
体 A— 1 体 A— 3 体 A— 4 系化合物 重合体 活性剤  Form A— 1 Form A— 3 Form A— 4 System Compound Polymer Activator
物  object
スチレン系樹脂組成物名 質量部 質量部 質量部 質量部 質量部 種類 質量部 種類 質量部 質量部 種類 質量部 棱 t脂 5 6 ― 100 ― ― ― E— 1 3 ― ― ― ― ― 棱脂 5 7 ― 100 ― ― ― E - 1 0. 5 ― ― ― ― 楱脂 5 8 ― 100 ― ― ― E— 1 13 一 ― ― ― 楱脂 5 9 ― 100 ― ― ― E - 2 3 ― ― ― ― 棱 ί脂 6 0 ― 100 ― ― E - 3 3 ― ― ― ― ― 椿 ί脂 6 1 100 ― ― ― E— 4 3 ― ― ― ― ― 楱 ί脂 6 2 ― 100 ― ― ― B 3 ― ― ― ― ― 楱 t脂 6 3 ― 100 ― ― C 3 ― ― ― ― 棱 t脂 6 4 100 ― ― D— 1 3 ― ― ― ― ― Styrenic resin composition name Mass part Mass part Mass part Mass part Mass part Type Mass part Type Mass part Mass part Type Mass part 棱 t Fat 5 6 ― 100 ― ― ― E― 1 3 ― ― ― ― ― Grease 5 7 ― 100 ― ― ― E-1 0. 5 ― ― ― ― Grease 5 8 ― 100 ― ― ― E ― 1 13 One ― ― ― Grease 5 9 ― 100 ― ― ― E-2 3 ― ― ― ― 棱Liquor 6 0 ― 100 ― ― E-3 3 ― ― ― ― ― ί Liquor 6 1 100 ― ― ― E ― 4 3 ― ― ― ― ― ί Grease 6 2 ― 100 ― ― ― B 3 ― ― ― ― ― 楱 grease 6 3 ― 100 ― ― C 3 ― ― ― ― 棱 grease 6 4 100 ― ― D ― 1 3 ― ― ― ― ―
W旨 6 5 100 ― ― ― ― E— 1 3 ― ― ― ― ― 横脂 6 6 ― 一 100 ― ― E— 1 3 ― ― ― ― ― W 6 5 100 ― ― ― ― E― 1 3 ― ― ― ― ― Weft 6 6 ― One 100 ― ― E ― 1 3 ― ― ― ― ―
s〔Sa01 Ow 表 例 例 例 例 例 例 例 例 例 例 例 1 2 3 4 5 6 7 8 9 10 11 種類 樹脂 1 樹脂 7 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 13 樹脂 15 榭脂 19 樹脂 23 樹脂 29 肉厚 (mm) 0. 1 0. 1 0. 1 0.1 0.1 0. 1 0.1 0. 1 0. 1 0.1 0. 1 中間層 種類 樹脂 56 樹脂 56 樹脂 63 樹脂 60 樹脂 56 樹脂 56 樹脂 56 樹脂 56 樹脂 56 樹脂 40 樹脂 40 シー卜 b 肉厚 （mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 層構成 s [Sa01 Ow Table Example Example Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8 9 10 11 Types Resin 1 Resin 7 Resin 1 Resin 1 Resin 1 Resin 1 Resin 13 Resin 15 Resin 15 Resin 19 Resin 23 Resin 29 Thickness (mm) 0. 1 0. 1 0. 1 0.1 0.1 0. 1 0.1 0. 1 0. 1 0.1 0. 1 Middle layer Type Resin 56 Resin 56 Resin 63 Resin 60 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 40 Resin 40 Sheet b thickness (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Layer structure
類 樹脂 1 樹脂 7 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 13 樹脂 15 樹脂 19 樹脂 23 樹脂 29 翻 c  Class Resin 1 Resin 7 Resin 1 Resin 1 Resin 1 Resin 1 Resin 13 Resin 15 Resin 19 Resin 23 Resin 29 Convert c
肉厚 (mm) 0. 1 0. 1 0. 1 0.1 0.1 0.1 0.1 0. 1 0.1 0.1 0. 1 総肉厚 （mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 全光線透過率は） 69.2 67.2 68.6 69.9 69.5 67. 1 69.4 69.9 70. 1 69.8 68.9 光学特 曇り度は） 99.2 99.4 99.3 99. 1 99.2 99.4 99.2 99.2 99. 1 99.2 99.3 性 拡散率は） 22.6 24.7 23.0 21.5 22.4 24.9 22.5 22. 1 21.3 21.6 22.9 b値 0.5 0.6 0.5 0.5 0.6 0.6 0.4 0.4 0.4 0.4 0.4 f f光性 色差 ΔΕ 0.5 0.6 0.5 0.5 0.7 0.5 0.4 0.4 0.7 0.6 0.6 寸法安定性 吸水反り （mm) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.6 0.7 0.7 0.7 帯電防止性 表面固有抵抗（Ω) 1X1010 lxio10 1X1010 1X1010 1X1010 lxio10 1X1012 1X1011 1X1010 1X1010 1X1010 耐傷付き性 良 良 良 良 良 良 良 良 良 良 良 Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Total thickness (mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Total light transmittance) 69.2 67.2 68.6 69.9 69.5 67. 1 69.4 69.9 70. 1 69.8 68.9 Optical characteristics Haze is 99.2 99.4 99.3 99. 1 99.2 99.4 99.2 99.2 99. 1 99.2 99.3 diffusivity is 22.6 24.7 23.0 21.5 22.4 24.9 22.5 22. 1 21.3 21.6 22.9 b value 0.5 0.6 0.5 0.5 0.6 0.6 0.4 0.4 0.4 0.4 0.4 ff Light color difference ΔΕ 0.5 0.6 0.5 0.5 0.7 0.5 0.4 0.4 0.7 0.6 0.6 Dimensional stability Water absorption warpage (mm) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.6 0.7 0.7 0.7 antistatic surface resistivity (Ω) 1X10 10 lxio 10 1X10 10 1X10 10 1X10 10 lxio 10 1X10 12 1X10 11 1X10 10 1X10 10 1X10 10 scratch resistance good good good good good good good good good good good
SsS01c3 表 IV— 7 例 例 例 例 例 例 例 例 例 例 例SsS01c3 Table IV— 7 Examples Example Example Example Example Example Example Example Example Example Example
12 13 14 15 16 17 18 19 20 21 22 種類 樹脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 35 樹脂 37 樹脂 1 樹脂 1 樹脂 19 樹脂 19 表層 a 12 13 14 15 16 17 18 19 20 21 22 Type Resin 23 Resin 23 Resin 23 Resin 23 Resin 23 Resin 23 Resin 35 Resin 37 Resin 1 Resin 1 Resin 19 Resin 19 Resin a
肉厚 (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 中間層 種類 樹脂 47 樹脂 44 樹脂 40 樹脂 40 榭脂 52 樹脂 40 榭脂 40 樹脂 40 榭脂 52 樹脂 40 樹脂 52 シート b 肉厚 (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 種類 樹脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 35 樹脂 37 樹脂 1 樹脂 1 樹脂 19 樹脂 19 麵 c  Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Intermediate layer Type Resin 47 Resin 44 Resin 40 Resin 40 Resin 52 Resin 40 Resin 40 Resin 40 Resin 52 Resin 40 Resin 52 Sheet b Thickness (mm ) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Type Resin 23 Resin 23 Resin 23 Resin 23 Resin 23 Resin 35 Resin 35 Resin 1 Resin 1 Resin 19 Resin 19 麵 c
肉厚 (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 総肉厚 （mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 全光線透過率 (« 69.5 70.7 70.3 68.1 70.7 70.1 70.4 70.0 71.1 70.7 72.0 光学特 曇り度 «) 99.2 99.1 99.1 99.3 99.1 99.1 99.1 99.1 99.0 99.1 99.0 性 拡散率 ） 21.9 20.3 21.1 23.8 20.3 21.4 21.0 21.2 19.5 20.4 19.3 b値 0.4 0.4 0.4 0.3 0.3 0.3 0.3 0.4 0.3 0.3 0.2 而 f光性 色差 ΔΕ 0.6 0.6 0.6 0.7 0.8 0.5 0.5 0.7 0.9 0.8 0.9 寸法安定性 吸水反り （mm) 0.7 0.7 0.7 0.7 0.7 0.6 0.6 0.7 0.7 0.7 0.7 帯電防止性 表面固有抵抗（Ω) 1X1010 1X1010 lxio10 1X1010 1X1010 1X1012 1X10" 1X1010 1X1010 1X1010 1X1010 耐傷付き性 良 良 良 良 良 良 良 良 良 良 良 Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Total thickness (mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Total light transmittance («69.5 70.7 70.3 68.1 70.7 70.1 70.4 70.0 71.1 70.7 72.0 Optical characteristics Haze «) 99.2 99.1 99.1 99.3 99.1 99.1 99.1 99.1 99.0 99.1 99.0 Sex diffusivity) 21.9 20.3 21.1 23.8 20.3 21.4 21.0 21.2 19.5 20.4 19.3 b value 0.4 0.4 0.4 0.3 0.3 0.3 0.3 0.4 0.3 0.3 0.2 ΔΕ 0.6 0.6 0.6 0.7 0.8 0.5 0.5 0.7 0.9 0.8 0.9 dimensional stability water warpage (mm) 0.7 0.7 0.7 0.7 0.7 0.6 0.6 0.7 0.7 0.7 0.7 antistatic surface resistivity (Ω) 1X10 10 1X10 10 lxio 10 1X10 10 1X10 10 1X10 12 1X10 "1X10 10 1X10 10 1X10 10 1X10 10 Scratch resistance Good Good Good Good Good Good Good Good Good Good Good
表 IV— 8Table IV— 8
Figure imgf000058_0001
Figure imgf000058_0001
例 例 例 例 例 例 例 例 例 例 例 Example Example Example Example Example Example Example Example Example Example Example
23 24 25 26 27 28 29 30 31 32 33 種類 樹脂 1 樹脂 1 樹脂 17 樹脂 16 榭脂 2 榭脂 3 樹脂 4 樹脂 5 樹脂 6 樹脂 8 榭脂 9 表層 a 23 24 25 26 27 28 29 30 31 32 33 Type Resin 1 Resin 1 Resin 17 Resin 16 Resin 2 Resin 3 Resin 4 Resin 5 Resin 6 Resin 8 Resin 9 Resin a
肉厚 （mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 中間層 種 樹脂 65 樹脂 66 榭脂 56 樹脂 56 樹脂 56 樹脂 56 樹脂 56 樹脂 56 樹脂 56 樹脂 56 樹脂 56 シート b 肉厚 (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8  Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Intermediate layer Type Resin 65 Resin 66 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Sheet b Thickness (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8
層構成 1.8 1.8 1.8 種類 樹脂 1 樹脂 1 樹脂 17 樹脂 16 樹脂 2 樹脂 3 樹脂 4 樹脂 5 樹脂 6 樹脂 8 樹脂 9 翻 c  Layer structure 1.8 1.8 1.8 Types Resin 1 Resin 1 Resin 17 Resin 16 Resin 2 Resin 3 Resin 4 Resin 5 Resin 6 Resin 8 Resin 9 Convert c
肉厚 （mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 総肉厚 （mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 全光線透過率は） 67.8 73.2 68.4 68.5 69.4 68.9 72.2 61.5 73.5 62.3 64.2 光学特 曇り度は） 99.4 98.8 99.3 99.3 99.2 99.2 98.9 99.5 98.7 99.5 99.4 性 拡散率 ） 24.1 16.9 23.5 23.3 21.5 22.9 18.9 28.4 16.8 27.7 26.8 b値 0.6 0.6 0.6 0.5 0.4 0.4 0.6 0.2 0.6 0.6 0.6 Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Total thickness (mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Total light transmittance) 67.8 73.2 68.4 68.5 69.4 68.9 72.2 61.5 73.5 62.3 64.2 99.4 98.8 99.3 99.3 99.2 99.2 98.9 99.5 98.7 99.5 99.4 Sex diffusivity) 24.1 16.9 23.5 23.3 21.5 22.9 18.9 28.4 16.8 27.7 26.8 b value 0.6 0.6 0.6 0.5 0.4 0.4 0.6 0.2 0.6 0.6 0.6
I f光性 色差 ΔΕ 0.5 1.3 1.2 0.5 1.3 0.2 0.5 0.5 0.5 0.5 0.5 寸法安定性 吸水反り （mm) 1.7 0.6 0.7 1.5 0.7 0.7 0.7 0.7 0.7 0.7 0.7 帯電防止性 表面固有抵抗（Ω) 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 耐傷付き性 良 良 良 良 良 良 良 良 良 良 良 I f Light color difference ΔΕ 0.5 1.3 1.2 0.5 1.3 0.2 0.5 0.5 0.5 0.5 0.5 Dimensional stability Water absorption warp (mm) 1.7 0.6 0.7 1.5 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Antistatic property Surface resistivity (Ω) 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 Scratch resistance Good Good Good Good Good Good Good Good Good Good Good
sfflw01 O 例 例 例 例 例 例 例 例 例 例 例 表 sfflw01 O Example Example Example Example Example Example Example Example Example Example Example Table
34 35 36 37 38 39 40 41 42 43 44 種類 樹脂 12 樹脂 14 樹脂 16 樹脂 17 樹脂 21 樹脂 22 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 表層 a  34 35 36 37 38 39 40 41 42 43 44 Type Resin 12 Resin 14 Resin 16 Resin 17 Resin 21 Resin 22 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Surface layer a
肉厚 (mm) 0.1 0. 1 0. 1 0.1 0.1 0.1 0.1 0. 1 0. 1 0.1 0. 1 中間層 種類 樹脂 56 樹脂 56 樹脂 56 樹脂 56 樹脂 56 樹脂 56 樹脂 57 樹脂 58 樹脂 59 樹脂 61 樹脂 64 シー卜 b 肉厚 （mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 層構成 1.8 種類 樹脂 12 樹脂 14 樹脂 16 樹脂 17 樹脂 21 樹脂 22 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 裏層 c  Thickness (mm) 0.1 0. 1 0. 1 0.1 0.1 0.1 0.1 0. 1 0. 1 0.1 0. 1 Intermediate layer Type Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 57 Resin 58 Resin 59 Resin 61 Resin 61 Resin 64 sheets 卜 b Thickness (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Layer structure 1.8 Type Resin 12 Resin 14 Resin 16 Resin 17 Resin 21 Resin 22 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Back layer c
肉厚 （mm) 0.1 0. 1 0. 1 0.1 0. 1 0.1 0.1 0.1 0. 1 0. 1 0. 1 総肉厚 （mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 全光線透過率は） 69.9 69.0 67.7 54.3 66.3 64.4 75.1 60.0 74.9 65.2 75.5 光学特 曇り度は） 99.1 99.2 99.3 99.7 99.3 99.4 98.1 99.5 98.2 99.4 98.0 性 拡散率 W 22.1 22.8 24.1 32.0 24.9 26.3 15.3 29.3 15.5 25.6 15.2 b値 0.3 1.0 1.1 0.6 0.2 0.2 0.4 0.6 0.5 0.5 0.5 而、 f光性 色差 ΔΕ 0.4 0.6 0.7 0.5 0.4 1.0 0.5 0.6 0.5 0.5 0.5 寸法安定性 吸水反り （mm) 0.6 1.1 1.2 0.7 0.7 0.8 0.7 0.7 0.7 0.7 0.7 帯電防止性 表面固有抵抗（Ω) 1X1014 1X1010 1 109 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 耐傷付き性 不良 良 良 良 良 良 良 良 良 良 良 Thickness (mm) 0.1 0. 1 0. 1 0.1 0. 1 0.1 0.1 0.1 0. 1 0. 1 0. 1 Total thickness (mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Total light transmittance is ) 69.9 69.0 67.7 54.3 66.3 64.4 75.1 60.0 74.9 65.2 75.5 Optical characteristics Haze is 99.1 99.2 99.3 99.7 99.3 99.4 98.1 99.5 98.2 99.4 98.0 diffusivity W 22.1 22.8 24.1 32.0 24.9 26.3 15.3 29.3 15.5 25.6 15.2 b value 0.3 1.0 1.1 0.6 0.2 0.2 0.4 0.6 0.5 0.5 0.5 Meta, f Light color difference ΔΕ 0.4 0.6 0.7 0.5 0.4 1.0 0.5 0.6 0.5 0.5 0.5 Dimensional stability Water absorption warp (mm) 0.6 1.1 1.2 0.7 0.7 0.8 0.7 0.7 0.7 0.7 0.7 Antistatic surface resistivity (Ω) 1X10 14 1X10 10 1 10 9 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 Scratch resistance Poor Good Good Good Good Good Good Good Good Good Good
SSs301 I 表 IV— 10 例 例 例 例 例 例 例 例 例 例 例SSs301 I Table IV— 10 Examples Example Example Example Example Example Example Example Example Example Example
45 46 41 48 49 50 51 52 53 54 55 種類 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 18 樹脂 20 樹脂 23 樹脂 23 樹脂 33 榭脂 32 肉厚 (mm) 0.1 0.003 0.8 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 中間層 種類 樹脂 62 榭脂 56 樹脂 56 樹脂 56 樹脂 56 樹脂 56 樹脂 56 樹脂 49 樹脂 50 樹脂 40 樹脂 40 シート b 肉厚 (mm) 1.8 1.8 1.8 0.8 10 1.8 1.8 1.8 1.8 1.8 1.8 層構成 45 46 41 48 49 50 51 52 53 54 55 Type Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 18 Resin 18 Resin 20 Resin 23 Resin 33 Resin 33 Oil 32 Thickness (mm) 0.1 0.003 0.8 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Intermediate layer Type Resin 62 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 56 Resin 49 Resin 50 Resin 40 Resin 40 Sheet b Thickness (mm) 1.8 1.8 1.8 0.8 10 1.8 1.8 1.8 1.8 1.8 1.8 Layer structure
種類 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 榭脂 18 樹脂 20 樹脂 23 樹脂 23 樹脂 33 樹脂 32 麵 c  Type Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 18 Resin 20 Resin 23 Resin 23 Resin 33 Resin 32 麵 c
肉厚 （mm) 0.1 0.003 0.8 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 総肉厚 （mm) 2.0 1.806 3.4 1.0 10.2 2.0 2.0 2.0 2.0 2.0 2.0 全光線透過率は） 57.7 69.9 68.8 76.4 52.9 66.9 70.9 68.3 74.7 69.2 69.3 光学特 曇り度は） 99..5 99.1 99.2 97.8 99.8 99.4 99.1 99.1 98.2 99.2 99.2 性 拡散率は） 30.1 21.6 23.1 13.9 32.6 25.1 20.2 23.3 15.6 22.6 22.4 b値 0.6 0.4 0.5 0.5 0.7 0.6 0.2 0.5 0.5 0.5 0.4 f光性 色差 ΔΕ 0.5 1.5 0.5 0.5 0.5 0.4 1.3 0.6 1.5 1.4 0.6 寸法安定性 吸水反り （mm) 0.7 0.7 1.5 0.7 0.7 0.7 0.7 1.8 0.6 0.6 1.6 帯電防止性 表面固有抵抗（Ω) 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 耐傷付き性 良 良 良 良 良 良 良 良 良 良 良 Thickness (mm) 0.1 0.003 0.8 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Total thickness (mm) 2.0 1.806 3.4 1.0 10.2 2.0 2.0 2.0 2.0 2.0 2.0 Total light transmittance) 57.7 69.9 68.8 76.4 52.9 66.9 70.9 68.3 74.7 69.2 69.3 99..5 99.1 99.2 97.8 99.8 99.4 99.1 99.1 98.2 99.2 99.2 Sex Diffusion rate) 30.1 21.6 23.1 13.9 32.6 25.1 20.2 23.3 15.6 22.6 22.4 b value 0.6 0.4 0.5 0.5 0.7 0.6 0.2 0.5 0.5 0.5 0.4 f Lightness Color difference ΔΕ 0.5 1.5 0.5 0.5 0.5 0.4 1.3 0.6 1.5 1.4 0.6 Dimensional stability Water absorption warp (mm) 0.7 0.7 1.5 0.7 0.7 0.7 0.7 1.8 0.6 0.6 1.6 Antistatic property Surface resistivity (Ω) 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 Scratch resistance Good Good Good Good Good Good Good Good Good Good Good
SS4 表 例 例 例 例 例 例 例 例 例 例 例SS4 Table Example Example Example Example Example Example Example Example Example Example Example
56 57 58 59 60 61 62 63 64 65 66 種類 樹脂 24 樹脂 25 樹脂 26 樹脂 27 樹脂 28 樹脂 30 樹脂 31 樹脂 34 樹脂 36 樹脂 38 樹脂 39 表層 a 56 57 58 59 60 61 62 63 64 65 66 Type Resin 24 Resin 25 Resin 26 Resin 27 Resin 28 Resin 30 Resin 31 Resin 34 Resin 36 Resin 38 Resin 39 Surface a
肉厚 (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 中間層 種類 樹脂 40 樹脂 40 樹脂 40 樹脂 40 樹脂 40 樹脂 40 樹脂 40 樹脂 40 樹脂 40 樹脂 40 樹脂 40 シ—卜 b 肉厚 (mm) 1.8 1.8 1.8 1.8 1.8 1.8 ■ 1.8 1.8 1.8  Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Middle layer Type Resin 40 Resin 40 Resin 40 Resin 40 Resin 40 Resin 40 Resin 40 Resin 40 Resin 40 Resin 40 Resin 40 Resin 40 Sheath b Thickness (mm) 1.8 1.8 1.8 1.8 1.8 1.8 ■ 1.8 1.8 1.8
層構成 1.8 1.8 種類 樹脂 24 樹脂 25 樹脂 26 樹脂 27 樹脂 28 樹脂 30 樹脂 31 樹脂 34 樹脂 36 樹脂 38 樹脂 39 裏層 c  Layer structure 1.8 1.8 types Resin 24 Resin 25 Resin 26 Resin 27 Resin 28 Resin 30 Resin 31 Resin 34 Resin 36 Resin 38 Resin 39 Back layer c
肉厚 (mm) 0.1 0.1 0. 1 0.1 0. 1 0.1 0. 1 0. 1 0.1 0. 1 0. 1 総肉厚 （mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 全光線透過率は） 70.2 69.6 73.0 62.1 74.5 62.8 65.0 70.4 69.4 68.4 55.4 光学特 曇り度 (¾) 99.1 99.2 98.8 99.5 98.4 99.5 99.4 99.1 99.2 99.3 99.6 性 拡散率 tt) 21.1 22.1 17.4 28.0 15.8 27.4 25.9 21.2 21.9 23.4 31.8 b値 0.3 1.4 0.5 0.6 0.2 0.2 0.2 0.3 1.0 1. 1 0.6 而' ί光性 色差 ΔΕ 1.4 0.3 0.6 0.6 0.9 0.9 0.9 0.5 0.7 0.9 0.6 寸法安定性 吸水反り （mm) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.5 1.0 1. 1 0.8 帯電防止性 表面固有抵抗（Ω) 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 1X1014 1X1010 1X109 1X1010 耐傷付き性 良 良 良 良 良 良 良 不良 良 良 良 Thickness (mm) 0.1 0.1 0. 1 0.1 0. 1 0.1 0. 1 0. 1 0.1 0. 1 0. 1 Total thickness (mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 70.2 69.6 73.0 62.1 74.5 62.8 65.0 70.4 69.4 68.4 55.4 Optical characteristics Haze (¾) 99.1 99.2 98.8 99.5 98.4 99.5 99.4 99.1 99.2 99.3 99.6 Sex diffusivity tt) 21.1 22.1 17.4 28.0 15.8 27.4 25.9 21.2 21.9 23.4 31.8 b value 0.3 1.4 0.5 0.6 0.2 0.2 0.2 0.3 1.0 1. 1 0.6 Metachromatic color difference ΔΕ 1.4 0.3 0.6 0.6 0.9 0.9 0.9 0.5 0.7 0.9 0.6 Dimensional stability Water absorption warp (mm) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.5 1.0 1. 1 0.8 Antistatic property Surface resistivity (Ω) 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 14 1X10 10 1X10 9 1X10 10 Scratch resistance Good Good Good Good Good Good Good Good Good
0112 表 IV— 1 2 例 例 例 例 例 例 例 例 例 例 例0112 Table IV— 1 2 Example Example Example Example Example Example Example Example Example Example Example
67 68 69 70 71 72 73 74 75 76 77 種類 榭脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 23 肉厚 （mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.003 0.8 0.1 中間層 種類 樹脂 41 樹脂 42 樹脂 43 樹脂 45 樹脂 48 樹脂 46 樹脂 54 樹脂 55 樹脂 40 樹脂 40 樹脂 40 シート b 肉厚 (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 0.8 層構成 67 68 69 70 71 72 73 74 75 76 77 Type 23 Resin 23 Resin 23 Resin 23 Resin 23 Resin 23 Resin 23 Resin 23 Resin 23 Resin 23 Resin 23 Resin 23 Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.003 0.8 0.1 Intermediate layer Type Resin 41 Resin 42 Resin 43 Resin 45 Resin 48 Resin 46 Resin 54 Resin 54 Resin 55 Resin 40 Resin 40 Resin 40 Sheet b Thickness (mm) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 0.8 Layer structure
種類 榭脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 23 樹脂 23. 樹脂 23 樹脂 23 肉厚 (mm) 0. 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.003 0.8 0. 1 総肉厚 （mm) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 1.806 3.4 1.0 全光線透過率 (¾) 76.0 60.9 75.8 66.0 76.6 58.2 66.5 65.1 70.6 69.6 77.1 光学特 曇り度は) 97.7 99.5 97.8 99.4 97.1 99.5 99.3 99.4 99.1 99.2 96.7 性 拡散率 (¾) 14.7 28.8 14.9 24.8 13.8 30.0 24.2 25.8 20.3 22.0 13.1  Type Resin 23 Resin 23 Resin 23 Resin 23 Resin 23 Resin 23 Resin 23 Resin 23 Resin 23. Resin 23 Resin 23 Thickness (mm) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.003 0.8 0. 1 Total Thickness (mm ) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 1.806 3.4 1.0 Total light transmittance (¾) 76.0 60.9 75.8 66.0 76.6 58.2 66.5 65.1 70.6 69.6 77.1 Optical haze) 97.7 99.5 97.8 99.4 97.1 99.5 99.3 99.4 99.1 99.2 96.7 Sex diffusivity (¾) 14.7 28.8 14.9 24.8 13.8 30.0 24.2 25.8 20.3 22.0 13.1
b値 0.0 0.2 0.1 0.1 0.1 0.2 -0.4 -0.3 0.0 0.1 0.1 而; f光性 色差 ΔΕ 1.0 1.0 0.9 1.0 0.9 1.0 0.8 1.6 2.0 0.8 0.9 寸法安定性 吸水反り （mm) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 1.6 0.7 帯電防止性 表面固有抵抗（Ω> 1X1010 1X1010 1X1010 1X1010 1X1010 1X1010 IX 0 1X1010 1X1010 1X1010 1X1010 耐傷付き性 良 良 良 良 良 良 良 良 良 良 良 b value 0.0 0.2 0.1 0.1 0.1 0.2 -0.4 -0.3 0.0 0.1 0.1 meta; f light color difference ΔΕ 1.0 1.0 0.9 1.0 0.9 1.0 0.8 1.6 2.0 0.8 0.9 Dimensional stability Water absorption warpage (mm) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 1.6 0.7 Antistatic surface specific resistance (Ω> 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 1X10 10 IX 0 1X10 10 1X10 10 1X10 10 1X10 10 Scratch resistance Good Good Good Good Good Good Good Good Good
( (
ト X  G
X 樹樹樹樹樹脂脂脂脂脂8201232323  X Tree Tree Resin Fat Fat Fat Fat 8201232323
（肉厚)mm  (Wall thickness) mm
樹樹脂樹樹脂樹脂脂脂 5355351401中間層  Tree resin resin resin fat 5355351401 Intermediate layer
卜シ— b肉厚（)mm  卜 Sh-b wall thickness () mm
層構成 X  Layer structure X
樹樹樹脂脂樹脂脂樹脂 2823230231  Tree resin resin resin resin 2823230231
厚（)肉mm to t> - )総肉厚（mm X  Thickness () meat mm to t>-) Total thickness (mm X
線率全光透過（  Total light transmittance (
度曇)り学特光  Rigaku Special Light
驟 性拡散率  性 Sexual diffusivity
w w W  w w W
f光性色差 ΔΕ  f Light color difference ΔΕ
（法安定性)寸吸水反りmm  (Legal stability) Dimensions water absorption warpage mm
οιΟΪΐ  οιΟΪΐ
裏 囊 抗帯防止性有抵（)電表面固Ω  Back 抵 Anti-banding resistance () Electric surface solid Ω
« 傷付性耐き  «Scratch resistance
[例 V] (熱変形温度が高い多層シートの例） [Example V] (Example of multilayer sheet with high thermal deformation temperature)
スチレン系共重合体 (I)の製造 Production of styrenic copolymer (I)
容積約 5リットルの第 1完全混合槽と約 15リットルの第 2完全混合槽を直列に接続し 、さらに予熱器を付した第 1脱揮槽と第 2脱揮槽を 2基直列に接続して構成した。スチ レン 40%、メチルメタタリレート（以下、「MMA」という。）60%で構成する単量体溶液 100部に対し、ェチルベンゼン 15部、 t—ブチルパーォキシイソプロピルモノカーボ ネート 0. 01部、 2, 4 ジフエ二ルー 4 メチル—1 ペンテン 0. 2部を混合し原料 溶液とした。この原料溶液を毎時 6. Okgで 135°Cに制御した第 1完全混合槽に供給 した。第 1完全混合槽出口での転ィ匕率は 28%であった。次に第 1完全混合槽より連 続的に抜き出し、 135°Cに制御した第 2完全混合槽に供給した。第 2完全混合槽出 口での転ィ匕率は 63%であった。次に第 2完全混合槽より連続的に抜き出し、予熱器 で加温し、 67kPa、 160°Cに制御した第 1脱揮槽に導入した。さらに第 1脱揮槽より 連続的に抜き出し、予熱器で加温し、 1. 3kPa、 230°Cに制御した第 2脱揮槽に導 入し単量体を除去した。これをストランド状に押出し切断することによりペレット形状の スチレン系共重合体 (1—1)を得た。 Connect a first complete mixing tank with a volume of about 5 liters and a second complete mixing tank with a capacity of about 15 liters in series, and further connect two first and second devolatilization tanks with a preheater in series. Configured. 15 parts of ethylbenzene and 0.01 parts of t-butylperoxyisopropyl monocarbonate for 100 parts of monomer solution composed of 40% styrene and 60% methyl methacrylate (hereinafter referred to as “MMA”) 2,4 Diphenyl 4-methyl-1 pentene 0.2 part was mixed to make a raw material solution. This raw material solution was supplied to the first complete mixing tank controlled at 135 ° C at 6. Okg per hour. The conversion rate at the outlet of the first complete mixing tank was 28%. Next, it was continuously extracted from the first complete mixing tank and supplied to the second complete mixing tank controlled at 135 ° C. The turnover rate at the second complete mixing tank outlet was 63%. Next, continuously withdraw from the second complete mixing tank and preheater And introduced into the first devolatilization tank controlled at 67 kPa and 160 ° C. Furthermore, it was continuously extracted from the first devolatilization tank, heated with a preheater, introduced into the second devolatilization tank controlled at 1.3 kPa and 230 ° C, and the monomer was removed. This was extruded and cut into strands to obtain pellet-shaped styrene copolymer (1-1).
[0114] スチレン 80%、メチルメタタリレート 20%で構成する単量体溶液を用いた以外は、 スチレン系共重合体 (I 1 )と同様に実施しスチレン系共重合体 (I 2)を得た。 スチレン 10%、メチルメタタリレート 90%で構成する単量体溶液を用いた以外は、 スチレン系共重合体 (I 1 )と同様に実施しスチレン系共重合体 (I 3)を得た。 得られたスチレン系重合体の組成を表 V— 1に示す。 [0114] A styrene copolymer (I 2) was prepared in the same manner as the styrene copolymer (I 1) except that a monomer solution composed of 80% styrene and 20% methyl methacrylate was used. Obtained. A styrene copolymer (I 3) was obtained in the same manner as the styrene copolymer (I 1) except that a monomer solution composed of 10% styrene and 90% methyl methacrylate was used. The composition of the obtained styrenic polymer is shown in Table V-1.
[0115] スチレン系共重合体 (II)の製造 [0115] Production of Styrene Copolymer (II)
容積約 5リットルの第 1完全混合槽と約 15リットルの第 2完全混合槽を直列に接続し 、さらに予熱器を付した第 1脱揮槽と第 2脱揮槽を 2基直列に接続して構成した。参 考例で得られた 4—tーブチルカテコールが 0. lppm含まれるスチレン 83%、メタタリ ル酸（以下、「MAA」という。） 17%で構成する単量体溶液 100部に対し、ェチルベ ンゼン 15部、 t—ブチルパーォキシイソプロピルモノカーボネート 0. 01部、 2, 4ージ フエ-ル一 4—メチル 1—ペンテン 0. 2部を混合し原料溶液とした。この原料溶液 を毎時 6. Okgで 135°Cに制御した第 1完全混合槽に供給した。第 1完全混合槽出口 での転ィ匕率は 28%であった。次に第 1完全混合槽より連続的に抜き出し、 135°Cに 制御した第 2完全混合槽に供給した。第 2完全混合槽出口での転化率は 63%であ つた。次に第 2完全混合槽より連続的に抜き出し、予熱器で加温し、 67kPa、 160°C に制御した第 1脱揮槽に導入した。さらに第 1脱揮槽より連続的に抜き出し、予熱器 で加温し、 1. 3kPa、 230°Cに制御した第 2脱揮槽に導入し単量体を除去した。これ をストランド状に押出し切断することによりペレット形状のスチレン系共重合体 (II— 1) を得た。得られたスチレン系共重合体 (Π— 1)の糸且成を表 V— 2に示す。  Connect a first complete mixing tank with a volume of about 5 liters and a second complete mixing tank with a capacity of about 15 liters in series, and further connect two first and second devolatilization tanks with a preheater in series. Configured. To 100 parts of a monomer solution composed of 83% styrene containing 0.1 ppm of 4-tert-butylcatechol and 17% metataric acid (MAA) obtained in the Reference Example, 15 parts of Nzen, 0.01 part of t-butylperoxyisopropyl monocarbonate and 0.2 part of 2,4-diphenyl 4-methyl 1-pentene were mixed to obtain a raw material solution. This raw material solution was supplied to the first complete mixing tank controlled at 135 ° C at 6. Okg per hour. The conversion rate at the outlet of the first complete mixing tank was 28%. Next, it was continuously extracted from the first complete mixing tank and supplied to the second complete mixing tank controlled at 135 ° C. The conversion rate at the outlet of the second complete mixing tank was 63%. Next, it was continuously extracted from the second complete mixing tank, heated by a preheater, and introduced into the first devolatilization tank controlled at 67 kPa and 160 ° C. Furthermore, it was continuously extracted from the first devolatilization tank, heated by a preheater, and introduced into the second devolatilization tank controlled at 1.3 kPa and 230 ° C to remove the monomer. This was extruded and cut into strands to obtain pellet-shaped styrene copolymer (II-1). Table V-2 shows the properties of the resulting styrene copolymer (Π-1).
[0116] スチレン系共重合体 (III)の製造 [0116] Production of Styrene Copolymer (III)
スチレン 20%、メチルメタタリレート 80%で構成する単量体溶液を用いた以外は、 スチレン系共重合体 (I)と同様に実施しスチレン系共重合体 (III— 1)を得た。  A styrene copolymer (III-1) was obtained in the same manner as the styrene copolymer (I) except that a monomer solution composed of 20% styrene and 80% methyl methacrylate was used.
得られたスチレン系共重合体 (III 1)の組成を表 V— 2に示す。 スチレン系共重合体 (II— 1) 36%とスチレン系共重合体 (III 1) 64%を混合し、（II ) ' (II細旨組成物 1を得た。 The composition of the obtained styrene copolymer (III 1) is shown in Table V-2. 36% of the styrene copolymer (II-1) and 64% of the styrene copolymer (III 1) were mixed to obtain (II) ′ (II detailed composition 1).
スチレン系共重合体 (II— 1) 0%とスチレン系共重合体 (III 1) 100%を混合し、 (II ) ' (II細旨組成物 2を得た。  Styrene copolymer (II-1) 0% and styrene copolymer (III 1) 100% were mixed to obtain (II) ′ (II detailed composition 2).
スチレン系共重合体 (II— 1) 90%とスチレン系共重合体 (III 1) 10%を混合し、 (II ) ' (II細旨組成物 3を得た。  90% of the styrene copolymer (II-1) and 10% of the styrene copolymer (III 1) were mixed to obtain (II) ′ (II detailed composition 3).
(II) · (III)榭脂組成物 1〜3の組成を表 V— 3に示す。  (II) · (III) The composition of the resin composition 1-3 is shown in Table V-3.
[表 42]  [Table 42]
表 V— 1  Table V— 1
Figure imgf000065_0001
Figure imgf000065_0001
[0118] [表 43] [0118] [Table 43]
表 V— 2  Table V— 2
Figure imgf000065_0002
Figure imgf000065_0002
[0119] [表 44] 表 V— 3 [0119] [Table 44] Table V— 3
Figure imgf000066_0001
Figure imgf000066_0001
[0120] スチレン系共重合体 I— 1〜1— 3、 (II) '(111)榭脂組成物 1〜3、架橋ビーズ C、 D、 E ー 1〜4、 F—l〜4及び、ヒンダードアミン系化合物としてビス（2, 2, 6, 6—テトラメチ ルー 4ーピペリジル）セバケート、ベンゾトリアゾール系化合物として 2—（2H—べンゾ トリァゾールー 2—ィル）—4, 6—ジ—tert—ペンチルフエノールを表 V— 4、 V—5に 示す配合比にて混合し、 40mm径の単軸押出し機にて、温度 240°C、スクリュー回 転数 lOOrpmにて混練し、ペレット化を行い、スチレン系榭脂組成物 1〜25 (榭脂 1 〜25と略す）のペレットを得た。配合を表 V—4〜V—5に示す。 [0120] Styrene-based copolymer I-1 to 1-3, (II) '(111) resin composition 1-3, crosslinked beads C, D, E-1-4, Fl-4, and Bis (2, 2, 6, 6-tetramethyl 4-piperidyl) sebacate as a hindered amine compound, 2- (2H-Benzotriazole-2-yl) -4, 6-di-tert-pentyl as a benzotriazole compound Phenol was mixed at the mixing ratio shown in Tables V-4 and V-5, kneaded at a temperature of 240 ° C and a screw speed of lOOrpm in a 40mm diameter single screw extruder, pelletized, and styrene. Pellets of system rosin composition 1-25 (abbreviated as mortar 1-25) were obtained. The composition is shown in Tables V-4 to V-5.
尚、表 V— 4のスチレン系榭脂組成物 1〜13は、表層 a、裏層 cのスチレン系榭脂組 成物（(A)成分）に対応しており、表 V— 5のスチレン系榭脂組成物 14〜25は、中間 層 bの榭脂組成物（ (B)成分）に対応して 、る。  The styrene-based resin compositions 1 to 13 in Table V-4 correspond to the styrene-based resin composition (component (A)) in the surface layer a and the back layer c. The styrene resin compositions in Table V-5 The system resin compositions 14 to 25 correspond to the resin composition (component (B)) of the intermediate layer b.
[0121] [表 45] [0121] [Table 45]
表 V- 4 Table V-4
配合  Formulation
ベンゾ卜  Benzo
スチレン スチレン スチレン ヒンダ一 リアゾー  Styrene Styrene Styrene Hinder One Rear Zone
系共重合 系共重合 系共重合 ドアミン 未溶融化合物 体 I— 1 体 I — 2 体 I— 3 ル系化合  Copolymer Copolymer Copolymer Doamine Unmelted Compound Body I— 1 Body I — 2 Body I— 3
系化合物  Compounds
物  object
スチレン系樹脂組成物名 質量部 質量部 質量部 質量部 質量部 種類 質量部 樹脂 1 100 ― ― 0. 3 0. 3 D— 1 3. 0 樹脂 2 100 ― ― 1. 5 1. 5 D— 1 3. 0 樹脂 3 100 ― ― 0. 3 0. 3 D— 1 8. 0 樹脂 4 100 ― ― 0. 3 0. 3 D— 3 3. 0 樹脂 5 ― 100 ― 0. 3 0. 3 D— 1 3. 0 SS4 樹脂 6 ― ― 100 0. 3 0. 3 D— 1 3. 0  Styrene-based resin composition name Mass part Mass part Mass part Mass part Mass part Type Mass part Resin 1 100--0. 3 0. 3 D-1 3. 0 Resin 2 100--1. 5 1. 5 D-1 3. 0 Resin 3 100 ― ― 0. 3 0. 3 D— 1 8. 0 Resin 4 100 ― ― 0. 3 0. 3 D― 3 3. 0 Resin 5 ― 100 ― 0. 3 0. 3 D— 1 3.0 SS4 resin 6 ― ― 100 0. 3 0. 3 D― 1 3. 0
樹脂 7 100 ― ― 0. 05 0. 05 D— 1 3. 0 樹脂 8 100 ― ― 3 3 D - 1 3. 0 樹脂 9 100 ― 一 0. 3 0. 3 D— 1 0. 5 樹脂 1 0 100 ― ― 0. 3 0. 3 D— 1 13. 0 樹脂 1 1 100 ― ― 0. 3 0. 3 D— 2 3. 0 樹脂 1 2 100 ― ― 0. 3 0. 3 D— 4 3. 0 樹脂 1 3 100 ― ― 0. 3 0. 3 E— 1 3. 0 Resin 7 100 ― ― 0. 05 0. 05 D― 1 3. 0 Resin 8 100 ― ― 3 3 D-1 3. 0 Resin 9 100 ― One 0. 3 0. 3 D― 1 0. 5 Resin 1 0 100 ― ― 0. 3 0. 3 D― 1 13.0 Resin 1 1 100 ― ― 0. 3 0. 3 D― 2 3. 0 Resin 1 2 100 ― ― 0. 3 0. 3 D― 4 3. 0 Resin 1 3 100 ― ― 0. 3 0. 3 E― 1 3. 0
SΛ- SΛ-
Figure imgf000068_0001
例 V—l〜V—30
Figure imgf000068_0001
Example V—l to V—30
スチレン系榭脂組成物 1〜25を用いて、フィードブロックを有する Tダイ方式の多層 押出機にて各構成の多層シートを作成した。尚、多層押出機は、メインの中間層用 力 S65mm φのフルフライトスクリューの単軸押出機 1台、表層用に 30mm φのフルフ ライトスクリューの単軸押出機各 1台からなり各々の溶融榭脂がフィードブロックで合 流多層化される試験押出機を使用した。シート化における各シリンダー温度は 230 °Cにて運転、成形した。  Using the styrenic resin compositions 1 to 25, multilayer sheets of each constitution were prepared with a T-die type multilayer extruder having a feed block. The multi-layer extruder is composed of one single-axis extruder with a main flight S65mmφ full flight screw and one single 30mmφ full-flight screw single-screw extruder for the surface layer. A test extruder in which the fats were joined and multilayered at the feed block was used. Each cylinder temperature in sheeting was operated and molded at 230 ° C.
得られた多層シートの光学特性、耐光性、吸水反りデータを表 V—6〜9に示した。 例 V (熱変形温度の高い多層シートの例）においては、曇り度 99%以上、全光線透 過率 60%以上、拡散率 20%以上、 b値 1未満である場合、光学特性が特に優れて いると判断できる。耐光性は色差 Δ Ε値力 以下、寸法安定性は吸水反りが lmm以 下、加熱変形 lmm以下である場合、優れていると判断できる。 The optical properties, light resistance, and water absorption warpage data of the obtained multilayer sheet are shown in Tables V-6-9. In Example V (an example of a multilayer sheet with a high thermal deformation temperature), the haze is 99% or more and the total light transmittance is When the excess rate is 60% or more, the diffusion rate is 20% or more, and the b value is less than 1, it can be judged that the optical characteristics are particularly excellent. It can be judged that light resistance is excellent when the color difference is less than ΔΕ, and dimensional stability is excellent when the water absorption warpage is 1 mm or less and the heat deformation is 1 mm or less.
例 V ι〜ν— 10、及び V— 14は、これらの特性を全て併せ持つ特に好ましい実 施例である。  Examples V ι to ν-10 and V-14 are particularly preferred examples that combine all these properties.
例¥—11〜¥—16、¥—18〜¥—23、¥—26及び¥—27はその他の実施例でぁ る。  Examples ¥ —11 to ¥ —16, ¥ —18 to ¥ —23, ¥ —26 and ¥ —27 are other examples.
例 V— 14〜V— 16、及び V— 24は比較例である。  Examples V-14 to V-16 and V-24 are comparative examples.
[表 47] [Table 47]
S¾O4 表 V— 6 S¾O4 Table V— 6
例 例 例 例 例 例 例 例 例 1 2 3 4 5 6 7 8 9 觀 樹脂 1 樹脂 2 樹脂 3 樹脂 1 樹脂 4 樹脂 1 樹脂 1 樹脂 1 樹脂 1 表層  Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8 9 觀 Resin 1 Resin 2 Resin 3 Resin 1 Resin 4 Resin 1 Resin 1 Resin 1 Resin 1 Surface
a 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.01 0.1 肉厚 （mm)  a 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.01 0.1 Wall thickness (mm)
種類 樹脂 14 樹脂 14 樹脂 14 樹脂 15 樹脂 14 樹脂 25 榭脂 16 樹脂 14 樹脂 14 中間層  Type Resin 14 Resin 14 Resin 14 Resin 15 Resin 14 Resin 25 Resin 16 Resin 14 Resin 14 Intermediate layer
シート層構成 b 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 5 肉厚 （mm)  Sheet layer configuration b 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 5 Thickness (mm)
種類 樹脂 1 樹脂 2 樹脂 3 樹脂 1 樹脂 4 樹脂 1 樹脂 1 樹脂 1 樹脂 1 裏層  Type Resin 1 Resin 2 Resin 3 Resin 1 Resin 4 Resin 1 Resin 1 Resin 1 Resin 1 Back layer
c 0.1 0.1 0.1 0.1 0-1 0.1 0.1 0.01 0.1 肉厚 （mm)  c 0.1 0.1 0.1 0.1 0-1 0.1 0.1 0.01 0.1 Wall thickness (mm)
2 2 2 2 2 2 2 1.82 5.2 総肉厚 （mm)  2 2 2 2 2 2 2 1.82 5.2 Total wall thickness (mm)
67.2 67.2 65.3 63.4 63.1 65.1 69.4 68.1 62.9 シート光学特性 全光線透過率 ( )  67.2 67.2 65.3 63.4 63.1 65.1 69.4 68.1 62.9 Sheet optical characteristics Total light transmittance ()
99.1 99.1 99.2 99.4 99.4 99.2 99.2 99.1 99.4 曇り度は）  99.1 99.1 99.2 99.4 99.4 99.2 99.2 99.1 99.4 Haze is)
23.7 23.5 23.7 25.0 24.8 23.9 21.9 22.8 24.6 拡散率 W  23.7 23.5 23.7 25.0 24.8 23.9 21.9 22.8 24.6 Diffusion rate W
0.3 0.4 0.3 0.3 0.3 0.3 0.3 0.3 0.4 b値  0.3 0.4 0.3 0.3 0.3 0.3 0.3 0.3 0.4 b value
耐光性 色差厶 E 0.4 0.3 0.4 0.4 0.4 0.4 0.4 0.6 0.5 吸水反り （mm) 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.31 0.31 加熱変形 （mm) 0.43 0.42 0.44 0.41 0.43 0.42 0.43 0.31 0.30 Light resistance Color difference 厶 E 0.4 0.3 0.4 0.4 0.4 0.4 0.4 0.6 0.5 Water absorption warpage (mm) 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.31 0.31 Heat deformation (mm) 0.43 0.42 0.44 0.41 0.43 0.42 0.43 0.31 0.30
表 VTable V
Figure imgf000071_0001
例 例 例 例 例 例 例 例 例
Figure imgf000071_0001
Example Example Example Example Example Example Example Example Example
1 0 1 1 1 2 1 3 1 4 1 5 1 6 1 7 1 8 樹脂 1 樹脂 1 樹脂 5 樹脂 6 樹脂 7 榭脂 8 樹脂 9 樹脂 10 樹脂 11 表層  1 0 1 1 1 2 1 3 1 4 1 5 1 6 1 7 1 8 Resin 1 Resin 1 Resin 5 Resin 6 Resin 7 Resin 8 Resin 9 Resin 10 Resin 11 Surface
a 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 肉厚 （mm)  a 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 0. 1 Thickness (mm)
種類 樹脂 17 樹脂 18 樹脂 14 樹脂 14 樹脂 14 樹脂 14 樹脂 14 樹脂 14 樹脂 14 中間層  Type Resin 17 Resin 18 Resin 14 Resin 14 Resin 14 Resin 14 Resin 14 Resin 14 Resin 14 Interlayer
シート層構成 b 1. 8 1. 8 し 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 肉厚 （mm)  Sheet layer structure b 1. 8 1. 8 and 8 1. 8 1. 8 1. 8 1. 8 1. 8 1. 8 Thickness (mm)
種類 樹脂 1 樹脂 1 樹脂 5 樹脂 6 樹脂 7 樹脂 8 樹脂 9 樹脂 10 樹脂 11 裏層  Type Resin 1 Resin 1 Resin 5 Resin 6 Resin 7 Resin 8 Resin 9 Resin 10 Resin 11 Back layer
c 0. 1 0. 1 0. 1 0. 1 0- 1 0. 1 0. 1 0- 1 0. 1 肉厚 (mm)  c 0. 1 0. 1 0. 1 0. 1 0- 1 0. 1 0. 1 0- 1 0. 1 Thickness (mm)
2 2 2 2 2 2 2 2 2 総肉厚 （mm)  2 2 2 2 2 2 2 2 2 Total wall thickness (mm)
66. 8 67. 1 67. 2 67. 1 67. 4 66. 8 70. 8 58. 9 68. 2 全光線透過率 (»  66. 8 67. 1 67. 2 67. 1 67. 4 66. 8 70. 8 58. 9 68. 2 Total light transmittance (»
99. 2 99. 1 99. 2 99. 1 99. 2 99. 3 97. 9 99. 4 99. 2 曇り度は）  99. 2 99. 1 99. 2 99. 1 99. 2 99. 3 97. 9 99. 4 99. 2 Haze is)
シート光学特性  Sheet optical properties
23. 5 23. 7 23. 4 23. 2 23. 5 23. 7 19. 4 25. 5 20. 3 拡散率は）  23. 5 23. 7 23. 4 23. 2 23. 5 23. 7 19. 4 25. 5 20. 3 Diffusion rate is)
0. 3 0. 4 0. 4 0. 3 0. 3 1. 1 0. 3 0. 3 1. 0 b値  0. 3 0. 4 0. 4 0. 3 0. 3 1. 1 0. 3 0. 3 1. 0 b value
耐光性 色差 Δ Ε 0. 4 1. 2 1. 1 0. 3 1. 2 0. 2 0. 4 0. 4 0. 4 吸水反り （mm) 0. 51 0. 32 0. 32 1. 14 0. 32 0. 34 0. 30 0. 33 0. 34 加熱変形 （mm) 1. 44 0. 24 0. 40 0. 41 0. 40 0. 44 0. 41 0. 42 0. 42 Light resistance Color difference Δ Ε 0. 4 1. 2 1. 1 0. 3 1. 2 0. 2 0. 4 0. 4 0. 4 Water absorption warpage (mm) 0. 51 0. 32 0. 32 1. 14 0 32 0. 34 0. 30 0. 33 0. 34 Heat distortion (mm) 1. 44 0. 24 0. 40 0. 41 0. 40 0. 44 0. 41 0. 42 0. 42
S3S0125 表 V— 8 S3S0125 Table V— 8
例 例 例 例 例 例 例 例 例 1 9 20 2 1 22 23 24 2 5 26 2 7 種類 樹脂 12 樹脂 13 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 表層  Example Example Example Example Example Example Example Example 1 9 20 2 1 22 23 24 2 5 26 2 7 Types Resin 12 Resin 13 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Surface layer
a 0. 1 0. 1 0.1 0.1 0.1 0.1 0.1 0.1 0.003 肉厚 （mm)  a 0. 1 0. 1 0.1 0.1 0.1 0.1 0.1 0.1 0.003 Wall thickness (mm)
種類 樹脂 14 樹脂 14 樹脂 19 樹脂 20 樹脂 21 樹脂 22 樹脂 23 樹脂 24 樹脂 14 中間層  Type Resin 14 Resin 14 Resin 19 Resin 20 Resin 21 Resin 22 Resin 23 Resin 24 Resin 14 Intermediate 14
シート層構成 b 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8  Sheet layer configuration b 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8
肉厚 （ 1.8 mm)  Wall thickness (1.8 mm)
種類 樹脂 12 樹脂 13 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 樹脂 1 裏層  Type Resin 12 Resin 13 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Back layer
c 0. 1 0.1 0.1 0.1 0-1 0.1 0.1 0-1 0.003 肉厚 (mm)  c 0. 1 0.1 0.1 0.1 0-1 0.1 0.1 0-1 0.003 Wall thickness (mm)
2 2 2 2 2 2 2 2 1.806 総肉厚 （mm)  2 2 2 2 2 2 2 2 1.806 Total wall thickness (mm)
59.6 55.9 70.4 58.4 70.2 58.4 71.1 55.9 67.6 全光線透過率 («  59.6 55.9 70.4 58.4 70.2 58.4 71.1 55.9 67.6 Total light transmittance («
99.5 99.7 98.0 99.4 98.4 99.4 98.2 99.7 99.1 曇り度は）  99.5 99.7 98.0 99.4 98.4 99.4 98.2 99.7 99.1 Cloudiness is)
シート光学特性  Sheet optical properties
25.4 27.8 18.7 24.6 19.7 25.3 17.9 25.9 23.6 拡散率 (《  25.4 27.8 18.7 24.6 19.7 25.3 17.9 25.9 23.6 Diffusion rate (<<
0.8 0.3 0.3 0.3 1.1 0.7 0.3 0.3 0.3 b値  0.8 0.3 0.3 0.3 1.1 0.7 0.3 0.3 0.3 b value
耐光性 色差厶 E 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 1. 1 吸水反り （mm) 0.33 0.33 0.32 0.33 0.31 0.33 0.32 0.34 0.32 加熱変形 （mm) 0.43 0.42 0.44 0.40 0.41 0.45 0.43 0.42 0.41 Light resistance Color difference 厶 E 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 1. 1 Water absorption warpage (mm) 0.33 0.33 0.32 0.33 0.31 0.33 0.32 0.34 0.32 Heat distortion (mm) 0.43 0.42 0.44 0.40 0.41 0.45 0.43 0.42 0.41
Figure imgf000073_0001
Figure imgf000073_0001
各物性値の測定方法は以下の通りである。  The measuring method of each physical property value is as follows.
(1) 全光線透過率、曇り度: ASTM D— 1003に準じて、日本電色工業社製 HAZ Eメーター（NDH - 2000)を用いて測定した。  (1) Total light transmittance, haze: Measured according to ASTM D-1003 using a HAZ E meter (NDH-2000) manufactured by Nippon Denshoku Industries Co., Ltd.
(2) 拡散率：日本電色工業社製変角光度計 (GC5000L)を用いて、受光角 0° の 光線透過率 I、受光角 70° 光線透過率 I を測定し、次式により算出した。  (2) Diffusivity: Using a variable angle photometer (GC5000L) manufactured by Nippon Denshoku Industries Co., Ltd., light transmittance I at a light receiving angle of 0 ° and light transmittance I at a light receiving angle of 70 ° were measured and calculated by the following formula: .
0 70  0 70
拡散率(％) = (1 Diffusion rate (%) = (1
70 /D 0 xioo  70 / D 0 xioo
(3) 屈折率:未溶融化合物については、アッベ式屈折計にて波長 589nm 23°Cの 雰囲気下にて測定した。また、スチレン系共重合体については、デジタル屈折率計（ ATAGO社製 RX— 2000)を用いて、接触液としてヨウ化カリウム飽和水溶液を使用 して、温度 25°Cで測定した。  (3) Refractive index: Unmelted compounds were measured with an Abbe refractometer in an atmosphere with a wavelength of 589 nm and 23 ° C. The styrene copolymer was measured at a temperature of 25 ° C. using a digital refractometer (RX-2000, manufactured by ATAGO) using a saturated aqueous solution of potassium iodide as a contact liquid.
(4) 耐光性:東洋精機製作所社製キセノンウエザーメーター、アトラス CI65Aを用 いて 400Hr照射し、光照射前後の色差 ΔΕを測定した。 日本電色社製色差計（∑— 80)を用いて、 L, a, bを測定し、耐光性評価の色差 ΔΕは次式により求めた。  (4) Light resistance: 400Hr was irradiated using a xenon weather meter manufactured by Toyo Seiki Seisakusho, Atlas CI65A, and the color difference Δ 色 before and after the light irradiation was measured. L, a, and b were measured using a color difference meter (∑-80) manufactured by Nippon Denshoku Co., Ltd., and the color difference ΔΕ for light resistance evaluation was determined by the following equation.
AE=((L-L')2+(a-a')2+(b-b')2)1/2 但し、 L, a, bは、耐光性評価前の色相、 L '， a' , b 'は、耐光性評価後（400H r照射後）の色相である。 AE = ((L-L ') 2 + (a-a') 2 + (b-b ') 2 ) 1/2 However, L, a, b are hues before light resistance evaluation, and L ′, a ′, b ′ are hues after light resistance evaluation (after 400 Hr irradiation).
(5) 吸湿性：得られた光拡散シートを 300mm X 300mmの寸法に切削し 50°C、湿 度 80%の雰囲気下に 7日間放置後の変形量をスケールで測定した。吸湿性は変形 量 lmm以下を良好とした。  (5) Hygroscopicity: The obtained light diffusion sheet was cut into dimensions of 300 mm x 300 mm, and the deformation after standing for 7 days in an atmosphere of 50 ° C and 80% humidity was measured on a scale. Hygroscopicity was good when the deformation was 1 mm or less.
(6) 黄色度：日本電色社製色差計（∑— 80)を用いて、 L, a, bを測定し、黄色度の 尺度として b値を示した。  (6) Yellowness: L, a, and b were measured using a color difference meter (∑-80) manufactured by Nippon Denshoku Co., Ltd., and the b value was shown as a measure of yellowness.
( 7) スチレン系共重合体の榭脂組成：スチレン系共重合体を重クロ口ホルムに溶解 して 2%溶液に調製して測定資料として、 FT— NMR (日本電子社製 FX— 90Q型） を用いて c13測定し、スチレンとメチルメタタリレートのピーク面積より算出した。 (7) Resin composition of styrene copolymer: Dissolve styrene copolymer in heavy chloroform to prepare 2% solution, and use FT-NMR (FX-90Q model, manufactured by JEOL Ltd.) as measurement data. ) Was used to measure c 13 and calculated from the peak areas of styrene and methyl methacrylate.
(8) 寸法安定性（吸水反り）：例1〜1¥にぉぃては180111111 180111111、例 Vにおい ては 300mm X 300mmの大きさに切削したシートを、 50°C、湿度 80%の雰囲気下 に 7日間放置した後、水平面に置いた成形体の四隅の水平面力 の距離をノギスで 測定、その 4つの値の平均値を吸水反りの値とし、この値を寸法安定性の尺度とした  (8) Dimensional stability (water absorption warpage): Example 1 to 1 ¥ 180111111 180111111, Example V: 300mm x 300mm size sheet, 50 ° C, 80% humidity atmosphere After standing for 7 days, the distance of the horizontal plane force at the four corners of the molded body placed on the horizontal plane was measured with calipers, and the average of the four values was taken as the value of water absorption warpage, and this value was taken as a measure of dimensional stability.
(9) 帯電防止性: JIS 1：—6911に準拠して温度23で、湿度50%1¾1で24時間調 湿したものの表面固有抵抗値を、 KAWAGUCHI社製表面固有抵抗測定機 (R50 3)を用いて測定し、この値を帯電防止性の尺度とした。 (9) Antistatic property: The surface resistivity value of the material conditioned at a temperature of 23 and a humidity of 50% 1¾1 for 24 hours in accordance with JIS 1: 6911 was measured using a surface resistivity measuring machine (R50 3) manufactured by KAWAGUCHI. This value was used as a measure of antistatic properties.
(10) 耐傷付き性：同種材のシートを 2枚重ね、底面積 10cm2で 300gの荷重をかけ た状態で、上方のシートを lcm幅に 1分間に 60回の速度で 60回振動させた後の表 面を目視で観察した。傷が全く認められないものを「優」、殆ど認められないものを「 良」、明らかに傷が認められるものを「不良」と判断した。 (10) Scratch resistance: Two sheets of the same material were stacked, and the upper sheet was vibrated 60 times at a speed of 60 times per lcm width with a load of 300 g with a bottom area of 10 cm 2 . The rear surface was visually observed. The case where no flaw was observed was judged as “excellent”, the case where flaws were hardly recognized as “good”, and the case where flaws were clearly recognized as “bad”.
(11) 加熱変形:得られた光拡散シートを 300mm X 300mmの寸法に切削し、 80°C、の雰囲気下に 7日間放置後の変形量をスケールで測定した。  (11) Heat deformation: The obtained light diffusion sheet was cut to a size of 300 mm × 300 mm, and the amount of deformation after standing for 7 days in an atmosphere at 80 ° C. was measured on a scale.
(12) スチレン系共重合体中のメタクリル酸単量体単位含有量の測定：  (12) Measurement of methacrylic acid monomer unit content in styrene copolymer:
I.スチレン系共重合体中のメタクリル酸単量体単位と残存メタクリル酸の合計量の測 定  I. Measurement of total amount of methacrylic acid monomer units and residual methacrylic acid in styrene copolymer
(1)スチレン系共重合体 2gにクロ口ホルム：エタノール混合溶液（2 : 1) 100mlを加え 溶解させる。（2)これに指示薬として 0. 5%フエノールフタレイン'エタノール溶液をカロ え、更に 0. 1N水酸ィ匕カリウム 'エタノール溶液で滴定する。指示薬の色が 30秒間消 えな 、時を終点とした。（3)空試験としてクロ口ホルム：エタノール混合溶液 (2： 1)を 10 Omlとり (2)と同様の操作を行った。（4)以下の式のよりスチレン系共重合体中のメタタリ ル酸含有量を求めた。 (1) Add 2 ml of styrene-based copolymer to 100 ml of black mouth form: ethanol mixed solution (2: 1) Dissolve. (2) Carry out 0.5% phenolphthalein 'ethanol solution as an indicator, and titrate with 0.1N potassium hydroxide' ethanol solution. When the indicator color did not disappear for 30 seconds, the time was the end point. (3) As a blank test, 10 ml of black mouth form: ethanol mixed solution (2: 1) was taken and the same operation as (2) was performed. (4) The content of metatalic acid in the styrene copolymer was determined from the following formula.
メタクリル酸含有量（％) =[{ (A-B) X M}/ (S X 1000)] X 100  Methacrylic acid content (%) = [{(A-B) X M} / (S X 1000)] X 100
A : (1)に要した滴定量 （ml)  A: Titration required for (1) (ml)
B : (3)に要した滴定量 （ml)  B: Titration required for (3) (ml)
S :スチレン系共重合体の質量 （g)  S: Mass of styrene copolymer (g)
M： 0. 1N水酸化カリウム ·エタノール溶液 lmlと当量となるメタクリル酸の質量（8 . 6 ung  M: 0.1N potassium hydroxide-ethanol solution Mass of methacrylic acid equivalent to 1 ml (8.6 ung
[0130] II.スチレン系共重合体中の残存メタクリル酸量の測定  [0130] II. Measurement of amount of residual methacrylic acid in styrene copolymer
スチレン系共重合体 0. 5gをクロ口ホルム 10mlに溶解し、 N, N—ジメチルホルムァ ミドを内部標準として測定して、以下の GC測定条件で測定した。  0.5 g of a styrene copolymer was dissolved in 10 ml of black mouth form, and N, N-dimethylformamide was measured as an internal standard, and the measurement was performed under the following GC measurement conditions.
装置名：島津製作所社製 GC14B FID検出器  Device name: GC14B FID detector manufactured by Shimadzu Corporation
カラム：ガラスカラム φ 3πιπι Χ 3πι  Column: Glass column φ 3πιπι Χ 3πι
充填剤：ジエチレングリコーノレサクシネート キヤリャ一：窒素  Filler: Diethyleneglycolenosuccinate Carrier: Nitrogen
温度：カラム 110°C、注入口 180°C  Temperature: Column 110 ° C, inlet 180 ° C
S¾料 0. 5g  S¾ charge 0.5 g
[0131] III. Iで測定したスチレン系共重合体中のメタクリル酸単量体単位と残存メタクリル酸 の合計量から、 IIで測定したスチレン系共重合体中の残存メタクリル酸量を差し引い た値をスチレン系共重合体中のメタクリル酸単量体単位含有量として求めた。但し、 スチレン系共重合体中の残存メタクリル酸の測定値が 0. 1%未満のものについては 、残存メタクリル酸量を 0%としてスチレン系共重合体中のメタクリル酸単量体単位含 有量を求めた。  [0131] III. Value obtained by subtracting the amount of residual methacrylic acid in the styrene copolymer measured in II from the total amount of methacrylic acid monomer units and residual methacrylic acid in the styrene copolymer measured in I Was determined as the methacrylic acid monomer unit content in the styrene copolymer. However, in the case where the measured value of residual methacrylic acid in the styrene copolymer is less than 0.1%, the content of methacrylic acid monomer units in the styrene copolymer with the residual methacrylic acid amount being 0% Asked.
産業上の利用可能性  Industrial applicability
[0132] 本発明の多層シートは、プロジェクシヨンテレビ等の画面の透過型スクリーンや液晶 TVフルネルレンズやレンチキュラーレンズ、光拡散板等として、広範な分野で好適 に用いることができる。 なお、 2004年 11月 26曰に出願された曰本特許出願 2004— 341624号、 2005 年 4月 6日に出願された日本特許出願 2005— 109374号、 2005年 4月 7日に出願 された日本特許出願 2005— 110800号、 2005年 4月 11曰に出願された日本特許 出願 2005— 113155号、及び 2005年 4月 26曰に出願された曰本特許出願 2005 — 127367号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本 発明の明細書の開示として、取り入れるものである。 [0132] The multilayer sheet of the present invention is a transmissive screen or a liquid crystal screen for a projection television or the like. It can be suitably used in a wide range of fields as a TV fullnel lens, a lenticular lens, a light diffusion plate, and the like. Japanese patent application 2004-341624 filed on November 26, 2004, Japanese patent application 2005-109374 filed on April 6, 2005, Japan filed April 7, 2005 Patent application 2005-110800, Japanese patent application filed on April 11, 2005, Japanese patent application 2005-113155, and Japanese patent application 2005-127367 filed on April 26, 2005 , And the entire contents of the abstract are hereby incorporated by reference as a disclosure of the specification of the present invention.

Claims

請求の範囲 The scope of the claims
[1] 多層構成のシートであって、表層 a及び裏層 cが下記 (A)成分を主成分とし、中間 層 bが下記 (B)成分を主成分とすることを特徴とする多層シート。  [1] A multilayer sheet, wherein the surface layer a and the back layer c have the following component (A) as a main component, and the intermediate layer b has the following component (B) as a main component.
(A)成分:スチレン系単量体単位 20〜50質量％及び (メタ）アクリル酸エステル系単 量体単位 80〜50質量0 /0力もなるスチレン系共重合体 100質量部と、該スチレン系 共重合体との屈折率差が 0. 005以内であり、平均粒子径が 5〜 15 mの未溶融化 合物を 1〜10質量部と、ヒンダードアミン系化合物を 0. 1〜2質量部と、ベンゾトリア ゾール系化合物を 0. 1〜2質量部と、を含有してなるスチレン系榭脂組成物。 Component (A): styrene-based monomer unit 20 to 50% by weight, and (meth) and styrene copolymer 100 parts by weight is also an acrylic acid ester-based monomer unit 80 to 50 weight 0/0 force, the styrene-based 1 to 10 parts by mass of an unmelted compound having a refractive index difference with the copolymer within 0.005 and an average particle diameter of 5 to 15 m, and 0.1 to 2 parts by mass of a hindered amine compound And a styrene-based resin composition comprising 0.1 to 2 parts by mass of a benzotriazole-based compound.
(B)成分:スチレン系共重合体 100質量部と、該スチレン系共重合体との屈折率差 が 0. 05〜0. 14であり、平均粒子径が 2〜10 /ζ πιの未溶融化合物 1〜10質量部と を、含有してなる榭脂組成物。  Component (B): 100 parts by mass of a styrene copolymer and an unmelted material having a refractive index difference of 0.05 to 0.14 and an average particle diameter of 2 to 10 / ζ πι A resin composition comprising 1 to 10 parts by mass of a compound.
[2] (Β)成分のスチレン系共重合体が、スチレン系単量体単位 50〜90質量％及び (メ タ）アクリル酸エステル系単量体単位 50〜10質量％からなるスチレン系共重合体で ある、請求項 1に記載の多層シート。  [2] The styrene copolymer of component (ii) is composed of 50 to 90% by mass of styrene monomer units and 50 to 10% by mass of (meth) acrylate monomer units. The multilayer sheet according to claim 1, which is a coalescence.
[3] (Β)成分のスチレン系共重合体力 スチレン系単量体単位 50〜90質量0 /0、（メタ） アクリル酸エステル系単量体単位 50〜 10質量％、及び共重合可能なビ-ルイ匕合物 単量体単位 0〜： L0質量％からなるスチレン系共重合体である、請求項 1に記載の多 層シート。 [3] (beta) styrene copolymer fitness styrenic monomer units from 50 to 90 weight of component 0/0, (meth) acrylic acid ester monomer units 50-10 wt%, and copolymerizable bi -Louis composite material The multilayer sheet according to claim 1, which is a styrene-based copolymer comprising monomer units 0 to L0% by mass.
[4] (Β)成分のスチレン系共重合体が、スチレン系単量体単位 80〜99質量0 /0、メタタリ ル酸単量体単位 20〜 1質量％及び共重合可能なビニル化合物単量体単位 0〜 10 質量0 /0からなるスチレン系共重合体 (II) 30〜70質量部と、スチレン系単量体単位 2 0〜60質量％及び (メタ）アクリル酸エステル系単量体単位 80〜40質量％力 なるス チレン系共重合体 (III) 70〜30質量部とからなる榭脂混合物である、請求項 1に記 載の多層シート。 [4] (Β) a styrene copolymer component is a styrene-based monomer unit 80 to 99 weight 0/0, Metatari Le acid monomer units 20-1% by weight and copolymerizable vinyl compound monomer styrene copolymers composed of the body unit 0-10 mass 0/0 (II) 30 to 70 parts by weight of a styrene-based monomer unit 2 0-60% by weight, and (meth) acrylic acid ester monomer units The multilayer sheet according to claim 1, wherein the styrene copolymer (III) has a strength of 80 to 40% by mass and is a resin mixture consisting of 70 to 30 parts by mass.
[5] (Α)成分に含有される未溶融化合物は、その一部を表層 a及び裏層 cの表面に突 出させ、表層 a及び裏層 cの表面に凹凸を形成してなる、請求項 1〜4のいずれか 1 項に記載の多層シート。  [5] A part of the unmelted compound contained in the component (ii) protrudes from the surface of the surface layer a and the back layer c to form irregularities on the surface of the surface layer a and the back layer c. Item 5. The multilayer sheet according to any one of Items 1 to 4.
[6] 未溶融化合物は、 1気圧の雰囲気下で、 200°C以上の融点又は軟ィ匕点を有する化 合物である、請求項 1〜5のいずれか 1項に記載の多層シート。 [6] Unmelted compounds have a melting point or soft saddle point of 200 ° C or higher in an atmosphere of 1 atm. The multilayer sheet according to any one of claims 1 to 5, which is a compound.
[7] (A)成分に含有される未溶融化合物が、単量体としてスチレン及びメタクリル酸メチ ルを含む架橋共重合体である請求項 1〜6のいずれ力 1項に記載の多層シート。 [7] The multilayer sheet according to any one of [1] to [6], wherein the unmelted compound contained in the component (A) is a cross-linked copolymer containing styrene and methyl methacrylate as monomers.
[8] (B)成分に含有される未溶融化合物が、単量体としてメタクリル酸メチルを含む架 橋重合体である請求項 1〜7のいずれか 1項に記載の多層シート。 [8] The multilayer sheet according to any one of [1] to [7], wherein the unmelted compound contained in the component (B) is a crosslinked polymer containing methyl methacrylate as a monomer.
[9] ヒンダードアミン系化合物力 ビス（2, 2, 6, 6—テトラメチルー 4ーピペリジル）セバ ケートである請求項 1〜8のいずれか 1項に記載の多層シート。 [9] The multilayer sheet according to any one of claims 1 to 8, which is bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate.
[10] ベンゾトリアゾール系化合物力 2- (2H ベンゾトリアゾール 2—ィル） 4— (1[10] Strength of benzotriazole compounds 2- (2H benzotriazole 2-yl) 4— (1
, 1, 3, 3—テトラメチルブチル）フエノールである請求項 1〜9のいずれか 1項に記載 の多層シート。 , 1, 3, 3-tetramethylbutyl) phenol. The multilayer sheet according to any one of claims 1 to 9.
[11] (A)成分と（B)成分の少なくとも一方に、ベンゾキサゾール系化合物を 0. 0005- 0. 5質量部含有する、請求項 1〜： L0のいずれか 1項に記載の多層シート。  [11] The multilayer according to any one of L1 to L0, wherein at least one of the component (A) and the component (B) contains 0.0005 to 0.5 part by mass of a benzoxazole-based compound. Sheet.
[12] ベンゾキサゾール系化合物が、 2, 5 チォフェンジィル（5 tーブチルー 1, 3— ベンゾキサゾール)である、請求項 11に記載の多層シート。  12. The multilayer sheet according to claim 11, wherein the benzoxazole-based compound is 2,5 thiofensyl (5 t-butyl-1,3-benzoxazole).
[13] (A)成分のスチレン系榭脂組成物力 さらに、スチレン系共重合体 100質量部に対 して、スチレン系共重合体との屈折率差が 0. 02以下のポリエーテルエステルアミド ブロック共重合体を 7〜20質量部、ァ-オン系界面活性剤及び Z又は非アミンノ- オン系界面活性剤を 0〜2質量部含有する、請求項 1〜12のいずれか 1項に記載の 多層シート。  [13] Strength of component (A) styrene-based resin Further, polyetheresteramide block having a refractive index difference of 0.02 or less with respect to 100 parts by mass of styrene-based copolymer The copolymer according to any one of claims 1 to 12, comprising 7 to 20 parts by mass of a copolymer, 0 to 2 parts by mass of an ionic surfactant and Z or a non-amine surfactant. Multi-layer sheet.
[14] ポリエーテルエステルアミドブロック共重合体力 単量体として次の（F—A)、 (F- B)、及び (F— C)力 なるポリエーテルエステルアミドブロック共重合体である請求項 13に記載の多層シート。  [14] Polyetheresteramide block copolymer force A polyetheresteramide block copolymer having the following (F—A), (F—B), and (F—C) force as a monomer: A multilayer sheet as described in 1.
(F-A)：炭素原子数 6以上のアミノカルボン酸若しくはラタタム、又は炭素原子数 6 以上のジァミンとジカルボン酸の塩。  (F-A): Aminocarboxylic acid or ratatam having 6 or more carbon atoms, or a salt of diamine and dicarboxylic acid having 6 or more carbon atoms.
(F-B) :一般式 (化 1)〜（化 3)の少なくとも 1種のジオールィ匕合物。  (F-B): At least one diol compound of the general formulas (Chemical Formula 1) to (Chemical Formula 3).
[化 1] (化 1 ) [Chemical 1] (Chemical 1)
Figure imgf000079_0001
Figure imgf000079_0001
(式中、 Rlはエチレンォキシド基、 R2はエチレンォキシド基又はプロピレンォキシド 基、 Xはハロゲン、アルキル基 (炭素数： 1〜6)又はスルホン酸基若しくはその金属塩 、 Lは 0〜4の整数、 m及び nは 16以上の整数を表す。 ) (Wherein Rl is an ethylene oxide group, R2 is an ethylene oxide group or propylene oxide group, X is a halogen, an alkyl group (carbon number: 1 to 6) or a sulfonic acid group or a metal salt thereof, L is 0 to Integer of 4, m and n represent an integer of 16 or more.
[化 2] [Chemical 2]
(化 2 ) (Chemical 2)
H -(RH-(R
Figure imgf000079_0002
Figure imgf000079_0002
(式中、 Rlはエチレンォキシド基、 R2はエチレンォキシド基又はプロピレンォキシド 基、 Xはハロゲン、アルキル基 (炭素数： 1〜6)又はスルホン基若しくはその金属塩、 Yはアルキレン基 (炭素数： 1〜6)、アルキリデン基 (炭素数： 1〜6)、シクロアルキリ デン基 (炭素数： 7〜 17)、ァリールアルキリデン基 (炭素数： 7〜 17)、 0、 SO、 SO、(Wherein Rl is an ethylene oxide group, R2 is an ethylene oxide group or propylene oxide group, X is a halogen, an alkyl group (carbon number: 1 to 6) or a sulfone group or a metal salt thereof, Y is an alkylene group ( Carbon number: 1-6), alkylidene group (carbon number: 1-6), cycloalkylidene group (carbon number: 7-17), arylealkylidene group (carbon number: 7-17), 0, SO, SO,
22
CO、 S、 CF、 C (CF ) 又は NH、 Lは 0〜4の整数、 m及び nは 16以上の整数を表CO, S, CF, C (CF) or NH, L is an integer of 0 to 4, m and n are integers of 16 or more
2 3 2 2 3 2
す。） The )
[化 3] [Chemical 3]
(化 3 )
Figure imgf000079_0003
(Chemical 3)
Figure imgf000079_0003
(式中、 R1はエチレンォキシド基、 R2はエチレンォキシド基又はプロピレンォキシド 基、 m及び nは 16以上の整数を表す。 ) (Where R1 is an ethylene oxide group, R2 is an ethylene oxide group or propylene oxide) The groups m and n represent an integer of 16 or more. )
(F-C)：炭素数 4〜20のジカルボン酸。  (F-C): a dicarboxylic acid having 4 to 20 carbon atoms.
[15] (A)成分中のァ-オン系界面活性剤及び非アミンノ-オン系界面活性剤の配合比 力 ァ-オン系界面活性剤 Z非アミンノ-オン系界面活性剤 =0. 5/99. 5〜15Z[15] Mixing ratio of cation surfactant and non-amine-non surfactant in component (A) Force-on surfactant Z Non-amine-non surfactant = 0.5 / 99. 5 ~ 15Z
85 (質量比）である請求項 13又は 14に記載の多層シート。 The multilayer sheet according to claim 13 or 14, which is 85 (mass ratio).
[16] (A)成分中のァ-オン系界面活性剤が、炭素数 10〜 14の有機スルホン酸金属塩 であり、非アミンノニオン系界面活性剤が、グリセリン脂肪酸エステルである請求項 13[16] The ionic surfactant in component (A) is an organic sulfonic acid metal salt having 10 to 14 carbon atoms, and the non-amine nonionic surfactant is a glycerin fatty acid ester.
〜 15のいずれ力 1項に記載の多層シート。 The multilayer sheet according to any one of ˜15.
[17] 表層 a及び裏層 cが 0. 005〜0. 5mm、中間層 bが l〜7mmである請求項 1〜16 いずれか 1項に記載の多層シート。 [17] The multilayer sheet according to any one of [1] to [16], wherein the surface layer a and the back layer c are 0.005 to 0.5 mm, and the intermediate layer b is 1 to 7 mm.
[18] 表層 a、中間層 b及び裏層 cが、押出し加工して得られた層である請求項 1〜17の いずれか 1項に記載の多層シート。 [18] The multilayer sheet according to any one of [1] to [17], wherein the surface layer a, the intermediate layer b, and the back layer c are layers obtained by extrusion.
[19] 表層 a、中間層 b及び裏層 cが、同時に押出し加工して得られた層である請求項 18 に記載の多層シート。 [19] The multilayer sheet according to [18], wherein the surface layer a, the intermediate layer b, and the back layer c are layers obtained by extruding at the same time.
[20] 請求項 1〜19のいずれか 1項に記載の多層シートを用いた光拡散シート。 [20] A light diffusion sheet using the multilayer sheet according to any one of claims 1 to 19.
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EP2573596A4 (en) * 2010-05-20 2015-05-13 Sharp Kk Method for manufacturing optical member
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WO2023041512A1 (en) 2021-09-14 2023-03-23 Ineos Styrolution Group Gmbh High clarity and low haze uv stabilized styrene and methyl methacrylate copolymers

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