WO2024024977A1 - スチレン系樹脂組成物、及び成形品 - Google Patents

スチレン系樹脂組成物、及び成形品 Download PDF

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Publication number
WO2024024977A1
WO2024024977A1 PCT/JP2023/027872 JP2023027872W WO2024024977A1 WO 2024024977 A1 WO2024024977 A1 WO 2024024977A1 JP 2023027872 W JP2023027872 W JP 2023027872W WO 2024024977 A1 WO2024024977 A1 WO 2024024977A1
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Prior art keywords
mass
resin composition
meth
styrene
monomer unit
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English (en)
French (fr)
Japanese (ja)
Inventor
松太郎 小林
大和 岩本
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PS Japan Corp
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PS Japan Corp
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Priority to CN202380053034.4A priority Critical patent/CN119546701A/zh
Priority to US19/099,527 priority patent/US20260035553A1/en
Priority to EP23846707.0A priority patent/EP4563642A4/en
Priority to KR1020247040783A priority patent/KR20250007006A/ko
Publication of WO2024024977A1 publication Critical patent/WO2024024977A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/46—Means for plasticising or homogenising the moulding material or forcing it into the mould
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K5/20—Carboxylic acid amides
    • 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
    • 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
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
    • B29K2025/04—Polymers of styrene
    • B29K2025/08—Copolymers of styrene, e.g. AS or SAN, i.e. acrylonitrile styrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/007—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0089—Impact strength or toughness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods

Definitions

  • the present disclosure relates to a styrenic resin composition and an injection molded article molded using the styrenic resin composition.
  • Styrene-unsaturated carboxylic acid resins such as styrene-methacrylic acid copolymer resins, have excellent heat resistance, transparency, rigidity, and appearance, and are inexpensive, so they are used as packaging materials for food containers such as lunch boxes and side dishes. It is widely used in foam boards for insulation of houses, housing materials for lighting equipment, and diffusion plates or light guide plates for liquid crystal televisions containing a diffusion agent. Among these, acrylic resin, which has excellent transparency, is widely used as a diffuser plate or a light guide plate used in the backlight of a liquid crystal television.
  • Patent Document 1 describes a composition containing a styrene-(meth)acrylic acid copolymer resin, an ether compound and/or an alcohol of C6 or higher, and a phenolic antioxidant and/or a phosphorus antioxidant. Techniques have been disclosed that provide excellent hue and transparency, and reduce changes in hue even after long-term exposure to light.
  • Patent Document 1 discusses transparency and changes in yellowness, it was insufficient in terms of mechanical strength, oil resistance, and scratch resistance.
  • conventional styrene-unsaturated carboxylic acid resins are corroded by oils on people's hands, such as transparent plates. Resistance to oil is required because it can cause cracking and whitening. Therefore, the problem to be solved by the present disclosure is to provide a styrenic resin composition that can be used for molded articles that have excellent weather resistance, mechanical strength, and oil resistance without reducing heat resistance and transparency. be.
  • styrene-unsaturated carboxylic acid resin A styrene-unsaturated carboxylic acid resin (A), (meth)acrylic resin (B), light stabilizer (C), and ultraviolet absorber (D)
  • a styrenic resin composition that has excellent weather resistance, mechanical strength, and oil resistance without reducing heat resistance and transparency by containing a predetermined amount of each, and an automotive molded product using the same. They succeeded in realizing this and completed the present invention. That is, the present disclosure is as follows.
  • the present disclosure provides a styrene-unsaturated carboxylic acid resin (A) having a styrene monomer unit (1) and an unsaturated carboxylic acid monomer unit (a1) from 10% by mass to 100% by mass and, A styrenic resin composition containing 0% by mass or more and 90% by mass or less of a (meth)acrylic resin (B) having an unsaturated carboxylic acid monomer unit (b1), Styrene containing 0 to 2.0% by mass of a light stabilizer (C) and 0.001 to 2.0% by mass of an ultraviolet absorber (D) based on the total amount (100% by mass) of the styrene resin composition. It is a type resin composition.
  • composition according to [1] or [2] further contains 0.001 to 1.0% by mass of a monohydric alcohol (E) having 10 or more carbon atoms based on the total amount of the styrene resin composition. styrenic resin composition.
  • E monohydric alcohol
  • the ultraviolet absorber (D) has the general formula (d) and the general formula (d'):
  • M di each independently represents a monovalent or more aromatic group
  • R d represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • L di each independently represents a divalent to pentavalent group
  • one or more hydrogen atoms of the benzene ring in the aralkyl group may be substituted with a phenolic hydroxyl group, an alkyl group having 1 to 15 carbon atoms, or a fused ring
  • d1 represents an integer of 0 to 4
  • d2 represents an integer of 1 to 4.
  • R 5 to R 7 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, and 1 to 15 carbon atoms.
  • d5 represents an integer from 0 to 4, and when d5 is 2 or more, R 8 may be the same or different.
  • One or more antioxidants selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and phosphorus antioxidants having a hindered phenol skeleton, each containing 0.001 to 0.
  • the content of the unsaturated carboxylic acid monomer unit (a1) based on the entire styrene-unsaturated carboxylic acid resin (A) is 8.5% by mass or more, [1] The styrenic resin composition according to any one of [8].
  • the unsaturated carboxylic acid monomer unit (a1) consists of a (meth)acrylic acid monomer unit (a1-1) and a (meth)acrylic acid ester monomer unit (a1-2).
  • the styrene-unsaturated carboxylic acid resin (A) comprises the styrene monomer unit (1), the (meth)acrylic acid monomer unit (a1-1), and the (meth)acrylic acid ester monomer.
  • the styrenic resin composition according to any one of [1] to [9], which is a copolymer (A1) having a body unit (a1-2).
  • a lighting cover comprising the styrenic resin composition according to any one of [1] to [14].
  • a styrenic resin composition that is used for molded articles that have excellent weather resistance, mechanical strength, and oil resistance without reducing heat resistance and transparency.
  • a molded article for automotive use that has excellent weather resistance, mechanical strength, and oil resistance without reducing heat resistance and transparency.
  • this embodiment a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. Note that the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.
  • the styrenic resin composition (hereinafter sometimes simply referred to as a resin composition) in this embodiment is a styrene resin composition having a styrene monomer unit (1) and an unsaturated carboxylic acid monomer unit (a1).
  • the styrenic resin composition in this embodiment may contain one or more selected from the group consisting of an alcohol having 10 or more carbon atoms (E) and a mold release agent (F), if necessary. Good too. Thereby, it is possible to provide a styrenic resin composition that has excellent weather resistance, mechanical strength, and oil resistance without reducing heat resistance and transparency.
  • the Vicat softening temperature is 110°C or higher.
  • the surface scratch hardness (pencil method) is H or higher.
  • the styrene-unsaturated carboxylic acid resin (A) in this embodiment is a copolymer resin (hereinafter referred to as It is also simply referred to as resin (A)) and contributes to improving the heat resistance of the entire styrenic resin composition.
  • the styrene-unsaturated carboxylic acid resin (A) may contain other monomer units ( It may further include a2).
  • the content of the styrene-unsaturated carboxylic acid resin (A) is 10% by mass or more and 100% by mass or less, and 10% by mass or more and less than 100% by mass with respect to the total amount (100% by mass) of the styrene resin composition. and preferably 10 to 98% by mass.
  • the lower limits of the content of styrene-unsaturated carboxylic acid resin (A) in the styrene resin composition are 17% by mass, 27% by mass, 37% by mass, 47% by mass, 53% by mass or more, and 56% by mass or more.
  • the upper limit values are 97% by mass or less, 95% by mass or less, and 92% by mass or less.
  • the content of the styrene-unsaturated carboxylic acid resin (A) may be any combination of the upper and lower limits.
  • the content of the styrene-unsaturated carboxylic acid resin (A) is set to 10% by mass or more, it is possible to impart fluidity to the styrene resin composition and obtain a resin composition with excellent molding cycles. , 50% by mass or more, it is possible to obtain a styrenic resin composition with excellent heat resistance.
  • the content is controlled to 98% by mass or less, the effect of improving oil resistance by the (meth)acrylic acid resin (B) described below can be sufficiently obtained.
  • the content of the styrene monomer unit (1) is 60 to 60% relative to the total amount of the styrene-unsaturated carboxylic acid resin (A). 98% by mass, preferably 70 to 97% by mass, more preferably 80 to 96% by mass, even more preferably 82 to 95% by mass, even more preferably 83 to 94% by mass, even more preferably 83 to 91% by mass. % by weight, particularly preferably from 85 to 91.5% by weight.
  • the styrenic monomer unit (1) is preferably contained in an amount of 50 to 85% by mass, preferably 52 to 85% by mass based on the total amount of the styrenic resin composition. It is 82% by weight, more preferably 54-79% by weight, even more preferably 56-77% by weight.
  • the styrenic monomer (1) is not particularly limited, but examples include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, paramethylstyrene, orthomethylstyrene, metamethylstyrene, chlorostyrene, Examples include bromostyrene. Particularly from an industrial standpoint, styrene and ⁇ -methylstyrene are preferred, and styrene is more preferred. As the styrenic monomer (1), these can be used alone or in combination of two or more.
  • the "styrenic monomer unit (1)" in this specification means a repeating unit constituting a polymer in which the styrenic monomer (1) is polymerized, and the styrenic monomer (1) ) is a repeating unit (or structural unit) in which a carbon-carbon double bond in the styrenic monomer (1) becomes a single bond (-C-C-) through a polymerization reaction or a crosslinking reaction.
  • other "monomeric units" in this specification have the same meaning.
  • the unsaturated carboxylic acid monomer unit (a1) has oil resistance and compatibility with the (meth)acrylic resin (B) described below. play a role in improving
  • the content of the unsaturated carboxylic acid monomer unit (a1) is 2 to 40% by mass, preferably 3 to 35% by mass, based on the total amount of the styrene-unsaturated carboxylic acid resin (A).
  • the content of the unsaturated carboxylic acid monomer unit (a1) is less than 2% by mass, the effect of improving heat resistance is insufficient.
  • the content of the unsaturated carboxylic acid monomer unit (a1) exceeds 40% by mass, processability will decrease due to increased resin viscosity, bubbles will occur during molding due to increased water absorption, and viscosity will be high during manufacturing. This is not desirable because it becomes too much.
  • the unsaturated carboxylic acid monomer unit (a1) in this embodiment includes an unsaturated carboxylic acid and its ester, and specifically, the (meth)acrylic acid monomer unit (a1-1 ) and (meth)acrylic acid ester monomer unit (a1-2).
  • the (meth)acrylic acid monomer unit (a1-1) plays a role in improving oil resistance and heat resistance.
  • the (meth)acrylic acid monomer (a1-1) include acrylic acid and methacrylic acid.
  • the (meth)acrylic acid monomer unit (a1-1) may be used alone or in combination of two or more.
  • the (meth)acrylic acid monomer unit (a1-1) is particularly preferably methacrylic acid, which has a large effect of improving heat resistance.
  • the content of the (meth)acrylic acid monomer unit (a1-1) is in the range of 2 to 40% by mass based on the total amount of the styrene-unsaturated carboxylic acid resin (A). More preferably 3 to 20% by mass, still more preferably 4 to 17% by mass, even more preferably 8 to 14% by mass, preferably 10 to 13% by mass, even more preferably 10.3 to 13% by mass. , more preferably 10.3 to 12.5% by weight, most preferably 10.5 to 12.5% by weight.
  • the content of the (meth)acrylic acid monomer unit (a1-1) By setting the content of the (meth)acrylic acid monomer unit (a1-1) to 2% by mass or more, it is possible to obtain an effect of improving heat resistance, and by setting the content to 40% by mass or less, the viscosity can be prevented from rising too much.
  • the content in the range of 10 to 13% by mass the styrene-unsaturated carboxylic acid resin (A ) can be obtained.
  • the (meth)acrylic acid ester monomer (a1-2) plays a role in improving oil resistance and mechanical strength.
  • the (meth)acrylic acid ester monomer (a1-2) the following general formula (1) is used.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 2 represents an ester substituent, specifically, an alkyl group having 1 to 12 carbon atoms. represents a group
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 2 represents an ester substituent, specifically, an alkyl group having 1 to 12 carbon atoms. represents a group
  • the number of carbon atoms in the ester substituent (R 2 in the above general formula (1)) of the (meth)acrylic acid ester monomer unit (a1-2) is preferably 10 or less, more preferably is 8 or less, more preferably 6 or less, even more preferably 4 or less, and most preferably 3 or less. It is. If it exceeds 10, the effect of lowering heat resistance will be large, which is not preferable.
  • Examples of the (meth)acrylic acid ester monomer (a1-2) in this embodiment include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylic acid ( (n-butyl), (t-butyl) (meth)acrylate, (isobutyl) (meth)acrylate, cyclohexyl (meth)acrylate, cybenzyl (meth)acrylate, (n-octyl) (meth)acrylate, Examples include (2-ethylhexyl) (meth)acrylate, decyl (meth)acrylate, and stearyl (meth)acrylate. These can be used alone or in combination.
  • (meth)acrylic acid ester monomer (a1-2) methyl (meth)acrylate, (n-butyl) (meth)acrylate, (meth)acrylic acid (n -octyl) and (meth)acrylic acid (2-ethylhexyl) are preferred, and methyl methacrylate is particularly preferred from the viewpoint of suppressing a decrease in heat resistance.
  • the content of the (meth)acrylic acid ester monomer unit (a1-2) with respect to the total amount of the styrene-unsaturated carboxylic acid resin (A) is, for example, 0 to 50% by mass. %, more preferably 1 to 20% by weight, even more preferably 2 to 17% by weight, even more preferably 3 to 12% by weight, even more preferably 4 to 10% by weight.
  • the styrene-unsaturated carboxylic acid resin (A) of the present embodiment contains a (meth)acrylic acid monomer unit (a1-1) and a (meth)acrylic acid ester monomer unit (a1-2). It may be a multicomponent polymer. That is, the styrene-unsaturated carboxylic acid resin (A) of the present embodiment is a binary copolymer of a styrene monomer (1) and a (meth)acrylic acid monomer unit (a1-1).
  • the styrene-unsaturated carboxylic acid resin (A) preferably contains (meth)acrylic acid ester monomer units (a1-2). Furthermore, when emphasizing improved compatibility with the (meth)acrylic resin (B) and high transparency of the mixture with the resin (B), the styrene-unsaturated carboxylic acid resin (A) A terpolymer in which a styrene monomer (1), a (meth)acrylic acid monomer unit (a1-1), and a (meth)acrylic acid ester monomer unit (a1-2) are copolymerized.
  • an unsaturated carboxylic acid ester monomer unit such as a (meth)acrylic acid ester monomer unit (a1-2) is an unsaturated carboxylic acid ester unit such as a (meth)acrylic acid unit (a1-1).
  • the styrene-unsaturated carboxylic acid resin (A) is composed of a styrene monomer (1), a (meth)acrylic acid monomer unit (a1-1), and a (meth)acrylic acid ester monomer unit.
  • a terpolymer copolymerized with (a1-2) is preferable.
  • the styrene-unsaturated carboxylic acid resin (A) is composed of a styrene monomer (1), a (meth)acrylic acid monomer unit (a1-1), and a (meth)acrylic acid ester monomer unit (a1-1). If it is a terpolymer copolymerized with 2), it is possible to increase the adhesive strength between the member made of the styrene resin composition and the member made of the (meth)acrylic resin. Also, effects can be obtained on heat resistance, light resistance, oil resistance, and surface hardness.
  • the styrene-unsaturated carboxylic acid resin (A) in this embodiment includes a styrene monomer unit (1), a (meth)acrylic acid monomer unit (a1-1), and a (meth)acrylic acid ester unit.
  • the content of the (meth)acrylic acid monomer unit (a1-1) is 2 to 2 with respect to the total amount of the styrene-unsaturated carboxylic acid resin (A). 30% by mass, and the content of (meth)acrylic acid ester monomeric units (a1-2) is preferably 0 to 20% by mass, more preferably (meth)acrylic acid monomeric units.
  • the content of (a1-1) is 3 to 20% by mass, and the content of (meth)acrylic acid ester monomer unit (a1-2) is 1 to 17% by mass, more preferably ( The content of the meth)acrylic acid monomer unit (a1-1) is 3.4 to 25% by mass, and the content of the (meth)acrylic acid ester monomer unit (a1-2) is 3 to 15%. % by mass, and even more preferably, the content of the (meth)acrylic acid monomer unit (a1-1) is 6 to 14% by mass, and the content of the (meth)acrylic acid ester monomer unit (a1-1) is 6 to 14% by mass.
  • the content of 2) is 4 to 10% by mass, and even more preferably, the content of (meth)acrylic acid monomer units (a1-1) is 9 to 12.5% by mass, and (meth) )
  • the content of the acrylic acid ester monomer unit (a1-2) is 4.5 to 7.1% by mass, and most preferably the content of the (meth)acrylic acid monomer unit (a1-1) is
  • the content of the (meth)acrylic acid ester monomer unit (a1-2) is 4.5 to 7.1% by weight.
  • Styrene-unsaturated carboxylic acid resin (A) contains styrene monomer (1), (meth)acrylic acid monomer unit (a1-1), and (meth)acrylic acid ester monomer unit (a1- 2) is a copolymerized terpolymer, the amount of (meth)acrylic acid monomer unit (a1-1) relative to the total amount of the styrene-unsaturated carboxylic acid resin (A) The content is 10.5 to 12.5% by mass, the content of (meth)acrylic acid ester monomer unit (a1-2) is 4.5 to 7.1% by mass, and (meth) The acrylic ester monomer unit (a1-2) is methyl methacrylate. This makes it possible to obtain a styrenic resin composition having an excellent balance of moldability, heat resistance, light resistance, oil resistance, and surface hardness.
  • the styrene-unsaturated carboxylic acid resin (A) in this embodiment is composed of the above-mentioned styrene monomer unit (1) and unsaturated carboxylic acid monomer unit (a1) ((meth)acrylic acid monomer unit It may further have other monomer units (a2) other than the monomer unit (a1-1) and/or (meth)acrylic acid ester monomer unit (a1-2).
  • the other monomer units (a2) include the styrene monomer (1), the unsaturated carboxylic acid monomer unit (a1) ((meth)acrylic acid monomer unit ( a1-1) and/or (meth)acrylic acid ester monomer unit (a1-2)), without any particular limitation, as long as the effects of the invention are not impaired. It may be copolymerized with monomers other than the two monomers shown in .
  • other monomers (a2) other than the three monomers shown above include maleic anhydride, maleic acid, fumaric acid, itaconic acid, (meth)acrylonitrile, dimethyl maleate, dimethyl fumarate, diethyl fumarate.
  • the other monomers are The content of (a2) is preferably 12% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.
  • styrene-unsaturated carboxylic acid resin (A) in this embodiment, the styrene monomer unit (1), the unsaturated carboxylic acid monomer unit (a1) ((meth)acrylic acid monomer unit (a1-1) and (meth)acrylic acid ester monomer unit (a1-2)) and other monomer units (a2), the content of each monomer unit was determined using pyrolysis GC/MS. Quantification can be performed using a calibration curve prepared using resins with known body units.
  • the melt flow rate at 200°C of the styrene-unsaturated carboxylic acid resin (A) in this embodiment is preferably 0.3 to 3.0, more preferably 0.4 to 2.5, and even more preferably 0.
  • the range is from .5 to 2.0, more preferably from 0.5 to 1.8, even more preferably from 0.5 to 1.1, even more preferably from 0.5 to 1.0.
  • the melt flow rate is 0.3 or more, it is preferable from the viewpoint of fluidity, and when it is 3.0 or less, it is preferable from the viewpoint of the mechanical strength of the resin.
  • the melt flow rate is a value measured at 200° C. and a load of 5 kg (49 N) in accordance with ISO 1133.
  • the weight average molecular weight (Mw) of the styrene-unsaturated carboxylic acid resin (A) in this embodiment is preferably 100,000 to 400,000, more preferably 120,000 to 320,000, still more preferably 140,000 to 320,000.
  • the range is 280,000, more preferably 160,000 to 240,000, most preferably 170,000 to 210,000.
  • the weight average molecular weight and number average molecular weight can be measured by gel permeation chromatography in terms of polystyrene standards.
  • the number average molecular weight (Mn) of the styrene-unsaturated carboxylic acid resin (A) of the present embodiment is preferably 40,000 to 150,000, more preferably 50,000 to 120,000, even more preferably 60,000. ⁇ 100,000.
  • the Z average molecular weight (Mz) of the styrene-unsaturated carboxylic acid resin (A) of the present embodiment is preferably 200,000 to 800,000, more preferably 250,000 to 500,000, even more preferably 300,000. ⁇ 450,000.
  • the Vicat softening temperature of the styrene-unsaturated carboxylic acid resin (A) in this embodiment is preferably 105 to 140°C, more preferably 107 to 135°C, even more preferably 108 to 130°C, even more preferably 115°C.
  • the temperature is from 127°C to 127°C, even more preferably from 120°C to 125°C, even more preferably from 121°C to 125°C.
  • the Vicat softening temperature of the styrene-unsaturated carboxylic acid resin (A) By setting the Vicat softening temperature of the styrene-unsaturated carboxylic acid resin (A) to 105°C or higher, the effect of improving the heat resistance of the composition can be obtained, and by setting the Vicat softening temperature to 140°C or lower, the (meth)acrylic resin It becomes easier to knead with (B). In particular, by setting the temperature to 120° C. or higher, a styrenic resin composition with excellent heat resistance can be obtained.
  • the method for measuring the Vicat softening temperature in this specification is based on ISO 306, with a load of 5 kg and a heating rate of 50° C./hour.
  • the method for producing the styrene-unsaturated carboxylic acid resin (A) of this embodiment involves using a styrene monomer (1), an unsaturated carboxylic acid monomer (a1) ((meth)acrylic acid monomer a step of preparing a mixed solution by mixing the unit (a1-1) and/or the (meth)acrylic acid ester monomer unit (a1-2)) and a solvent; and a step of polymerizing and reacting the mixed solution.
  • the method includes a polymerization step of producing a product and a step of recovering the reaction product.
  • the method of polymerizing the styrene-unsaturated carboxylic acid resin (A) is not particularly limited, but for example, radical polymerization, among which bulk polymerization or solution polymerization can be preferably employed.
  • the polymerization method mainly includes a polymerization step in which polymerization raw materials (monomer components) are polymerized, and a devolatilization step in which volatile components such as unreacted monomers and polymerization solvents are removed from the polymerization product. It is preferable to have the following.
  • a polymerization initiator is typically included in the polymerization raw material composition.
  • organic peroxides such as 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)cyclohexane, n-butyl-4,4-bis(t-butylperoxy)butane, - Peroxyketals such as (butylperoxy)valerate, dialkyl peroxides such as di-t-butyl peroxide, t-butylcumyl peroxide, and dicumyl peroxide, diacyl peroxides such as acetyl peroxide and isobutyryl peroxide, and diisopropyl peroxide.
  • Examples include peroxydicarbonates such as carbonate, peroxyesters such as t-butyl peroxyacetate, ketone peroxides such as acetylacetone peroxide, and hydroperoxides such as t-butyl hydroperoxide. From the viewpoint of decomposition rate and polymerization rate, 1,1-bis(t-butylperoxy)cyclohexane is particularly preferred.
  • a chain transfer agent may be used as necessary during polymerization of the styrene-unsaturated carboxylic acid resin (A).
  • chain transfer agents include ⁇ -methylstyrene linear dimer, n-dodecylmercaptan, t-dodecylmercaptan, n-octylmercaptan, and the like.
  • solution polymerization using a polymerization solvent can be employed.
  • a polymerization solvent aromatic solvents such as toluene, ethylbenzene, propylbenzene, and butylbenzene are preferred, and if necessary, polar solvents such as alcohols or ketones are combined to polymerize the styrene-unsaturated carboxylic acid resin (A).
  • a solvent system with controlled solubility may be used.
  • the polymerization solvent is preferably used in an amount of 3 to 35 parts by mass, more preferably 3 to 35 parts by mass, based on 100 parts by mass of the total monomers constituting the styrene-unsaturated carboxylic acid resin (A). is in the range of 5 to 30 parts by mass.
  • the amount of the polymerization solvent exceeds 35 parts by mass based on 100 parts by mass of the total monomers, the polymerization rate decreases and the molecular weight of the resulting resin also decreases, so that the mechanical strength of the resin tends to decrease.
  • the polymerization solvent is less than 3 parts by mass, it may become difficult to control heat removal during polymerization.
  • the monomer in an amount of 3 to 35 parts by mass based on 100 parts by mass of the total monomers, since quality can be easily made uniform and polymerization temperature can be controlled.
  • monohydric alcohol (E) having 10 or more carbon atoms which is an optional component of the styrenic resin composition of the present embodiment, from the polymerization system, (C) is added to 100% by mass of the total polymerization solvent.
  • the components are added in a proportion of 0.5 to 10% by mass.
  • the apparatus used in the polymerization step to obtain the styrene-unsaturated carboxylic acid resin (A) in this embodiment is not particularly limited, and may be appropriately selected according to a general styrene resin polymerization method.
  • a polymerization apparatus in which one or more complete mixing type reactors are connected can be used.
  • the devolatilization step and when carried out by bulk polymerization, the polymerization is continued until the unreacted monomer is finally reduced to preferably 50% by mass or less, more preferably 40% by mass or less, and the unreacted monomer is In order to remove volatile components such as, devolatilization treatment is performed using a known method.
  • a normal devolatilization device such as a flash drum, a twin-screw devolatilizer, a thin film evaporator, or an extruder can be used, but a devolatilization device with a small retention area is preferable.
  • the temperature of the devolatilization treatment is usually about 190 to 280°C, and more preferably 190 to 260°C from the viewpoint of suppressing decomposition.
  • the pressure for the devolatilization treatment is usually about 0.13 to 4.0 kPa, preferably 0.13 to 3.0 kPa, and more preferably 0.13 to 2.0 kPa.
  • Desirable devolatilization methods include, for example, a method in which volatile components are removed under reduced pressure under heating, and a method in which volatile components are removed through an extruder or the like designed for the purpose of removing volatile components.
  • the styrenic resin composition in this embodiment contains (meth)acrylic resin (B) (also simply referred to as resin (B)) in an amount of 0% by mass or more and 90% by mass or less based on the total amount of the styrenic resin composition. contains.
  • the (meth)acrylic resin (B) has an unsaturated carboxylic acid monomer unit (b1). By containing a predetermined amount of (meth)acrylic resin (B), it contributes to improving the oil resistance and mechanical strength of the entire styrene resin composition.
  • (meth)acrylic resin (B) in this specification refers to one in which the content of unsaturated carboxylic acid monomer units (b1) is 50% by mass based on the entire (meth)acrylic resin (B).
  • This is a general term for the above synthetic resins.
  • the number average molecular weight (Mn), weight average molecular weight (Mw), and Z average molecular weight (Mz) of the (meth)acrylic resin (B) are as described in the Examples section below. This is a value measured in terms of standard polystyrene based on data detected with a differential refractometer using permeation chromatography (GPC).
  • the content of the (meth)acrylic resin (B) is 0% by mass or more and 90% by mass or less with respect to the total amount (100% by mass) of the styrene resin composition, and the (meth)acrylic resin (B)
  • the lower limit of the content is 0% by mass or more, more than 0% by mass, 2% by mass or more, 10% by mass or more, 11% by mass or more, 14% by mass or more, 17% by mass or more, 20% by mass or more, 20% by mass. % or more, 21 mass% or more, 22 mass% or more, 23 mass% or more, 24 mass% or more, 25 mass% or more, 26 mass% or more, 29 mass% or more, and the upper limit is 83 mass%.
  • % or less 73% by mass or less, 53% by mass or less, 44% by mass or less, 41% by mass or less, 38% by mass or less, 34% by mass or less, 35% by mass or less, and 30% by mass or less.
  • the content of the (meth)acrylic resin (B) should be 0 with respect to the total amount (100% by mass) of the styrene resin composition. ⁇ 30% by weight, preferably 0 to 20% by weight, more preferably 0 to 15% by weight, even more preferably 0 to 10% by weight, even more preferably 0 to 5% by weight.
  • the unsaturated carboxylic acid monomer unit (b1) constituting the (meth)acrylic resin (B) of this embodiment is a (meth)acrylic acid monomer unit (b1-1) and a (meth)acrylic acid monomer unit (b1-1).
  • the unsaturated carboxylic acid monomer unit (b1) includes a (meth)acrylic acid monomer unit (b1-1) and a (meth)acrylic acid ester monomer unit (b1-2).
  • the (meth)acrylic resin (B) is a copolymer having a methacrylate monomer unit and an acrylate monomer unit. This provides the effect of improving oil resistance and mechanical strength, as well as thermal decomposition resistance.
  • the (meth)acrylic acid monomer (b1-1) includes acrylic acid and methacrylic acid.
  • the (meth)acrylic acid ester monomer unit (b1) constituting the (meth)acrylic resin (B) of this embodiment includes a methacrylic acid ester monomer unit and an acrylic acid ester monomer unit.
  • examples of the (meth)acrylic acid ester monomer (b1) include methyl acrylate, ethyl acrylate, (n-butyl) acrylate, (2-ethylhexyl) acrylate, (n-octyl) acrylate, and acrylic acid (n-butyl).
  • Methyl acrylate, acrylic acid (n-butyl), methyl methacrylate, methacrylic acid (2-ethylhexyl), methacrylic acid (n-octyl) ) is preferred.
  • the (meth)acrylic ester monomer (b1-2) can be used alone or in combination, and it is preferable to combine two types of (meth)acrylic ester monomers. From the viewpoint of achieving both heat resistance and thermal decomposition, the combination of monomer units constituting the (meth)acrylic resin (B) of this embodiment is selected from among the monomer units listed above. A copolymer of an acid ester species and an acrylic ester species is preferred, and a methyl methacrylate-methyl acrylate copolymer is more preferred.
  • the preferred (meth)acrylic resin (B) of this embodiment is preferably a binary or tertiary copolymer, in which methacrylic ester species (methacrylic ester monomer units) and acrylic ester species ( methacrylic ester-acrylic ester copolymer copolymerized with acrylic ester monomer unit), and the acrylic ester monomer unit is copolymerized with respect to the total amount of the methacrylic ester-acrylic ester copolymer.
  • a copolymer containing 0.1 to 25% by mass of acrylic ester monomer units is preferred, and a copolymer containing 0.5 to 17 mass % of acrylic ester monomer units is more preferred, and 1.
  • a copolymer containing 0 to 7.0% by mass of an acrylic ester monomer unit is more preferable, and a copolymer containing 1.2 to 4.5 mass % of an acrylic ester monomer unit is even more preferable.
  • Most preferred is a copolymer containing 1.5 to 3.0% by mass of
  • the preferred (meth)acrylic resin (B) of the present embodiment is a methyl methacrylate-methyl acrylate copolymer, and the amount of methyl acrylate monomer units is 0.5 to 0.5 to 100% based on the total amount of the copolymer.
  • a copolymer containing 17% by mass of methyl acrylate monomer units is more preferred, and a copolymer containing 1.0 to 5.0% by mass of methyl acrylate monomer units is even more preferred. This makes it possible to more effectively suppress the deterioration of the heat resistance improved by the styrene-unsaturated carboxylic acid resin (A).
  • the content of the (meth)acrylic acid ester monomer unit (b1-2) in the (meth)acrylic resin (B) is (meth) It is preferably 54% by mass or more, more preferably 64% by mass or more, even more preferably 71% by mass or more, even more preferably 86% by mass or more, and most preferably 91% by mass or more based on the total amount of acrylic resin (B). % by mass or more.
  • the content of the (meth)acrylic acid ester monomer unit (b1-2) in the (meth)acrylic resin (B) is (meth) It is preferably 100% by mass or less based on the total amount of acrylic resin (B), more preferably 97% by mass or less, even more preferably 91% by mass or less, even more preferably 86% by mass or less, and most preferably 81% by mass or less. mass% or less.
  • the upper limit of the content of (meth)acrylic acid monomer units (b1-1) in the (meth)acrylic resin (B) is ) It is preferably 15% by mass or less based on the total amount of acrylic resin (B), more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and most preferably It is 2% by mass or less.
  • the lower limit of the content of the (meth)acrylic acid monomer unit (b1-1) in the (meth)acrylic resin (B) is 0% by mass based on the total amount of the (meth)acrylic resin (B). It is preferably at least 0.5% by mass, still more preferably at least 0.7% by mass, even more preferably at least 1.0% by mass, and most preferably at least 1.5% by mass.
  • the above upper and lower limits can be arbitrarily combined.
  • the (meth)acrylic resin (B) of this embodiment includes the above-mentioned unsaturated carboxylic acid monomer unit (b1) (for example, (meth)acrylic acid monomer (b1-1) and/or (meth) )
  • the acrylic acid ester monomer unit (b1-2) may further contain other monomer units (b2). That is, the other monomer unit (b2) is not particularly limited as long as it is copolymerizable with the unsaturated carboxylic acid monomer unit (b1) (), as long as it does not impair the effects of the invention. It may be copolymerized with monomers other than those shown above.
  • other monomers (b2) other than the monomers shown above include styrene, maleic anhydride, maleic acid, fumaric acid, itaconic acid, dimethyl maleate, dimethyl fumarate, diethyl fumarate, ethyl fumarate. , maleimide, and nuclear-substituted maleimide.
  • the content of the other monomer units (b2) is preferably 0 to 30% by mass, and preferably 0 to 20% by mass, based on the total amount of the (meth)acrylic resin (B). It is more preferably 0 to 15% by mass, even more preferably 0 to 7% by mass.
  • the upper limit of the weight average molecular weight (Mw) of the (meth)acrylic resin (B) is 8 million or less, 6 million or less, 5 million or less, 3 million or less, 2 million or less in terms of standard polystyrene using the GPC method described below.
  • the preferred order is 1 million or less, 900,000 or less, 500,000 or less, 400,000 or less, 300,000 or less, 200,000 or less, 150,000 or less, 130,000 or less, 120,000 or less, and 110,000 or less, and the lower limit is The preferred order is 40,000 or more, 50,000 or more, 60,000 or more, 70,000 or more, 80,000 or more, and 90,000 or more.
  • the above upper limit and lower limit can be arbitrarily combined, but in particular, by setting it to 70,000 or more, a resin composition with excellent strength can be obtained.
  • the molecular weight By setting the molecular weight to 1,000,000 or less, the viscosity difference with the styrene-unsaturated carboxylic acid resin (A) can be suppressed, and as a result, (meth)acrylic in the styrene resin composition
  • the resin (B) can be dispersed well, the generation of unmelted substances derived from the (meth)acrylic resin (B) can be suppressed, and a molded article with a good appearance can be obtained using the composition.
  • the viscosity of the resin composition can be lowered, a resin composition with good injection molding cycles can be obtained.
  • the value of the weight average molecular weight (Mn) of the (meth)acrylic resin (B) is preferably 20,000 to 1,500,000, more preferably 25,000 to 300,000, in terms of standard polystyrene by the GPC method described below. Even more preferably, it is in the range of 30,000 to 120,000.
  • the value of the weight average molecular weight (Mz) of the (meth)acrylic resin (B) is preferably 80,000 to 10,000,000, more preferably 90,000 to 800,000, and even more It is preferably in the range of 100,000 to 300,000.
  • the value of the dispersity (Mw/Mn) of the (meth)acrylic resin (B) is preferably 1.1 to 6.0, more preferably 1.3 to 4 in terms of standard polystyrene by the GPC method described below. .0, more preferably in the range of 1.5 to 3.7. In particular, by setting it within the range of 1.5 to 3.7, a styrenic resin composition with an excellent balance between moldability and strength can be obtained.
  • the (meth)acrylic resin (B) of this embodiment may contain a high molecular weight component of 1 million or more.
  • the high molecular weight component of 1 million or more has an unsaturated carboxylic acid monomer (b1), and among the (meth)acrylic resins (B) contained in the styrene resin composition,
  • the proportion of the (meth)acrylic resin (B), which is a high molecular weight component of 1 million or more, is preferably 1.0% by mass or less based on the total amount of the styrene resin composition.
  • the (meth)acrylic resin (B) of the present embodiment contains a high molecular weight component of 1 million or more at 0.0% by mass or more and 1.0% by mass based on the total amount of the styrene resin composition. It is more preferable that the weight average molecular weight (Mw) of the (meth)acrylic resin (B) as a whole is from 70,000 to 300,000.
  • the content of all (meth)acrylic acid monomer units contained in the styrenic resin composition is 1 to 20% by mass with respect to the total amount (100% by mass) of the styrenic resin composition.
  • the content is preferably in the range of 2 to 15% by weight, more preferably 3 to 10% by weight, even more preferably 4 to 8% by weight.
  • the content of all (meth)acrylic acid monomer units contained in the styrenic resin composition should be adjusted to the total amount of the styrenic resin composition ( 100% by mass), preferably 7 to 20% by mass, preferably 8 to 18% by mass, more preferably 10 to 15% by mass, even more preferably 10.3 to 12.5% by mass. be.
  • the above-mentioned content of all (meth)acrylic acid monomers refers to the total amount of (meth)acrylic acid monomer units present in the styrenic resin composition.
  • B) and the contents of (meth)acrylic acid monomer units in the optionally added resin are also converted.
  • the content of all (meth)acrylic acid ester monomer units contained in the styrenic resin composition is 6 to 55% by mass with respect to the total amount (100% by mass) of the styrenic resin composition. It is preferably contained, preferably 10 to 50% by mass, more preferably 14 to 45% by mass, even more preferably 16 to 40% by mass, even more preferably 20 to 37% by mass. is within the range of When the content of the (meth)acrylic acid ester monomer in the entire composition is within the above range, the effect of improving oil resistance and strength can be sufficiently obtained.
  • the content of all (meth)acrylic acid ester monomer units contained in the styrenic resin composition should be adjusted to the total amount of the styrenic resin composition ( 100% by mass), preferably 0 to 15% by mass, more preferably 0 to 10% by mass, more preferably 0 to 7% by mass, and more preferably 0 to 6% by mass. Mass%.
  • the content of all (meth)acrylic acid ester monomers refers to the total amount of (meth)acrylic acid ester monomer units present in the styrene-based resin composition. The respective contents of (meth)acrylic acid ester monomer units in the resin (B) and the optionally added resin are also converted.
  • the (meth)acrylic acid monomer units By controlling the content of all (meth)acrylic acid monomer units and all (meth)acrylic acid ester monomer units contained in the styrenic resin composition within the above range, the (meth)acrylic acid monomer units A styrenic resin composition that can simultaneously efficiently obtain the effect of improving heat resistance due to the mer unit and the effect of improving oil resistance due to the (meth)acrylic acid ester monomer unit, resulting in excellent heat resistance and oil resistance. It is possible to obtain a product and a sheet formed by molding the product.
  • the method for producing the (meth)acrylic resin (B) of this embodiment is not particularly limited, but includes bulk polymerization in which a (meth)acrylic acid ester monomer and other monomers are polymerized as necessary; It can be produced by processes such as solution polymerization in which a solvent is added, suspension polymerization in which an organic layer is dispersed in water using a suspending agent, and emulsion polymerization.
  • Light stabilizer (C) Although the light stabilizer (C) of this embodiment does not have ultraviolet absorbing ability itself, it captures the photo radicals generated when the styrene resin composition absorbs ultraviolet rays and renders them harmless. It can have the function of preventing deterioration and coloring of the styrenic resin composition.
  • the light stabilizer (C) is preferably a hindered amine compound, and examples include hindered amine compounds such as secondary amine type, tertiary amine type, and N-alkoxy type.
  • the light stabilizer (C) can be used alone or in combination of two or more kinds, and by using the ultraviolet absorber (D) described below in combination, a higher light resistance effect, in other words, a styrene resin composition or It is possible to suppress discoloration and decrease in strength after exposure due to long-term outdoor use of the molded product.
  • the light stabilizer (C) mainly exerts its function on the resin surface where many photo radicals are generated, so if you want to make it more effective, a low-molecular type is preferable, but it is difficult to prevent mold contamination due to excessive bleed-out. To prevent this, it is necessary to adjust the molecular weight to an appropriate level.
  • the light stabilizer (C) is preferably a secondary amine type from the viewpoint of weather resistance upon addition and initial color tone.
  • the content of the light stabilizer (C) of the present embodiment is 0% by mass to 2.0% by mass, preferably 0.001% to 2.0% by mass, based on the total amount of the styrenic resin composition.
  • the upper limit values are 1.8% by mass or less, 1.6% by mass or less, 1.4% by mass or less, 1.2% by mass or less, 1.0% by mass or less, 0.8% by mass or less, 0 In the following order: .7 mass% or less, 0.6 mass% or less, 0.5 mass% or less, 0.4 mass% or less, 0.3 mass% or less, 0.2 mass% or less, 0.1 mass% or less
  • the lower limit values are 0.005% by mass or more, 0.010% by mass or more, 0.021% by mass or more, 0.051% by mass or more, 0.061% by mass or more, 0.071% by mass or more, 0. The preferable order is 0.079% by mass or more and 0.089% by mass or more.
  • the content of the light stabilizer (C) can be selected from any combination of
  • the light stabilizer (C) of this embodiment is preferably a hindered amine compound.
  • the hindered amine compounds include bis(1,2,2,6-pentamethyl-4-piperidyl) sebacate, bis(1-undecaneoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) ) Sebacate, N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine, butyl(3,5-di-t-butyl-4-hydroxybenzyl)malone acid bis(1,2,2,6,6-pentamethyl-4-piperidyl), N,N'-1,6-hexanediylbis(N-(2,2,6,6-t
  • Examples include LA-77G, Adekastab LA-81, JF-90G and JF-95 manufactured by Johoku Kagaku Co., Ltd., Chimassorb 2020FDL, Chimassorb 944FDL, Tinuvn 622SF, and Uvinul 4050FF manufactured by BASF Japan.
  • the ultraviolet absorber (D) of this embodiment absorbs ultraviolet rays absorbed by the styrenic resin composition instead of the styrene resin composition and converts it into heat or chemical energy. It has the function of suppressing the generation of photoradicals due to absorption of ultraviolet rays, and suppressing deterioration and coloring of the resin.
  • the ultraviolet absorber (D) has two or more aromatic rings bonded via a linking group containing an atom having an unpaired electron (oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, etc.), and Preferably, the compound has one or more aromatic rings having a phenolic hydroxyl group.
  • the compound may have a chemical structure that absorbs light, becomes excited, and then converts it into chemical energy.
  • Examples of the ultraviolet absorber (D) of this embodiment include benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cyanoacrylate compounds, oxalic acid anilide compounds, malonic ester compounds, and Examples include amidine compounds and salicylate compounds.
  • These ultraviolet absorbers (D) can be used alone or in combination of two or more, and by using the above-mentioned light stabilizer (C) and ultraviolet absorber (D) together, a higher light resistance effect can be achieved. For example, it is possible to suppress discoloration and decrease in strength of the styrenic resin composition after exposure.
  • an ultraviolet absorber (D) that can absorb ultraviolet wavelengths (250 to 350 nm) that are easily absorbed by the resin added to the styrene resin composition is preferable.
  • Preferred ultraviolet absorbers (D) of this embodiment include, for example, benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cyanoacrylate compounds, malonic acid ester compounds, and oxalic acid anilide compounds. It is more preferable to use one or more selected from the group consisting of:
  • preferred ultraviolet absorbers (D) of this embodiment include the following general formulas (d) and (d'):
  • M di each independently represents a monovalent or more aromatic group
  • R d represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • L di each independently represents a divalent to pentavalent group
  • one or more hydrogen atoms of the benzene ring in the aralkyl group may be substituted with a phenolic hydroxyl group, an alkyl group having 1 to 15 carbon atoms, or a fused ring
  • d1 represents an integer of 0 to 4
  • d2 represents an integer of 1 to 4.
  • R 5 to R 7 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, and 1 to 15 carbon atoms.
  • d5 represents an integer from 0 to 4, and when d5 is 2 or more, R 8 may be the same or different.
  • One or more compounds selected from the group consisting of the compounds represented by are preferred.
  • M di each independently represents an aromatic group of monovalent or higher valence in which unsubstituted or one or more hydrogen atoms can be substituted with a substituent R 2 , and M di represents an unsubstituted or one or more hydrogen atom It is preferable that the atom is an aromatic ring having a valence of more than one and less than 4 that can be substituted with a substituent R2 , and the following formula (I) or (II):
  • d1 in the general formula (d) is an integer of 0 or more and 4 or less, and preferably 0, 1, 2 or 3.
  • R 1 is a linear or branched alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, or an alkoxy group having 1 to 13 carbon atoms having an ester bond.
  • d1 is an integer of 2 or more, a plurality of R1s may be the same or different.
  • a compound represented by the following general formula (d) is preferable.
  • the compound represented by the above general formula (d) is a group consisting of the following general formula (d-1), general formula (d-2), general formula (d-3) and general formula (d-4).
  • M 1 is a group represented by the above formula (II).
  • M 2 and M 3 are groups represented by the above formula (I)
  • M 5 is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 1 to 15 carbon atoms, and 7 carbon atoms.
  • R d4 represents an alkyl group having 1 to 10 carbon atoms
  • Examples of the compound represented by the above general formula (d-1) include the following general formula (d-1.1) or (d-1.2):
  • R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkoxy group, and m is 1 or more and 5 or less represents an integer of ) is preferred.
  • R 10 is preferably an aralkyl group having 7 to 25 carbon atoms, more preferably An aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 18 carbon atoms.
  • R 5 to R 7 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a phenyl group, an alkyl group having 1 to 15 carbon atoms, and 1 to 15 carbon atoms.
  • 15 alkenyl group or an aralkyl group having 7 to 25 carbon atoms, provided that -CH 2 - in the alkyl group may be substituted with -O- or -C( O)-;
  • One or more hydrogen atoms of the benzene ring in the aralkyl group may be substituted with a phenolic hydroxyl group, an alkyl group having 1 to 15 carbon atoms, or a fused ring (including a heterocycle (e.g., benzotriazole ring))
  • R 8 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a phenyl group, an alkyl group
  • d5 represents an integer from 0 to 4, and when d5 is 2 or more, R 8 may be the same or different.
  • R 6 and R 7 include a group represented by the following general formula (V) or a cyano group (-CN).
  • R 9 is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 1 to 15 carbon atoms, or an alkenyl group having 7 to 25 carbon atoms.
  • Represents an aralkyl group, provided that -CH 2 - in the alkyl group may be substituted with -O- or -C ( O).
  • R 9 in the above general formula (V) is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. , more preferably an alkyl group having 1 to 5 carbon atoms, even more preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably an alkyl group having 1 to 2 carbon atoms.
  • the position of R 8 in the above general formula (d') is preferably the para position in the benzene ring in the general formula (d').
  • d5 is more preferably 0 or 1 from the viewpoint of stability.
  • the content of the ultraviolet absorber (D) of the present embodiment is 0.001 to 2.0% by mass based on the total amount of the styrene resin composition, and the upper limit is 1.8% by mass or less, 1.6% by mass or less, 1.4% by mass or less, 1.2% by mass or less, 1.0% by mass or less, 0.8% by mass or less, 0.7% by mass or less, 0.6% by mass or less, 0
  • the content is .002% by mass or more, 0.004% by mass or more, 0.006% by mass or more, 0.010% by mass or more, and 0.021% by mass or more.
  • the content of the ultraviolet absorber (D) can be selected from any combination of the above upper and lower limits.
  • benzotriazole compounds include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert -octylphenol, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 6-(2 -benzotriazolyl)-4-tert-octyl-6'-tert-butyl-4'-methyl-2,2'-methylenebisphenol]2-(2'-hydroxy-3'-tert-butyl-5' -methylphenyl)-5-chlorobenzotriazole, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, etc., and the specific product name Examples include ADEKA's ADE
  • triazine compounds examples include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2, 4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, N,N',N''-tri(m-tolyl)-1,3,5 -Triazine-2,4,6-triamine, 2,4,6-tris(4-butoxy-2-hydroxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl) -6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, ethylhexyltriazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethyl) phenyl)-1,3,5-triazine, 2,4,6-tritri
  • benzophenone compounds examples include 2-hydroxy-4-(octyloxy)benzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 2,4-dihydroxybenzophenone.
  • examples include benzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and specific product names include ADEKA Stab 1413, Chimassorb 81 and Chimassorb 81FL, manufactured by BAST Japan.
  • cyanoacrylate compounds examples include 2,2-bis ⁇ [(2-cyano-3,3-diphenylacryloyl)oxy]methyl ⁇ propane-1,3-diyl bis(2-cyano-3,3- Examples include diphenyl acrylate, ethyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl (2Z)-3-cyano-2,3-diphenylprop-2-enoate, and specific product names include , Uvinul3030, Uvinul3035, and Uvinul3039 manufactured by BASF Japan.
  • malonic acid ester compounds examples include (4-methoxybenzylidene) malonic acid ester, tetraethyl 2,2'-(1,4-phenylene dimetanylylidene) dimalonate, and specifically, Clariant Co., Ltd.
  • examples include HOSTAVIN PR-25 GR and HOSTAVIN B-CAP.
  • oxalic acid anilide compounds examples include (N-(2-ethylphenyl)-N'-(2-ethoxyphenyl)oxalic acid diamide), and specific examples include HOSTAVIN VSU P manufactured by Clariant. It will be done.
  • the ultraviolet absorber (D) may be used as a mixture of two or more types, and in a preferable form, the ultraviolet absorption peak derived from the aromatic group of the styrene resin decreases due to photodegradation.
  • preferred embodiments of the ultraviolet absorber (D) include a compound represented by the above general formula (d-2.1), a compound represented by the above general formula (d-1.1), or It is particularly preferable to contain a compound represented by the above general formula (d-3.1).
  • a UV absorber (D) that can efficiently absorb wavelengths of 250 to 300 nm a combined UV absorber that combines a triazine UV absorber with a benzotriazole UV absorber or a benzophenone UV absorber is used. Agents are preferred.
  • malonic acid ester-based or oxalic acid anilide-based UV absorbers that have little absorption in the visible light range (wavelengths of 380 nm or more) and only in the ultraviolet range (near 250 to 350 nm) may be used. It is preferable to use a small amount of an ultraviolet absorber and a triazine-based ultraviolet absorber, which is an ultraviolet absorber that can efficiently absorb wavelengths of 250 to 300 nm.
  • the ultraviolet absorber (D) is preferably an ultraviolet absorber that has little absorption in the visible light region (wavelength 380 nm or more) and absorption in the ultraviolet region (around 250 to 350 nm).
  • a suitable ultraviolet absorber (D) malonic acid ester compounds and oxalic acid anilide compounds having absorption only in the vicinity of 250 nm to 350 nm are particularly preferred.
  • benzophenone compounds and cyanoacrylate compounds which have little absorption in the visible light region and cause little discoloration when added, can also be suitably used.
  • the ultraviolet absorber (D) can efficiently absorb a region (wavelength 250 to 300 nm) in which the ultraviolet absorption peak derived from the aromatic group of the styrene resin becomes sensitized due to photodegradation.
  • Ultraviolet absorbers (D) are effective, and specifically, triazine compounds are examples of ultraviolet absorbers (D) that can efficiently absorb wavelengths of 250 to 300 nm.
  • a triazine compound as the ultraviolet absorber (D)
  • a sufficient effect can be obtained even if the amount added is reduced, and it is possible to reduce discoloration of the resin at the time of addition.
  • the monohydric alcohol (E) having 10 or more carbon atoms is an optional component of the styrene-based resin composition, and is an optional component of the styrene-unsaturated carboxylic acid composition during molding. Suppresses gelation of the resin (A), contributes to improving the appearance of a styrenic resin composition with a good appearance and a molded article made of a styrene resin composition, and also provides a mold release effect during injection molding. .
  • the content of the monohydric alcohol (E) having 10 or more carbon atoms is 0.01 to 1.0% by mass, preferably 0.01 to 1.0% by mass, based on the total amount (100% by mass) of the styrene resin composition. 03 to 0.8% by weight, more preferably 0.05 to 0.6% by weight, even more preferably 0.07 to 0.5% by weight.
  • the content of monohydric alcohol (E) having 10 or more carbon atoms By setting the content of monohydric alcohol (E) having 10 or more carbon atoms to 0.07 to 0.5% by mass, sufficient gel suppression effect and mold release effect can be obtained without particularly reducing heat resistance. .
  • the content of monohydric alcohol (E) having 10 or more carbon atoms should be 0% relative to the total amount of the styrene resin composition. The amount is preferably from .1 to 0.5% by weight, more preferably from 0.1 to 0.4% by weight, even more preferably from 0.1 to 0.3% by weight.
  • a styrenic resin composition with particularly high mold release effect can be obtained without reducing heat resistance. be able to. If the added amount of alcohol having 10 or more carbon atoms is less than 0.1% by mass, mold releasability tends to decrease, especially in molded products with complex shapes, and if it exceeds 0.5% by mass, heat resistance may deteriorate. There are concerns about deterioration and worsening of mold contamination.
  • the monohydric alcohol (E) having 10 or more carbon atoms is an alcohol having 10 or more carbon atoms containing one hydroxyl group, and has a heteroatom such as oxygen or nitrogen in the carbon chain constituting the alcohol (E).
  • the carbon chain may contain bonds other than single bonds, such as double bonds, triple bonds, ester bonds, and amide bonds.
  • the number of carbon atoms is preferably 16 or more, more preferably 17 or more, and even more preferably 18 or more and 50 or less.
  • the monohydric alcohol (E) having 10 or more carbon atoms may be contained in a styrenic resin composition or a molded article made of a styrene resin composition.
  • monohydric alcohol (E) having 10 or more carbon atoms is present (or The monohydric alcohol (E) may be left in the resin composition as the final product by adding styrene-unsaturated carboxylic acid resin (A) and (meth)acrylic resin (B). ) may be added during kneading and mixed in an extruder.
  • the carbon chain constituting the monohydric alcohol (E) does not contain heteroatoms and is composed only of alkyl groups. is preferred.
  • Monohydric alcohols whose carbon chains are composed only of alkyl groups have excellent thermal stability and compatibility with styrene resins, and therefore have the effect of suppressing mold fouling during molding.
  • the number of carbon atoms in the alcohol is preferably 15 or more, more preferably 16 or more, even more preferably 17 or more and 50 or less, particularly preferably 18 or more and 30 or less.
  • the boiling point of the monohydric alcohol (E) having 10 or more carbon atoms is preferably 260°C or higher, more preferably 270°C or higher, even more preferably 290°C or higher. If the boiling point of the alcohol is less than 260°C, the volatility will be high and there is a tendency for an off-odor to occur during molding.
  • the monohydric alcohol (E) having 10 or more carbon atoms is not particularly limited, but includes, for example, 1-hexadecanol, isohexadecanol, 1-octadecanol, 5,7,7-trimethyl-2- (1,3,3-trimethylbutyl)-1-octanol, isooctadecanol, 1-isoisoeicosanol, stearyl alcohol, 8-methyl-2-(4-methylhexyl)-1-decanol, 2-heptyl -1-undecanol, 2-heptyl-4-methyl-1-decanol, 2-(1,5-dimethylhexyl)-(5,9-dimethyl)-1-decanol, polyoxyethylene alkyl ethers, etc. .
  • the polyoxyethylene alkyl ethers are preferably compounds represented by the following general formula (2).
  • R is an alkyl group having 12 to 20 carbon atoms, and X represents the average addition number of ethylene oxide and is an integer of 1 to 15.
  • Specific product names of preferred alcohols (E) include “Fine Oxocol 180” manufactured by Nissan Chemical Co., Ltd., “Calcol 8098” manufactured by Kao Corporation, and “Emulgen 109P” manufactured by Kao Corporation.
  • the styrenic resin composition preferably contains a mold release agent (F).
  • the release agent (F) can be contained in the form of an internal lubricant (F1) that is kneaded when preparing the styrenic resin composition, or as an external lubricant (F1) that is dry-blended after granulating the styrenic resin composition. F2) may be used, or the two forms may be combined.
  • the content of the mold release agent (F) in this embodiment is preferably 0.001 to 2.0% by mass with respect to the total amount (100% by mass) of the styrene resin composition, and the upper limit is , 1.8% by mass or less, 1.7% by mass or less, 1.6% by mass or less, 1.5% by mass or less, 1.4% by mass or less, 1.3% by mass or less, 1.2% by mass or less, More preferably in the order of 1.1% by mass or less, 1.0% by mass or less, 0.9% by mass or less, 0.8% by mass or less, 0.7% by mass or less, and 0.6% by mass or less, and the lower limit is is 0.003 mass% or more, 0.005 mass% or more, 0.007 mass% or more, 0.009 mass% or more, 0.012 mass% or more, 0.031 mass% or more, 0.066 mass% or more , 0.090% by mass or more, 0.11% by mass or more, 0.16% by mass or more, 0.21% by mass or more, 0.26% by mass or more
  • a styrenic resin composition with excellent mold release properties can be obtained, and in particular, by setting the content in the range of 0.01 to 0.8% by mass, A styrenic resin composition with an excellent balance of moldability and heat resistance can be obtained.
  • a monohydric alcohol (E) having 10 or more carbon atoms is used as the mold release agent (F).
  • the content of monohydric alcohol (E) is preferably 0.1 to 0.5% by mass, more preferably 0.1 to 0.4% by mass, based on the total amount of the styrenic resin composition. , more preferably 0.1 to 0.3% by mass.
  • the content of the internal lubricant (F1) is the total amount of the styrenic resin composition (100 mass %), preferably 0.05 to 2.0% by mass, more preferably 0.10 to 1.5% by mass, more preferably 0.10 to 1.0% by mass, and even more preferably 0.13 to 1.0% by mass.
  • the content is 1.0% by weight, more preferably 0.17 to 0.8% by weight.
  • the content of the mold release agent as the external lubricant (F2) is as follows: Preferably in the range of 0.005 to 0.5 mass%, more preferably 0.007 to 0.2 mass%, even more preferably 0.008 to 0.1 mass%, based on the total amount (100 mass%). be. In particular, by setting the amount in the range of 0.008 to 0.1% by mass, mold contamination can be suppressed and a styrenic resin composition with excellent mold release properties can be obtained.
  • Examples of the mold release agent (F) of this embodiment include stearic acid, zinc stearate, calcium stearate, glycerin, glycerol monostearate, glycerol distearate, ethylene bisstearamide, stearamide, oleic acid amide, and Examples include acid amides, hydrogenated castor oil, and the like. From the viewpoint of the ability to impart mold release properties to styrene resin, stearic acid, zinc stearate, and calcium stearate are preferred.
  • a styrenic resin composition with excellent mold release properties and initial color tone of the resin can be obtained.
  • Specific product names of preferred mold release agents (F) include “Excel S-95”, “Excel VS-95”, “Excel O-95R”, “Excel P-40”, and “Excel P” manufactured by Kao Corporation. -40P”, “Excel 122V”, “Excel 200”, “Excel O-95N”, “Excel O-95F”, “Step SS”, “Rikemar S-100”, “Rikemar S-100P” manufactured by Riken Vitamin Co., Ltd. , “Rikemar H-100”, etc.
  • the content of glycerol monostearate and glycerol distearate used as the mold release agent (F) is preferably 0.01 to 0.5% by mass, based on the total amount (100% by mass) of the styrenic resin composition. is 0.03 to 0.45% by mass, even more preferably 0.05 to 0.4% by mass, even more preferably 0.05 to 0.35% by mass, and even more preferably 0.08 to 0.30% by mass. % by weight, even more preferably from 0.10 to 0.30% by weight, even more preferably from 0.10 to 0.25% by weight.
  • glycerol monostearate or glycerol distearate is contained in an amount of 0.03 to 0.45% by mass based on the total amount (100% by mass) of the styrenic resin composition, particularly excellent mold release properties and initial color tone of the resin are obtained.
  • a styrenic resin composition can be obtained.
  • the styrenic resin composition of this embodiment is made by adding various additives commonly used in styrene resins in order to achieve known effects. You can also do that. Examples of such additives include stabilizers, higher fatty acid surfactants, antioxidants, plasticizers, antiblocking agents, antistatic agents, antifogging agents, and mineral oil.
  • thermoplastics such as styrene-maleic anhydride copolymer, methyl methacrylate-butyl acrylate block copolymer, methyl methacrylate-(2-ethylhexyl acrylate) block copolymer, and styrene-butadiene block copolymer
  • a crosslinked material (G) such as an elastomer or a reinforcing material such as core-shell type MBS resin particles may also be added to the extent that the physical properties are not impaired.
  • the content of the crosslinked body (G) is preferably 3% by mass or less, more preferably 2% by mass or less based on the total amount of the styrene resin composition. % or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, even more preferably 0.05% by mass or less, particularly preferably 0.
  • the crosslinked material (G) includes, in addition to the reinforcing material, (meth)acrylic acid ester monomer, styrene monomer, and butadiene.
  • examples include crosslinked resin particles made of a copolymer obtained by polymerizing one or more monomers selected from the group consisting of:
  • antioxidants such as octadecyl-3-(3,5-tert-butyl-4-hydroxyphenyl)propionate, 4,6-bis(octylthio methyl)-o-cresol, bis(3-tert-butyl-4-hydroxy-5-methylbenzenepropanoic acid) ethylene bis(oxyethylene), 2,2'-dimethyl-2,2'-(2,4, 8,10-Tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1'-diylbis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate ], 2- ⁇ 1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl ⁇ -4,6-bis(2-methylbutan-2-yl)phenyl prop-2- Enoate, 2-tert-butoxyethylene
  • a phosphorus-based antioxidant having a hindered phenol skeleton such as dioxaphosphepine (product name: Sumilizer GP manufactured by Sumitomo Chemical Co., Ltd.) can be used.
  • These stabilizers may be used alone or in combination of two or more as appropriate. There is no particular restriction on the timing of addition, and it may be added during either the polymerization step or the devolatilization step.
  • the stabilizer can also be mixed into the product using a mechanical device such as an extruder or mixer.
  • the (total) content of the antioxidant in this embodiment is 0.001 to 1.0% by mass based on the total amount of the styrenic resin composition.
  • the lower limit of the preferred range of the amount added is 0.001% by mass or more, more preferably 0.005% by mass or more, more preferably 0.008% by mass or more, and even more preferably 0.01% by mass. or more, more preferably 0.05% by mass or more, more preferably 0.08% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.21% by mass or more. be.
  • the upper limit of the preferable range of the amount added is 1.0% by mass or less, more preferably 0.9% by mass or less, more preferably 0.8% by mass or less, more preferably 0.7% by mass or less, and more preferably 0.7% by mass or less. Preferably it is 0.6% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.4% by mass or less.
  • the (total) content of the phenolic antioxidant in this embodiment is 0.001 to 1.0% by mass based on the total amount of the styrenic resin composition.
  • the lower limit of the preferable range of the amount of phenolic antioxidant added is 0.001% by mass or more, more preferably 0.005% by mass or more, more preferably 0.008% by mass or more, and more preferably is 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 0.08% by mass or more, more preferably 0.1% by mass or more, and more preferably 0. .21% by mass or more.
  • the upper limit of the preferred range of the amount added is 1.0% by mass or less, more preferably 0.9% by mass or less, more preferably 0.8% by mass or less, more preferably 0.7% by mass or less, and more preferably 0.7% by mass or less. Preferably it is 0.6% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.4% by mass or less.
  • the (total) content of the phosphorus-based antioxidant in this embodiment is 0.001 to 1.0% by mass based on the total amount of the styrene-based resin composition.
  • the lower limit of the preferred range of the amount of phosphorus antioxidant added is 0.001% by mass or more, more preferably 0.005% by mass or more, more preferably 0.008% by mass or more, and more preferably is 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 0.08% by mass or more, more preferably 0.1% by mass or more, and more preferably 0. .21% by mass or more.
  • the upper limit of the preferable range of the amount added is 1.0% by mass or less, more preferably 0.9% by mass or less, more preferably 0.8% by mass or less, more preferably 0.7% by mass or less, and more preferably 0.7% by mass or less. Preferably it is 0.6% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.4% by mass or less.
  • the above blending ratio of the antioxidant can be particularly effective in preventing discoloration of the resin.
  • Sumilizer GS compound name: 2-[1-(2-hydroxy-3,5-di-tert -pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate
  • Sumilizer GM compound name: 2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5 -Methylphenyl) methyl]-4-methylphenyl and a phosphorus-based antioxidant
  • Irgafos168 compound name: tris(2,4-di-tert-butylphenyl) phosphite
  • Adekastab PEP-36 (compound name: 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa- 3,9-diphosphaspiro[5.5]undecane)
  • Adekastab TPP (compound name: triphenylphosphite)
  • Adekastab 3010 (compound name: triisodecyl phosphite)
  • Adekastab PEP-8 (compound name: 3,9-dioctadecane) -1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane) has a high thermal stability imparting effect during processing and is resistant to discoloration.
  • sulfur-based antioxidants can also be used, such as dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'- Examples include thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate, and 2-mercaptobenzimidazole.
  • a styrenic resin composition having excellent initial color tone and thermal stability can be obtained.
  • the light stabilizer (C) captures the optical radicals generated when the styrenic resin composition absorbs ultraviolet rays and renders them harmless, thereby preventing deterioration and coloring of the styrene resin composition due to the radicals.
  • the compound has a hindered amine skeleton that has the function of preventing
  • antioxidants are classified into phenolic antioxidants having a hindered phenol skeleton and phosphorus antioxidants having a phosphite structure.
  • antioxidants and light stabilizers (C) since it is difficult to strictly classify antioxidants and light stabilizers (C), in this specification, when calculating the content of light stabilizers (C) and/or antioxidants, for example, hindered In the case of an antioxidant that has both a phenol skeleton and a phosphite structure, the amount added is calculated by counting it as both a phenol antioxidant and a phosphorus antioxidant. Furthermore, even when it has both a hindered amine skeleton and a hindered phenol skeleton, the content is calculated by counting it as both a light stabilizer and a phenol antioxidant.
  • the physical properties of the styrenic resin composition in this embodiment will be described below.
  • the Vicat softening temperature of the styrenic resin composition is preferably 105°C or higher, more preferably 110°C or higher, even more preferably 115°C or higher, even more preferably 118°C or higher, even more preferably is 121°C or higher.
  • the Vicat softening temperature can be measured in accordance with ISO306 under the conditions of a 5 kg load and a temperature increase rate of 50° C./h.
  • the surface scratch hardness of the styrenic resin composition is H or higher.
  • the surface scratch hardness is based on the scratch hardness (pencil method) described in JIS K 5600-5-4, with a pencil lead tip load of 750 g, a pencil angle of 45 degrees, and a scratching speed of 0.5 to 1.0 mm/sec.
  • the surface scratch hardness of the styrene resin composition is H or higher, when a molded product of the styrene resin composition is used for a transparent plate for a car (for example, a transparent cover plate for a speedometer or a cover for a lighting equipment) It is possible to suppress cracks caused by human hands, scratches, or whitening caused by oil stains.
  • the melt flow rate of the styrenic resin composition at 200°C and a load of 5 kg is preferably in the range of 0.1 to 2.0 g/10 minutes, more preferably 0.2 to 1.5 g. /10 minutes, more preferably 0.4 to 1.0 g/10 minutes, even more preferably 0.5 to 1.0 g/10 minutes.
  • the melt flow rate is 0.5 to 1.0 g/10 minutes, a resin particularly excellent in the balance between moldability and strength can be obtained.
  • the styrenic resin composition of the present embodiment optionally contains a rubbery polymer containing a conjugated diene monomer unit such as high impact polystyrene, MBS resin, ABS resin, styrenic elastomer, or core-shell type butadiene rubber particles. You may. In this embodiment, the content of conjugated diene monomer units derived from high-impact polystyrene, MBS resin, ABS resin, styrenic elastomer, core-shell type butadiene rubber particles, etc.
  • a conjugated diene monomer unit such as high impact polystyrene, MBS resin, ABS resin, styrenic elastomer, or core-shell type butadiene rubber particles.
  • styrene-based It is preferably 0 to 25% by mass, more preferably 0 to 10% by mass, more preferably 0.05 to 7% by mass, even more preferably 0.10 to 5% by mass, based on the entire resin composition. Even more preferably, it is 0.20 to 3% by mass.
  • the styrenic resin composition in this embodiment contains a styrene component and an unsaturated carboxylic acid component.
  • the styrene component herein refers to the styrene monomer unit (1) and other styrene monomer units contained in the monomer (b2).
  • the unsaturated carboxylic acid component is a general term for the unsaturated carboxylic acid monomer unit (a1) and the unsaturated carboxylic acid monomer unit (b2), in other words, the (meth)acrylic acid unit mer unit (a1-1), (meth)acrylic acid ester monomer unit (a1-2), (meth)acrylic acid monomer unit (b1-1), and (meth)acrylic acid ester monomer unit A general term for unsaturated carboxylic acid monomer units that can be included as (b1-2).
  • the content of the styrene component is preferably 50 to 85% by mass, more preferably 55 to 83% by mass, based on the total amount (100% by mass) of the styrene resin composition. % by mass, more preferably 58 to 80% by mass.
  • the content of the unsaturated carboxylic acid component is preferably 10 to 80% by weight, more preferably is more preferably 20 to 72% by mass, more preferably 34 to 51% by mass.
  • the content of the unsaturated carboxylic acid component is in the range of 17 to 50% by mass, a styrenic resin composition with an excellent balance of heat resistance, oil resistance, and strength can be obtained.
  • the content is set to 25% by mass or more, resistance to oil exceeding 90°C can be obtained.
  • the unsaturated carboxylic acid monomer unit in this embodiment is preferably a (meth)acrylic acid monomer unit, and the (meth)acrylic acid monomer unit in the styrenic resin composition is It is preferably 2 to 40% by weight, more preferably 3 to 20% by weight, even more preferably 4 to 17% by weight, even more preferably 8 to 14% by weight, based on the total amount (100% by weight) of the composition. %, preferably 10-13% by weight, more preferably 10.3-13% by weight, even more preferably 10.3-12.5% by weight, most preferably 10.5-12.5% by weight.
  • the effect of improving heat resistance can be obtained by setting the content of (meth)acrylic acid monomer units in the styrenic resin composition to 2% by mass or more, and by controlling the content to 40% by mass or less. This can prevent the viscosity from increasing too much.
  • by setting the content in the range of 10 to 13% by mass it is possible to obtain a styrenic resin composition that is both highly effective in improving heat resistance and suppressing gel formation to a level applicable to transparent sheet applications. .
  • the unsaturated carboxylic acid ester monomer unit in this embodiment is preferably a methyl (meth)acrylate monomer unit
  • the (meth)acrylic acid monomer unit in the styrenic resin composition is preferably a methyl (meth)acrylate monomer unit.
  • the content is preferably 6 to 55% by mass, preferably 10 to 50% by mass, more preferably 14 to 45% by mass, and even more preferably 16 to 40% by mass based on the total amount (100% by mass) of the resin composition. %, more preferably in the range of 20 to 37% by weight.
  • the content of the (meth)acrylic acid ester monomer in the entire composition is within the above range, the effect of improving oil resistance and strength can be sufficiently obtained.
  • the content of all methyl (meth)acrylate monomer units contained in the styrenic resin composition should be adjusted to the total amount of the styrenic resin composition ( 100% by mass), preferably 0 to 15% by mass, more preferably 0 to 10% by mass, more preferably 0 to 7% by mass, and more preferably 0 to 6% by mass. Mass%.
  • the content of all (meth)acrylic acid ester monomers refers to the total amount of (meth)acrylic acid ester monomer units present in the styrene-based resin composition.
  • the respective contents of (meth)acrylic acid ester monomer units in the resin (B) and the optionally added resin are also converted.
  • the haze (cloudiness) of the 2 mm plate which is a test piece formed from the styrene resin composition
  • the haze (cloudiness) of the 2 mm plate is preferably 15% or less, more preferably 7%, even more preferably 3% or less, and most preferably is 1.5% or less.
  • the method for producing a 2 mm plate is to mold a styrene resin composition into a 2 mm plate by injection molding under the following conditions, as described in Examples below. Molding machine: Toshiba Machine Co., Ltd.
  • composition of styrenic resin composition contains resin (A), resin (B), light stabilizer (C), and ultraviolet absorber (D), and contains resin (A) and resin (B).
  • the total content may preferably be 65 to 100% by mass, more preferably 75 to 95% by mass, based on the entire styrenic resin composition.
  • the styrenic resin composition of the present embodiment contains a resin (A), a resin (B), a light stabilizer (C), an ultraviolet absorber (D), and an additive.
  • the total content of B), the light stabilizer (C), the ultraviolet absorber (D), and the additive is preferably 70 to 100% by mass, more preferably 80% by mass, based on the entire styrenic resin composition. 95% by weight.
  • the styrenic resin composition of this embodiment has resin (A), resin (B), and resin (C), and the total content of resin (A), resin (B), and resin (C) is , preferably accounts for 70 to 100% by mass, more preferably 80 to 90% by mass, based on the entire styrenic resin composition.
  • the styrenic resin composition of the present embodiment contains a resin (A), a resin (B), a light stabilizer (C), an ultraviolet absorber (D), and a monohydric alcohol (E).
  • the styrenic resin composition of this embodiment contains resin (A), resin (B), light stabilizer (C), ultraviolet absorber (D), monohydric alcohol (E), and mold release agent (F). and the total content of resin (A), resin (B), light stabilizer (C), ultraviolet absorber (D), monohydric alcohol (E), and mold release agent (F) is styrene-based It may preferably account for 70 to 100% by weight, more preferably 80 to 90% by weight, based on the entire resin composition.
  • the styrene resin composition of this embodiment includes a resin (A), a resin (B), a light stabilizer (C), an ultraviolet absorber (D), a monohydric alcohol (E), and a mold release agent (F). and the total of resin (A), resin (B), light stabilizer (C), ultraviolet absorber (D), monohydric alcohol (E), mold release agent (F), and additives.
  • the content may preferably be 85 to 100% by mass, more preferably 90 to 95% by mass, based on the entire styrenic resin composition.
  • Particularly preferred form of styrenic resin composition is a styrene-unsaturated carboxylic acid resin (A) having a styrene monomer unit (1) and an unsaturated carboxylic acid monomer unit (a1) of 59% by mass or more and 89% by mass.
  • the content of all styrenic monomer units in the styrenic resin composition is 58.8 to 71.6% by mass
  • the (meth)acrylic resin (B) is a copolymer containing a methyl methacrylate monomer unit and a methyl acrylate monomer unit
  • the total content of all methyl methacrylate monomer units and all methyl acrylate monomer units in the styrenic resin composition is 16 to 40% by mass with respect to the entire styrenic resin composition.
  • a styrene resin composition This results in a styrene resin composition that has excellent compatibility with acrylic resins and is used in molded products that have excellent weather resistance, mechanical strength, and oil resistance without reducing heat resistance and transparency. can be provided.
  • the method for producing the styrenic resin composition is not particularly limited to the method of blending, melting, kneading, and granulating each raw material component, and a method commonly used in the production of styrenic resin compositions is used. be able to.
  • the above ingredients blended (mixed) using a drum tumbler, Henschel mixer, etc. are melted and kneaded using a Banbury mixer, single screw extruder, twin screw extruder, kneader, etc., and then granulated using a rotary cutter, fan cutter, etc.
  • a resin composition can be obtained by doing this.
  • the resin temperature during melting and kneading is preferably 180 to 270°C.
  • the cylinder temperature of an extruder or the like is preferably set to a temperature 10 to 20° C. lower than the resin temperature. If the resin temperature is less than 180°C, mixing will be insufficient, which is not preferable. On the other hand, if the resin temperature exceeds 270° C., thermal decomposition of the resin occurs, which is not preferable.
  • a method for manufacturing a molded article using the styrene resin composition of this embodiment is as follows.
  • the styrenic resin composition is processed using the above-mentioned melt-kneading molding machine, or the pellets of the obtained styrene-based resin composition are used as a raw material by injection molding, injection compression molding, extrusion molding, blow molding, or press molding.
  • a molded article can be manufactured by a vacuum forming method, a foam molding method, or the like. Among these, injection molding is preferred.
  • ⁇ Injection molded products> Another aspect of the present disclosure is a molded product manufactured by injection molding the styrene resin composition described above, which has excellent heat resistance, transparency, weather resistance, mechanical strength, and surface hardness, and is suitable for automotive applications. It can be suitably used. Specific examples include lighting covers containing styrene resin compositions and injection molded products for vehicles.
  • Injection volume 10 ⁇ L Measurement temperature: 40°C Flow rate: 0.35 mL/min Detector: Differential refractometer To create the calibration curve, 11 types of TSK standard polystyrene manufactured by Tosoh (F-850, F-450, F-128, F-80, F-40, -20, F-10, F-4, F-2, F-1, A-5000) were used. A calibration curve was created using a linear linear approximation formula.
  • melt mass flow rate (g/10 min) The melt mass flow rate (g/10 min) of each resin and resin composition manufactured in Examples and Comparative Examples was measured at 200°C and a load of 49N in accordance with ISO1133. Measured at
  • the Vicat softening temperature of each resin and resin composition manufactured in Examples and Comparative Examples was measured in accordance with ISO306.
  • the load was 50N, and the temperature increase rate was 50°C/h.
  • the Vicat softening temperature exceeds 105°C, it was possible to obtain an injection molded product that is resistant to thermal deformation even at high temperatures of 100°C or higher.
  • Measuring equipment Agilent 6850 series GC system Detector: FID Column: DB-WAX Length: 60m Film thickness: 0.50 ⁇ m Diameter: 0.320mm ⁇ Injection volume: 1 ⁇ L Split ratio: 50:1 Column temperature: Hold at 100°C for 5 minutes ⁇ Raise the temperature to 130°C at 10°C/min ⁇ Raise the temperature to 180°C at 10°C/min ⁇ Hold at 180°C for 10 minutes ⁇ Raise the temperature to 220°C at 20°C/min ⁇ Hold at 220°C for 10 minutes Inlet temperature: 230°C Detector temperature: 300°C Carrier gas: helium When detecting the peak of monohydric alcohol (E) having 10 or more carbon atoms, in order to avoid overlapping other peaks and saturation of the peak intensity, pretreatment such as dilution of the sample and use of The column to be used and the detection conditions may be adjusted as appropriate.
  • E monohydric alcohol
  • Inlet temperature 300°C Detector temperature: 300°C Split ratio: 1/300 Carrier gas: Helium Detection method: Mass spectrometer (MSD) Sample amount: 50 ⁇ g Detection mode: scan mode or SIM mode When detecting each monomer peak, in order to avoid overlapping peaks and saturation of peak intensity, pretreatment such as sample dilution rate, column used, and detection conditions should be performed as appropriate. may be adjusted as appropriate.
  • YI (yellowness) measurement of 300 mm long optical path test piece Each resin composition produced in the Examples and Comparative Examples was molded into a 300 mm long optical path test piece by injection molding in a constant temperature room at 23°C and 50% humidity. After conditioning for 48 hours or more, YI was measured using a Nippon Denshoku long optical path spectral transmission color meter ASA-1), and the n3 average was taken as the value. In particular, when placing importance on the initial color tone, emphasis may be placed on the YI value in a long optical path.
  • ⁇ Haze Haze after test (%) - Haze before test (%) ⁇ Evaluation criteria> ⁇ ... ⁇ haze is less than 1% ⁇ ... ⁇ haze is 1% or more and 3% or less ⁇ ... ⁇ haze is greater than 3% and 5% or less ⁇ ... ⁇ haze is greater than 5%
  • the polymerization temperature of the complete mixing reactor was 130°C.
  • the temperature of the single-screw extruder was set at 210 to 230°C and the pressure was set at 10 torr to devolatilize volatile components such as unreacted monomers and polymerization solvent.
  • the devolatilized volatile components were condensed in a condenser through which a -5°C refrigerant was passed and recovered as an unreacted liquid, and the styrene resin was recovered as resin pellets.
  • the physical properties of resin a-1 obtained by the above analysis method are shown in Table 1 below.
  • Resin a-4 was obtained as a styrene homopolymer with the composition and physical properties shown in Table 1 in the same manner as above using only styrene as a monomer.
  • the obtained resins a-1 to a-13 contained residual styrene monomers of about 100 to 500 ⁇ g/g, ethylbenzene of about 10 to 200 ⁇ g/g, and 2-ethyl-1-hexanol of 30 to 120 ⁇ g/g. It contained about 1,000 to 5,000 ⁇ g/g of styrene dimer and trimer, and impurities derived from the residue of the polymerization raw material composition. These quantitative determinations were performed in the same manner as in the quantitative determination of monohydric alcohol (E) having 10 or more carbon atoms using gas chromatography described above.
  • E monohydric alcohol
  • the polymerization reaction solution was taken out from the 60 L reactor and passed through a sieve with a sieve opening of 1.7 mm to remove giant aggregates, and then the aqueous layer and solid matter were separated using a Buchner funnel to obtain bead-shaped polymers.
  • the bead-shaped polymer was washed and dehydrated five times with about 20 L of distilled water on a Buchner funnel, dried, and pelletized using a single-screw extruder to obtain resin b-1 as a pelletized resin.
  • Ta the polymerization reaction solution was taken out from the 60 L reactor and passed through a sieve with a sieve opening of 1.7 mm to remove giant aggregates, and then the aqueous layer and solid matter were separated using a Buchner funnel to obtain bead-shaped polymers.
  • the bead-shaped polymer was washed and dehydrated five times with about 20 L of distilled water on a Buchner funnel, dried, and pelletized using a single-screw extruder to obtain resin
  • Resins b-2 to b-8 were prepared in the same manner as resin b-1 by adjusting the feed amount of each monomer and polymerization conditions.
  • the compositions and physical properties of the obtained resins b-1 to b-8 are shown in Table 2.
  • the following alcohol species were used as the monohydric alcohol (E) having 10 or more carbon atoms.
  • the monohydric alcohol (E-1) Fine Oxocol 180 (compound name: 5,7,7-trimethyl-2-(1,3,3-trimethylbutyl)-1-octanol) manufactured by Nissan Chemical Co., Ltd. was used. did.
  • Calcol 8098 compound name: stearyl alcohol
  • E-3 Emulgen 109P (polyoxyethylene (9) lauryl ether monoalcohol) manufactured by Kao Corporation was used.
  • Light stabilizer c-1 CAS number: 52829-07-9
  • Light stabilizer c-2 CAS number: 705257-84-7
  • Light stabilizer c-3 CAS number: 64022-61-3
  • Light stabilizer c-4 CAS number: 41556-26-7
  • Light stabilizer c-5 CAS number: 101357-37-3 and 85631-01-2 mixture
  • crosslinked body (G)> Preparation of crosslinked body g-1- Production of MMA-nBA copolymerized crosslinked beads (C) which are unmelted compounds
  • polymerization was carried out at a temperature of 125° C. for 3 hours. After the reaction was completed, washing, dehydration, and drying were performed to obtain a crosslinked product (g-1).
  • the average particle diameter of the crosslinked product (g-1) was 4 ⁇ m, and the refractive index was 1.470.
  • crosslinked product (g-2) was 8 ⁇ m, and the refractive index was 1.545.
  • -Preparation of crosslinked body g-3- 100 parts by mass of methyl methacrylate, 5 parts by mass of divinylbenzene as a crosslinking agent, 0.2 parts by mass of benzoyl peroxide as a polymerization initiator, 0.001 parts by mass of sodium dodecylbenzenesulfonate as a suspension stabilizer, and 0.5 parts by mass of tricalcium phosphate and 200 parts by mass of pure water were charged, and polymerization was carried out at a temperature of 95°C for 6 hours and then at a temperature of 125°C for 3 hours.
  • crosslinked product (g-3) had an average particle diameter of 8 ⁇ m and a refractive index of 1.494.
  • -Preparation of crosslinked product g-4 In a pressure-resistant container with a stirrer, 200 parts by mass of pure water, 0.008 parts by mass of ethylenediaminetetraacetic acid disodium salt, 0.002 parts by mass of sodium polyoxyethylene alkyl ether phosphate, 0.0012 parts by mass of ferrous sulfate, After charging 0.03 parts by mass of ethylenediaminetetraacetate dinatriate and deoxidizing, 100 parts by mass of butadiene, 0.05 parts by mass of sodium formaldehyde sulfoxylate, and 0.2 parts by mass of para-menthane hydroperoxide were added, and then After dropping 1.4 parts by mass of sodium polyoxyethylene alkyl ether phosphate over a period of time, the
  • a rubber-like polymer crosslinked product (g-4) was obtained as a powder by processing, washing with water, and dehydrating and drying.
  • crosslinked body (g-5) Metablane W-450A (product name) manufactured by Mitsubishi Chemical Corporation
  • Crosslinked body (g-6) Techpolymer MBX-5 (product name) manufactured by Sekisui Plastics Co., Ltd.
  • antioxidant h-1 Irganox1076 manufactured by BASF Japan Compound name: Octadecyl-3-(3,5-tert-butyl-4-hydroxyphenyl)propionate
  • Phenolic antioxidant h-2 Sumilizer GA-80 manufactured by Sumitomo Chemical Co., Ltd.
  • styrenic resin composition The detailed manufacturing method of the styrenic resin composition will be shown below.
  • -Example 1- 70.0 parts by mass of resin a-1 listed in Table 1 as styrene-unsaturated carboxylic acid resin (A), and 30.0 parts by mass of resin b-1 listed in Table 2 as (meth)acrylic resin (B) part, and 0.12 parts by mass of the light stabilizer c-1 listed in Table 3 as the light stabilizer (C), that is, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, and an ultraviolet absorber.
  • A styrene-unsaturated carboxylic acid resin
  • B (meth)acrylic resin
  • C the light stabilizer
  • the screw rotation speed was 150 rpm
  • the cylinder temperature was 180 to 230°C
  • the feed rate was 10 kg/h.
  • the resin temperature was 250-260°C.
  • the evaluation results of the obtained styrenic resin composition (1) and its molded products are shown in Table 7-1.
  • Examples 2 to 45- Styrenic resin compositions (2) to (45) and molded products thereof were obtained in the same manner as in Example 1, except that the formulations were changed as shown in Tables 7-1 to 7-3 below. The evaluation results for each composition and molded article are shown in Tables 7-1 to 7-3.
  • Comparative Examples 1 to 6 Resin compositions and molded articles thereof of Comparative Examples 1 to 6 were obtained in the same manner as in Example 1 except that the formulations were changed as shown in Table 8 below. Table 8 shows the evaluation results for each composition and molded article.
  • Examples 46 to 135- The styrenic resin compositions (46) to (135) of Examples 46 to 135 and their molded products were prepared in the same manner as in Example 1 except that the formulations were changed as shown in Tables 9-1 to 10-3 below. Obtained. The evaluation results for each composition and molded article are shown in Tables 9-1 to 10-3.
  • the styrenic resin composition of the present disclosure can be used for molded articles with excellent weather resistance, mechanical strength, and oil resistance without reducing heat resistance and transparency.
  • the molded product of the present disclosure can be widely used in applications such as automotive materials, food container packaging materials, housing insulation materials, lighting equipment housing materials, monitor or display materials, and light guide plates or light diffusion plates. .

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013151055A1 (ja) * 2012-04-02 2013-10-10 Ｐｓジャパン株式会社 ポリスチレン系樹脂組成物及びこれを成形してなる導光板
WO2018008579A1 (ja) * 2016-07-06 2018-01-11 デンカ株式会社 偏光子保護フィルム用樹脂組成物、偏光子保護フィルム
JP2020105403A (ja) * 2018-12-27 2020-07-09 Ｐｓジャパン株式会社 耐熱スチレン系樹脂組成物、押出シート、成形品
WO2021161898A1 (ja) * 2020-02-10 2021-08-19 旭化成株式会社 熱可塑性樹脂組成物
JP2022041091A (ja) * 2020-08-31 2022-03-11 Ｐｓジャパン株式会社 スチレン系樹脂組成物及び成形品

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7064827B2 (ja) 2017-03-06 2022-05-11 東洋スチレン株式会社 光学用スチレン系樹脂組成物、成形品および導光体
CN116710517A (zh) * 2020-11-30 2023-09-05 英力士苯领集团股份公司 低雾度和高清晰度的抗紫外线smma共聚物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013151055A1 (ja) * 2012-04-02 2013-10-10 Ｐｓジャパン株式会社 ポリスチレン系樹脂組成物及びこれを成形してなる導光板
WO2018008579A1 (ja) * 2016-07-06 2018-01-11 デンカ株式会社 偏光子保護フィルム用樹脂組成物、偏光子保護フィルム
JP2020105403A (ja) * 2018-12-27 2020-07-09 Ｐｓジャパン株式会社 耐熱スチレン系樹脂組成物、押出シート、成形品
WO2021161898A1 (ja) * 2020-02-10 2021-08-19 旭化成株式会社 熱可塑性樹脂組成物
JP2022041091A (ja) * 2020-08-31 2022-03-11 Ｐｓジャパン株式会社 スチレン系樹脂組成物及び成形品

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
no. 178671-58-4
See also references of EP4563642A4

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