Classifications

• • 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
• • 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
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/04—Polymerisation in solution
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/04—Polymerisation in solution
  • C08F2/06—Organic solvent
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • 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
• • 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
  • C08F4/00—Polymerisation catalysts
  • C08F4/28—Oxygen or compounds releasing free oxygen
  • C08F4/32—Organic compounds
  • C08F4/34—Per-compounds with one peroxy-radical
• • 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
  • C08F6/00—Post-polymerisation treatments
  • C08F6/001—Removal of residual monomers by physical means
  • C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
• • 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
  • C08K5/14—Peroxides
• • 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
• • 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
• • 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

Definitions

• the present invention provides styrenic monomer units and (meth)acrylic acid ester units that have excellent safety and productivity, injection moldability, and color and light resistance of molded products in cosmetics and food packaging applications, and have low odor.
• the present invention relates to a resin composition containing a copolymer containing a mer unit.
• Styrenic resins represented by polystyrene have excellent color, rigidity, moldability, etc., and are also inexpensive, so they are used for household goods, toys, housing materials for OA equipment, food packaging containers, etc.
• it since it is a non-toxic and safe material with excellent processing properties such as sheet processability, foaming properties, and vacuum formability, it has been widely used for applications such as food packaging containers.
• Patent Documents 1 to 3 describe unreacted monomers remaining in a copolymer containing a styrene monomer unit and a (meth)acrylic acid ester monomer unit and styrene contained as a by-product.
• productivity, appearance and odor during molding of copolymers can be improved by reducing the sulfur content based on the dimer, styrene trimer, and sulfur-based chain transfer agent to a predetermined amount or less.
• a polyfunctional organic peroxide or two or more types of monofunctional organic peroxides as essential components for the polymerization initiator, a sufficient amount of polymerization initiator exists in the high conversion region, and the styrene dimer , has been disclosed to suppress the production of trimers, and to suppress the remaining of a large amount of monomers and the decrease in productivity.
• the present invention provides styrenic monomer units and (meth)acrylic acid ester units that have excellent safety and productivity, injection moldability, and color and light resistance of molded products in cosmetics and food packaging applications, and have low odor.
• An object of the present invention is to provide a resin composition containing a copolymer containing a mer unit.
• the present invention (1) A resin composition containing a copolymer containing a styrene monomer unit and a (meth)acrylic acid ester monomer unit, The total content of unreacted monomers is 2000 mass ppm or less, The sulfur content is more than 0 mass ppm and 150 mass ppm or less, The yellowness of the 2 mmt injection molded plate is 0.6 or less, A resin composition characterized by: (2) 100000 times the reciprocal of the product of the total content of the unreacted monomers and the sulfur content (100000/(total content of the unreacted monomers x the sulfur content)) The resin composition according to (1), which has a molecular weight of 0.5 to 8.0.
• the ratio of the total content of the unreacted monomers to the sulfur content is from 8 to 50, or (1) (2) The resin composition described in (2).
• the resin composition described in (2) is A, and the yellowness of the plate after 360 hours of ultraviolet irradiation at an irradiation intensity of 60 W/m is B, the following relationships are satisfied: (1) to (3) ).
• the total content of the styrene monomer units and the (meth)acrylic acid ester monomer units contained in 100% by mass of the copolymer is more than 96% by mass;
• the copolymer further contains other copolymerizable monomer units, The content of the other copolymerizable monomer units is 100 in total of the styrene monomer units, the (meth)acrylic acid ester monomer units, and the other copolymerizable monomer units.
• the other copolymerizable monomer unit is one or more selected from the group consisting of acrylic acid, acrylonitrile, methacrylonitrile, butyl acrylate, ethyl acrylate, methyl acrylate, phenylmaleimide, and cyclohexylmaleimide. , (1) to (8).
• (11) including a step of polymerizing a styrene monomer and a (meth)acrylic acid ester monomer, The method for producing a resin composition according to any one of (1) to (10), wherein in the polymerization step, a linear alkyl mercaptan chain transfer agent and an ⁇ -methylstyrene dimer chain transfer agent are used together. . (12) The method according to (11), wherein the ratio of the amount of the linear alkyl mercaptan chain transfer agent added to the amount of the ⁇ -methylstyrene dimer chain transfer agent added is 0.08 to 0.25. A method for producing a resin composition. (13) An injection molded article using the resin composition according to any one of (1) to (10). (14) A home appliance casing or a container for food, stationery, or cosmetics, using the injection molded product according to (13). Regarding.
• styrenic monomer units and (meth)acrylic acid esters have excellent safety and productivity in cosmetic and food packaging applications, injection moldability, and color and light resistance of molded products, and have low odor.
• a resin composition containing a copolymer containing a monomer unit can be provided.
• the copolymer containing a styrene monomer unit and a (meth)acrylic acid ester monomer unit according to the present embodiment is derived from a styrene monomer and a (meth)acrylic acid ester monomer, respectively.
• a copolymer containing a styrene monomer unit and a (meth)acrylic acid ester monomer unit may be simply referred to as "copolymer P.”
• the copolymer P according to this embodiment may contain other copolymerizable monomer units other than styrene monomer units and (meth)acrylic acid ester monomer units within a range that does not impede the effects of the present invention. It may also contain mercury units.
• the monomer units constituting the copolymer P according to this embodiment will be explained.
• the styrenic monomer unit is a structural unit of the copolymer P derived from the styrenic monomer used in copolymerization.
• the styrene monomer include styrene, ⁇ -methylstyrene, and styrene in which a portion of the benzene nucleus is substituted with an alkyl group. In one embodiment, styrene is preferred among these from the viewpoint of rigidity and moldability. These styrene monomers may be used alone or in combination of two or more.
• the copolymer P according to this embodiment preferably contains 20 to 80% by mass of styrene monomer units in 100% by mass of the copolymer P. More preferably, the content of styrenic monomer units is 30 to 70% by mass, and even more preferably 35 to 55% by mass. Specifically, for example, it is preferable to contain 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 or 80% by mass, and between any two of the numerical values exemplified here. may be within the range of If the amount of styrenic monomer units is less than 30% by mass, the moldability may be insufficient, and if it exceeds 70% by mass, the hue may be insufficient.
• the content of styrene monomer units in copolymer P is calculated from the mass of the styrene monomer relative to the mass of all monomers used in the polymerization. It can also be calculated by, for example, performing 1H-NMR measurement on the obtained copolymer P.
• the content of the styrene monomer unit means the total amount of the styrene monomer unit used in combination.
• the (meth)acrylic acid ester monomer unit is a structural unit of the copolymer P derived from the (meth)acrylic acid ester monomer used in copolymerization.
• Examples of (meth)acrylic acid ester monomer units include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and 2-methylhexyl.
• acrylic acid esters such as acrylate, 2-ethylhexyl acrylate, and decyl acrylate. In one embodiment, methyl methacrylate is preferred among these from the viewpoints of cost, hue, and heat resistance.
• These (meth)acrylic acid ester monomers may be used alone or in combination of two or more types.
• the copolymer P according to this embodiment preferably contains 20 to 80% by mass of (meth)acrylic acid ester monomer units in 100% by mass of the copolymer P. More preferably, the content of (meth)acrylic acid ester monomer units is 30 to 70% by mass, and even more preferably 45 to 65% by mass. Specifically, for example, it is preferable to contain 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 or 80% by mass, and between any two of the numerical values exemplified here.
• the content of the (meth)acrylic acid ester monomer units in the copolymer P is calculated from the mass of the (meth)acrylic acid ester monomer relative to the mass of all monomers used in the polymerization. It can also be calculated by, for example, performing 1H-NMR measurement on the obtained copolymer P. In addition, when (meth)acrylic acid ester monomer units are used together, the content of (meth)acrylic acid ester monomer units is the same as that of the (meth)acrylic acid ester monomer units used together. means the total amount.
• the copolymer P according to the present embodiment may contain other copolymerizable monomers other than the styrene monomer unit and the (meth)acrylic acid ester monomer unit within a range that does not impede the effects of the present invention. May optionally include body units.
• Examples of other copolymerizable monomer units include acrylic acid, acrylonitrile, methacrylonitrile, butyl acrylate, ethyl acrylate, methyl acrylate, phenylmaleimide, and cyclohexylmaleimide. These other copolymerizable monomer units may be used alone or in combination of two or more types.
• the content of the other copolymerizable monomer units is 100 in total of the styrene monomer units, the (meth)acrylic acid ester monomer units, and the other copolymerizable monomer units. It is preferably 0 to 10% by mass, more preferably 8% by mass or less.
• the copolymer P according to this embodiment has a total content of styrene monomer units and (meth)acrylic acid ester monomer units contained in 100% by mass of the copolymer P of more than 96% by mass.
• the content is preferably 98% by mass or more, and more preferably 98% by mass or more.
• the copolymer P consists essentially only of styrene monomer units and (meth)acrylate monomer units. Note that "consisting essentially only of styrene monomer units and (meth)acrylic acid ester monomer units” means that other units other than styrene monomer units and (meth)acrylic acid ester monomer units are used.
• the content of methacrylic acid monomer units contained in 100% by mass of the copolymer P is preferably less than 4% by mass, and preferably less than 2% by mass. is more preferable.
• the resin composition according to the present embodiment may contain some of the monomers used in the copolymerization of the copolymer P as unreacted monomers.
• the total content of unreacted monomers contained in the resin composition according to the present embodiment is 2000 mass ppm or less, preferably 1800 mass ppm or less, and more preferably 1600 mass ppm or less. be. Specifically, for example, it is preferably 2000, 1800, 1600, 1400, 1200, 1000, 800, 600, or 500 mass ppm, and even if it is within the range between any two of the numerical values exemplified here. good.
• the content of unreacted monomers in the resin composition can be measured by an internal standard method using, for example, gas chromatography.
• the content of unreacted monomers is , means the total amount of these monomers used together.
• the content of unreacted monomers in the resin composition can be controlled, for example, by adjusting the type and amount of the chain transfer agent used during polymerization of the copolymer P. It can also be controlled by adjusting the devolatilization conditions after obtaining the copolymer P and the ratio of monomers used when polymerizing the copolymer P.
• the resin composition according to the present embodiment may contain sulfur due to the sulfur-based chain transfer agent used during copolymerization of the copolymer P.
• the sulfur content contained in the resin composition according to the present embodiment is more than 0 mass ppm and 150 mass ppm or less. Preferably it is 30 mass ppm or more, more preferably 40 mass ppm or more. Specifically, for example, it is preferably 0.1, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, or 150 mass ppm, and the numerical values exemplified here. It may be within the range between any two. When the sulfur content is 150 mass ppm or less, odor is sufficiently reduced.
• the sulfur content of the resin composition can be measured, for example, by using a flat plate of the resin composition and quantifying sulfur by the fluorescence method of X-ray analysis.
• the sulfur content of the resin composition can be controlled, for example, by adjusting the type and amount of the chain transfer agent used during polymerization of the copolymer P.
• the yellowness index (YI) of a 2 mm thick injection molded plate obtained from the resin composition according to the present embodiment is 0.6 or less, preferably 0.55 or less, and more preferably 0.50 or less. Specifically, for example, it is preferably 0.1, 0.2, 0.3, 0.4, 0.5, or 0.6, and within the range between any two of the numerical values exemplified here. It may be.
• the yellowness index (YI) is 0.6 or less, there are advantages in that the molded product has excellent hue and colorability.
• the yellowness index (YI) of a 2 mmt injection molded plate obtained from the resin composition can be measured using, for example, a color difference meter ( ⁇ -80 manufactured by Nippon Denshoku Kogyo Co., Ltd.).
• the yellowness index (YI) of the 2 mmt injection molded plate obtained from the resin composition can be controlled, for example, by adjusting the type and amount of the chain transfer agent used during polymerization of the copolymer P. It can also be controlled by adjusting the type and proportion of monomers used in the polymerization of the copolymer P and the devolatilization conditions for the obtained copolymer P.
• ⁇ Change amount of yellowness ⁇ YI> When the yellowness index (YI) of a 2 mm thick injection molded plate obtained from the resin composition according to the present embodiment is A, and the yellow index (YI) of the plate after being irradiated with ultraviolet rays for 360 hours at an irradiation intensity of 60 W/m is B. , it is preferable that the following relationship is satisfied. B-A ⁇ 0.8 More preferably, the value of BA is less than 0.75, even more preferably less than 0.70. When the value of BA is less than 0.8, resistance to ultraviolet rays is good, there is little yellowing especially when used and stored outdoors, and excellent optical properties can be maintained.
• the value of BA can be controlled, for example, by adjusting the type and amount of the chain transfer agent used during polymerization of the copolymer P. It can also be controlled by the type and proportion of monomers used in the polymerization of copolymer P, and by the use of stabilizers.
• the resin composition according to the present embodiment has a composition that is 100,000 times the reciprocal of the product of the total content of unreacted monomers and the sulfur content (100,000/(total content of unreacted monomers x sulfur content). )) is preferably 0.5 to 8.0, more preferably 0.8 to 7.5, even more preferably 1.0 to 2.5. Specifically, for example, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.3, 1.4, 1.5, 2.0, It is preferably 3.0, 4.0, 5.0, 6.0, 7.0, or 8.0, and may be within a range between any two of the numerical values exemplified here.
• the value of (100000/(total content of unreacted monomers x sulfur content)) can be determined, for example, by adjusting the type and amount of chain transfer agent used during polymerization of copolymer P. Can be controlled. It can also be controlled by adjusting the type and proportion of monomers used in the polymerization of the copolymer P and the devolatilization conditions for the obtained copolymer P.
• the ratio of the total content of unreacted monomers to the sulfur content is 8 to 50. It is preferably from 10 to 40, even more preferably from 20 to 30. Specifically, for example, it is preferably 8, 10, 15, 20, 25, 30, 35, 40, or 50, and may be within a range between any two of the numerical values exemplified here. If the ratio of the total content of unreacted monomers to the sulfur content is within this range, there is an excellent balance between odor reduction and safety in cosmetics and food packaging applications.
• the ratio of the total content of unreacted monomers to the sulfur content can be controlled, for example, by adjusting the type and amount of the chain transfer agent used during polymerization of the copolymer P. It can also be controlled by adjusting the devolatilization conditions of the obtained copolymer P.
• the resin composition according to the present embodiment preferably has an MFR value of 1 to 5 g/10 min, more preferably 1.5 to 4 g/10 min, and more preferably 1. 8 to 3 g/10 min. Specifically, it is preferably 1, 2, 3, 4, or 5 g/10 min, and may be within a range between any two of the numerical values exemplified here. If the MFR value is within this range, fluidity will be good and moldability will be excellent.
• the resin composition according to the present embodiment preferably has an MFR value of 70 to 110 g/10 min, more preferably 80 to 95 g/10 min, at a test temperature of 240°C and a nominal load of 10 kg. It is 10 minutes.
• it is preferably 70, 75, 80, 85, 90, 95, 100, or 110 g/10 min, and may be within a range between any two of the numerical values exemplified here. If the MFR value is within this range, fluidity will be good and moldability will be excellent.
• the MFR value is a value measured at 200° C. and 5 kg or 240° C. and 10 kg according to JIS K-7210.
• the MFR value can be controlled, for example, by adjusting the type and amount of the chain transfer agent used during polymerization of the copolymer P, and by adjusting the molecular weight of the copolymer P. It can also be controlled by adjusting the type and proportion of monomers used in the polymerization of copolymer P.
• the copolymer P according to this embodiment is obtained by a step of polymerizing a styrene monomer and a (meth)acrylic acid ester monomer, and is preferably produced by radical polymerization. Specifically, suspension polymerization, bulk polymerization, solution polymerization, etc. are used, and suspension polymerization is preferable. In suspension polymerization, it is easy to remove the heat generated by polymerization, and polymerization can be performed up to a high conversion rate, so that unreacted monomers can be efficiently suppressed.
• Polymerization solvent examples include alkylbenzenes such as benzene, toluene, ethylbenzene, and xylene, ketones such as acetone and methyl ethyl ketone, and aliphatic hydrocarbons such as hexane and cyclohexane.
• alkylbenzenes such as benzene, toluene, ethylbenzene, and xylene
• ketones such as acetone and methyl ethyl ketone
• aliphatic hydrocarbons such as hexane and cyclohexane.
• the polymerization initiator is preferably a radical polymerization initiator, such as known and commonly used ones such as 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, and 2,2-di(t-butylperoxy)butane.
• Peroxy ketals such as di(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-di(t-amylperoxy)cyclohexane, cumene hydroperoxide, t-butyl hydroperoxide, etc.
• alkyl peroxides such as t-butylperoxyacetate, t-amylperoxyisononanoate, t-butylcumyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t -Dialkyl peroxides such as hexyl peroxide, peroxy esters such as t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxyisopropyl carbonate, polyethers Peroxycarbonates such as tetrakis (t-butylperoxycarbonate), N,N'-azobis(cyclohexane-1-carbonitrile), N,N'-azobis(2-methylbutyronitrile), N,N' -Azobis(2,4-dimethylvaleronitrile), N,N'-azobis[2-(hydroxy)
• a chain transfer agent may be added during the polymerization for the purpose of adjusting the molecular weight.
• chain transfer agents include sulfur-based chain transfer agents, ⁇ -methylstyrene dimer, and terpinolene. These chain transfer agents may be used alone or in combination of two or more types.
• sulfur chain transfer agent examples include linear alkylmercaptan chain transfer agents, branched alkylmercaptan chain transfer agents, aromatic mercaptans, and ethylene thioglycol.
• linear alkylmercaptan chain transfer agent examples include n-dodecylmercaptan, n-octylmercaptan, n-decylmercaptan, n-hexylmercaptan, and n-butylmercaptan.
• Examples of branched alkyl mercaptan chain transfer agents include t-dodecyl mercaptan, sec-dodecyl mercaptan, and isobutyl mercaptan. From the viewpoint of chain transfer effect and the amount of sulfur component produced in the copolymer P, n-dodecyl mercaptan is preferred. These sulfur chain transfer agents may be used alone or in combination of two or more. The sulfur-based chain transfer agent can cause a sulfur component derived from the sulfur-based chain transfer agent to be generated in the resin composition.
• ⁇ -methylstyrene dimer does not cause a sulfur component derived from a sulfur-based chain transfer agent to be produced in the resin composition.
• the method for producing copolymer P according to the present embodiment includes a step of polymerizing a styrene monomer and a (meth)acrylic acid ester monomer, in which a linear alkylmercaptan chain transfer agent and ⁇ -methylstyrene are used. It is preferable to use it together with a dimer chain transfer agent. By using a chain transfer agent in combination, a balance between odor reduction and safety in cosmetic and food packaging applications can be achieved.
• the method for producing copolymer P according to the present embodiment is such that in the step of polymerizing a styrene monomer and a (meth)acrylic acid ester monomer, the amount of the linear alkyl mercaptan chain transfer agent added is The ratio of the ⁇ -methylstyrene dimer chain transfer agent to the amount added is preferably 0.08 to 0.25, more preferably 0.08 to 0.20, and 0.10 to 0.20. It is even more preferable that there be. Specifically, for example, it is preferably 0.08, 0.10, 0.12, 0.14, 0.16, 0.18, 0.20, 0.22, or 0.25, and here It may be within the range between any two of the illustrated numerical values.
• the ratio of the amount of linear alkyl mercaptan chain transfer agent added to the amount of ⁇ -methylstyrene dimer chain transfer agent added is within this range, odor reduction and safety balance in cosmetics and food packaging applications can be achieved. becomes even better.
• the amount of linear alkyl mercaptan chain transfer agents added means the total amount of these linear alkyl mercaptan chain transfer agents used together. do.
• the resin composition according to the present embodiment may contain known antioxidants, lubricants, mold release agents, plasticizers, pigments, dyes, foaming agents, foam nucleating agents, inorganic fillers, antistatic agents, sliding agents, etc., as necessary. Additives may also be added.
• GP-PS general purpose polystyrene
• HI-PS high impact polystyrene
• MBS methyl methacrylate-butadiene-styrene copolymer
• AS acrylonitrile-styrene copolymer
• ABS acrylonitrile-butadiene copolymer
• -Styrene copolymer PE (polyethylene), PP (polypropylene), PPO (polyphenylene oxide), and other known resins
• PE polyethylene
• PP polypropylene
• PPO polyphenylene oxide
• the resin composition according to this embodiment can be made into an injection molded article by a known method. Furthermore, the obtained injection molded product can be used for housings of home appliances or containers for foods, stationery, cosmetics, and the like.
• Capillary gas chromatograph GC-4000 (manufactured by GL Sciences, Inc.) Column: InertCap WAX manufactured by GS Science Co., Ltd., inner diameter 0.25 mm, length 30 m, film thickness 50 ⁇ m Injection temperature: 180°C Column temperature: 60°C to 170°C Detector temperature: 210°C Split ratio: 5/1 (3) Measurement of sulfur content: Using a 2 mmt injection molded plate obtained from a resin composition under molding conditions of a cylinder temperature of 230°C and a mold temperature of 60°C, sulfur was determined by the fluorescence method of X-ray analysis. .
• YI yellowness index
• MFR value The obtained resin composition was measured at 200°C and 5 kg or at 240°C and 10 kg according to JIS K-7210.
• Safety and productivity in food and cosmetic packaging applications A 2mmt plate obtained by injection molding under molding conditions of cylinder temperature 230°C and mold temperature 60°C is immersed in an 8% ethanol solution to approximately 50°C. for about 24 hours, or immersed in n-heptane and heated for about 30 minutes at about 50°C. After taking out the plate, the solution was evaporated to dryness, the weight of the remaining material was measured, and the weight of the remaining material was measured. The safety in food and cosmetic packaging applications was evaluated based on the elution amount per unit area (mg/cm 2 ) according to the following criteria.
• the styrene resin was manufactured by continuous solution polymerization using a radical polymerization method.
• a complete mixing tank type stirred tank was used as the first reactor, and a plug flow type reactor with a static mixer was used as the second reactor, which were connected in series to constitute a polymerization process.
• the capacity of the first reactor was 30L, and the capacity of the second reactor was 12L.
• a raw material solution was prepared with a composition of 35 parts by mass of styrene, 53 parts by mass of methyl methacrylate, and 12 parts by mass of ethylbenzene, and was continuously supplied to the polymerization process at a flow rate of 8.0 kg/hr.
• the polymer concentration at the exit of the polymerization process was 65%, and the conversion rate of styrene and methyl methacrylate was 72%.
• the polymer solution continuously taken out from the reactor was supplied to a vacuum devolatilization tank with a preheater, and unreacted styrene, methyl methacrylate, ethylbenzene, etc. were separated.
• the temperature of the preheater was adjusted so that the polymer temperature in the devolatilization tank was 240° C., and the pressure in the devolatilization tank was 1 kPa.
• the polymer was extracted from the vacuum devolatilization tank using a gear pump, extruded into a strand, cooled with cooling water, and then cut to obtain a pellet-shaped copolymer.
• Table 1 (Table 1-1 to Table 1-2) shows the formulation, analysis, and evaluation results of the resin composition.
• Example 2 The same procedure was carried out except that 0.038 parts by mass of n-dodecyl mercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer in Example 1 were changed to 0.04 parts by mass of n-dodecylmercaptan and 0.40 parts by mass of ⁇ -methylstyrene dimer. The same procedure as in Example 1 was carried out. Table 1 (Table 1-1 to Table 1-2) shows the formulation, analysis, and evaluation results of the resin composition.
• Example 3 The same procedure was carried out except that 0.038 parts by mass of n-dodecylmercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer in Example 1 were changed to 0.04 parts by mass of n-dodecylmercaptan and 0.35 parts by mass of ⁇ -methylstyrene dimer. The same procedure as in Example 1 was carried out.
• Table 1 (Table 1-1 to Table 1-2) shows the formulation, analysis, and evaluation results of the resin composition.
• Example 4 The same procedure was carried out except that 0.038 parts by mass of n-dodecyl mercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer in Example 1 were changed to 0.04 parts by mass of n-dodecylmercaptan and 0.30 parts by mass of ⁇ -methylstyrene dimer. The same procedure as in Example 1 was carried out. Table 1 (Table 1-1 to Table 1-2) shows the formulation, analysis, and evaluation results of the resin composition.
• Example 5 The same procedure was carried out except that 0.038 parts by mass of n-dodecyl mercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer in Example 1 were replaced with 0.05 parts by mass of n-dodecylmercaptan and 0.25 parts by mass of ⁇ -methylstyrene dimer. The same procedure as in Example 1 was carried out. Table 1 (Table 1-1 to Table 1-2) shows the formulation, analysis, and evaluation results of the resin composition.
• Example 6 The same procedure as in Example 2 was carried out except that 54 parts by mass of styrene and 46 parts by mass of methyl methacrylate were used instead of 40 parts by mass of styrene and 60 parts by mass of methyl methacrylate.
• Table 1 (Table 1-1 to Table 1-2) shows the formulation, analysis, and evaluation results of the resin composition.
• Example 7 The same procedure was carried out except that 0.038 parts by mass of n-dodecyl mercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer in Example 1 were changed to 0.07 parts by mass of n-dodecylmercaptan and 0.40 parts by mass of ⁇ -methylstyrene dimer. The same procedure as in Example 1 was carried out. Table 1 (Table 1-1 to Table 1-2) shows the formulation, analysis, and evaluation results of the resin composition.
• Example 8> The same procedure was carried out except that 0.038 parts by mass of n-dodecyl mercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer in Example 1 were changed to 0.10 parts by mass of n-dodecylmercaptan and 0.50 parts by mass of ⁇ -methylstyrene dimer. The same procedure as in Example 1 was carried out. Table 1 (Table 1-1 to Table 1-2) shows the formulation, analysis, and evaluation results of the resin composition.
• Example 9 The same procedure was carried out except that 0.038 parts by mass of n-dodecylmercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer in Example 1 were replaced with 0.01 parts by mass of n-dodecylmercaptan and 0.25 parts by mass of ⁇ -methylstyrene dimer. The same procedure as in Example 1 was carried out.
• Table 1 Table 1-1 to Table 1-2 shows the formulation, analysis, and evaluation results of the resin composition.
• Example 10 The same procedure was carried out except that 0.038 parts by mass of n-dodecyl mercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer in Example 1 were changed to 0.11 parts by mass of n-dodecylmercaptan and 0.05 parts by mass of ⁇ -methylstyrene dimer. The same procedure as in Example 1 was carried out. Table 1 (Table 1-1 to Table 1-2) shows the formulation, analysis, and evaluation results of the resin composition.
• Example 11 Example 1 except that 0.038 parts by mass of n-dodecyl mercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer were replaced with 0.11 parts by mass of n-dodecylmercaptan and no ⁇ -methylstyrene dimer. I did the same thing.
• Table 1 Table 1-1 to Table 1-2 shows the formulation, analysis, and evaluation results of the resin composition.
• Example 12 The same procedure was carried out except that 0.038 parts by mass of n-dodecylmercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer in Example 1 were changed to 0.02 parts by mass of n-dodecylmercaptan and 0.30 parts by mass of ⁇ -methylstyrene dimer. The same procedure as in Example 1 was carried out.
• Table 1 (Table 1-1 to Table 1-2) shows the formulation, analysis, and evaluation results of the resin composition.
• Example 13 The same procedure was carried out except that 0.038 parts by mass of n-dodecyl mercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer in Example 1 were changed to 0.02 parts by mass of n-dodecylmercaptan and 0.40 parts by mass of ⁇ -methylstyrene dimer.
• Table 1 Table 1-1 to Table 1-2 shows the formulation, analysis, and evaluation results of the resin composition.
• Example 14 The same procedure was carried out except that 0.038 parts by mass of n-dodecyl mercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer in Example 1 were replaced with 0.01 parts by mass of n-dodecylmercaptan and 0.20 parts by mass of ⁇ -methylstyrene dimer.
• Table 1 Table 1-1 to Table 1-2 shows the formulation, analysis, and evaluation results of the resin composition.
• Example 1 Example except that 0.038 parts by mass of n-dodecyl mercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer in Example 1 were replaced with 0.20 parts by mass of n-dodecylmercaptan, and ⁇ -methylstyrene dimer was not used. This was done in the same manner as in step 1.
• Table 2 shows the formulation, analysis, and evaluation results of the resin composition.
• Example 3 Example except that 0.038 parts by mass of n-dodecyl mercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer in Example 1 were replaced with 0.54 parts by mass of ⁇ -methylstyrene dimer, and n-dodecyl mercaptan was not used. This was done in the same manner as in step 1. Table 2 shows the formulation, analysis, and evaluation results of the resin composition.
• Example 4 Example except that 0.038 parts by mass of n-dodecyl mercaptan and 0.42 parts by mass of ⁇ -methylstyrene dimer in Example 1 were replaced with 0.60 parts by mass of t-dodecylmercaptan, and ⁇ -methylstyrene dimer was not used. This was done in the same manner as in step 1.
• Table 2 shows the formulation, analysis, and evaluation results of the resin composition.
• Example 6 Example except that 0.04 parts by mass of n-dodecyl mercaptan and 0.40 parts by mass of ⁇ -methylstyrene dimer in Example 6 were replaced with 0.25 parts by mass of t-dodecylmercaptan, and ⁇ -methylstyrene dimer was not used. This was done in the same manner as in step 6. Table 2 shows the formulation, analysis, and evaluation results of the resin composition.
• Example 7 The same procedure as in Example 1 was performed except that 79 parts by mass of styrene and 21 parts by mass of methyl methacrylate were used instead of 40 parts by mass of styrene and 60 parts by mass of methyl methacrylate in Example 12.
• Table 2 shows the formulation, analysis, and evaluation results of the resin composition.
• the resin compositions according to Examples have excellent safety and productivity in cosmetic and food packaging applications, injection moldability, and molded product performance. It is found to have excellent hue and light resistance, and low odor. Furthermore, since the amount of change in yellowness before and after irradiation with ultraviolet rays is small, it is suitable for use in environments where exposure to ultraviolet rays is possible. On the other hand, it can be seen that the resin compositions according to comparative examples are inferior in one or more of the following aspects: safety and productivity in cosmetic and food packaging applications, injection moldability, hue and light resistance of molded products, and odor.
• the degree of yellowness before irradiation with ultraviolet rays or the amount of change in the degree of yellowness before and after irradiation with ultraviolet rays is large, it is not suitable for use in an environment where exposure to ultraviolet rays is possible.
• the resin composition containing the copolymer P containing a styrene monomer unit and a (meth)acrylic acid ester monomer unit according to the present invention can be used for safety and productivity in cosmetics and food packaging applications, and for injection molding. It has excellent color and light resistance of molded products, and has little odor.
• the resin composition according to the present invention can be mixed with other resins to form a resin composition, and can be suitably used as an injection molded product for housings of home appliances or containers for foods, stationery, cosmetics, etc., and can be used for industrial purposes. Has availability.

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