Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
• • 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
• • 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
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

• the present invention relates to a resin composition in which a die is not attached to a die in an extrusion manufacturing process and a molded product thereof.
• Styrene resin is used in various fields such as personal computers, printers, copiers, and other office automation equipment, TVs, audios, and other home electric appliances due to its characteristics.
• polyester resins are widely used in various industrial applications such as films, sheets, tableware, and packaging containers because of their excellent mechanical properties.
• a polymer alloy of styrene-based resin and polylactic acid is usually manufactured by extrusion molding, but at that time, resin degradation products and undispersed additives cause mesiness at the die exit of the extruder.
• the generated nymph exists along with the strands and adheres to the pelletized pellets.This not only causes the appearance of the pellet itself to be poor, but also causes the colored points on the surface of the molded article after molding such as injection molding. Remains, and the appearance becomes poor, which is a problem.
• Patent Document 1 a method of adding a higher fatty acid amide or a higher fatty acid alkali metal salt to a styrene resin composition containing a polyphenylene ether is exemplified.
• Patent Document 1 a method of adding a higher fatty acid amide or a higher fatty acid alkali metal salt to a styrene resin composition containing a polyphenylene ether is exemplified (Patent Document 1).
• Patent Document 1 a method of adding a higher fatty acid amide or a higher fatty acid alkali metal salt to a styrene resin composition containing a polyphenylene ether
• the object of the present invention is to provide a resin composition in which the eyelids do not adhere to the die during the extrusion manufacturing process.
• the present invention is as follows. 1. A resin composition containing (A) a styrene-based resin and (B) a polyester-based resin, which is 0.1 part by mass with respect to a total of 100 parts by mass of the (A) styrene-based resin and the (B) polyester-based resin. A resin composition comprising the above (C) acrylic resin in an amount of 2 parts by mass or less. 2. (B) The resin composition according to the above item 1, wherein the polyester resin is polylactic acid. 3.
• the resin composition according to 1 or 2 above which is contained in an amount of not more than 10 parts by mass.
• the (C) acrylic resin has a weight average molecular weight Mw of 50,000 or more and 400,000 or less, and a monomer having an alkyl group having a carbon number of 1 or more and 20 or less, and a monomer capable of being copolymerized therewith. 4.
• the resin composition according to any one of 1 to 3 above which is a copolymer composed of a body. 5. Furthermore, the above (D) polyolefin wax is contained in an amount of 0.1 parts by mass or more and 1.5 parts by mass or less based on 100 parts by mass of the total of (A) styrene resin and (B) polyester resin. 5. The resin composition according to any one of 1 to 4. 6. A molded article comprising the resin composition according to any one of 1 to 5 above.
• the resin composition of the present invention is one in which a die that causes a defective molding appearance does not adhere to the die in the extrusion manufacturing process. Therefore, the molded product obtained by molding the resin composition of the present invention has an excellent appearance and can be effectively used in applications such as office automation equipment, home appliances, tableware, and packaging containers.
• the styrene resin (A) used in the present invention is obtained by polymerizing an aromatic vinyl compound monomer.
• aromatic vinyl compound-based monomer known ones such as styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and 2,4-dimethylstyrene can be used, but preferably It is styrene. These monomers may be used alone or in combination.
• monomers such as acrylonitrile, (meth)acrylic acid, (meth)acrylic acid ester, and maleic anhydride which are copolymerizable with these monomers can also be used to the extent that they do not impair the performance of the (A) styrene resin. If present, it may be added and polymerized.
• the styrene resin (A) may be rubber-modified by adding a conjugated diene rubber polymer as required.
• Conjugated diene rubber polymers used for rubber modification include polybutadiene, styrene-butadiene random or block copolymers, polyisoprene, polychloroprene, styrene-isoprene random, block or graft copolymers, ethylene-propylene rubber. , Ethylene-propylene-diene rubber and the like, but polybutadiene, styrene-butadiene random, block or graft copolymers are particularly preferable. Further, these may be partially hydrogenated.
• styrene resin examples include polystyrene (GPPS), rubber-modified polystyrene (HIPS), ABS resin (acrylonitrile-butadiene-styrene copolymer), AS resin (acrylonitrile-styrene copolymer), MS Examples thereof include resins (methyl methacrylate-styrene copolymer), AAS resins (acrylonitrile-acrylic rubber-styrene copolymer), AES resins (acrylonitrile-ethylene propylene-styrene copolymer) and the like.
• HIPS is particularly preferable because it can increase the impact resistance of the resin composition.
• the molecular weight of the matrix portion of HIPS is not particularly limited, but the reduced viscosity ( ⁇ sp/C) is preferably 0.5 or more and 1.0 or less. When it is 0.5 or more, the molten strand of the resin is less likely to be broken, which is advantageous for stable production, which is preferable. Further, when it is 1.0 or less, the fluidity of the molten resin can be secured, which is preferable.
• the content of the rubber-like polymer in HIPS is not particularly limited, but is preferably 3% by mass or more and 10% by mass or less. When the content of the rubber-like polymer is in this range, the molded article has a good balance between impact resistance and rigidity, which is preferable.
• polyester resin (B) used in the present invention is a general term for polymers having an ester bond, which are obtained by polymerizing a polycarboxylic acid and a polyalcohol.
• the polyester resin (B) can be obtained, for example, by polymerization from a dicarboxylic acid and a diol, and examples of such a polyester resin include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, and Examples thereof include polyhexamethylene terephthalate and polyhexamethylene naphthalate, but the present invention is not limited thereto.
• dicarboxylic acid component examples include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid.
• aromatic dicarboxylic acids such as 4,4′-diphenyl ether dicarboxylic acid and 4,4′-diphenyl sulfone dicarboxylic acid.
• aliphatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, dimer acid, dodecanedioic acid, cyclohexanedicarboxylic acid, and ester derivatives thereof can be mentioned.
• carboxylic acid components may be used alone or in combination of two or more, and further, an oxy acid such as hydroxybenzoic acid may be partially copolymerized.
• diol component examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane.
• Diol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2-bis(4 -Hydroxyethoxyphenyl)propane, isosorbate, spiroglycol and the like can be mentioned.
• the polyester resin (B) can be obtained by polymerizing a monomer having both a carboxylic acid and an alcohol with a single compound, and such a polyester resin includes polylactic acid.
• polylactic acid is preferred from the viewpoint of carbon neutrality.
• polylactic acid poly(L-lactic acid) is used. From the viewpoint of reducing carbon dioxide emissions, plant-derived raw materials are preferable.
• poly(L-lactic acid) its crystallization rate varies depending on the ratio of D-lactic acid component contained as a monomer component.
• poly(L-lactic acid) composed only of L-lactic acid is preferable, and when the D-lactic acid component is contained, the ratio is 5.0. It is preferably not more than mol %. It is particularly preferably 1.5 mol% or less.
• the weight average molecular weight (Mw) of polylactic acid is preferably 50,000 or more and 400,000 or less, and particularly preferably 100,000 or more and 300,000 or less.
• the ratio of (A) styrene resin to (B) polyester resin is not particularly limited, but when the total of (A) styrene resin and (B) polyester resin is 100 parts by mass, (A) ) It is preferable that the styrene resin is 55 parts by mass or more and 90 parts by mass or less, and the polyester resin (B) is 10 parts by mass or more and 45 parts by mass or less. It is preferable that the ratio of the polyester resin (B) is within this range, because the environmental load reducing effect and the price competitiveness can both be achieved.
• the (C) acrylic resin refers to a polymer obtained by polymerizing an acrylic monomer or the like.
• the acrylic resin (C) has excellent compatibility with the polyester resin (B) and reduces friction between the resin composition and the die outlet, and therefore the resin composition containing the polyester resin (B).
• (C) contains an acrylic resin, the effect of preventing eyebrow can be obtained.
• the content of the (C) acrylic resin is 0.1 parts by mass or more and 2 parts by mass or less with respect to a total of 100 parts by mass of the (A) styrene resin and the (B) polyester resin, from the viewpoint of the effect of suppressing the body damage. Is. (C) If the content of the acrylic resin exceeds 2 parts by mass, the acrylic resin bleeds out on the surface of the strand during extrusion production, and the acrylic resin itself transferred and adhered to the die outlet portion becomes a source of mesiness. Is.
• the type of the acrylic monomer that constitutes the acrylic resin (C) is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, Acrylate monomers such as benzyl acrylate, cyclohexyl acrylate, phenyl acrylate and chloroethyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, phenyl
• a homopolymer of a methacrylate monomer such as methacrylate or chloroethyl methacrylate, or a copolymer obtained by copolymerizing two or more of these monomers
• the acrylic resin (C) may be a resin obtained by adding a vinyl monomer copolymerizable with the above acrylic monomers in addition to these acrylic monomers, as long as the effects of the present invention are not impaired.
• a vinyl monomer copolymerizable with the above acrylic monomers in addition to these acrylic monomers, as long as the effects of the present invention are not impaired.
• ⁇ -olefin Polymers obtained by adding monomers such as vinyl aromatics, unsaturated nitriles, unsaturated carboxylic acids or their esters, and polyunsaturated compounds such as ethylene glycol di(meth)acrylate may also be used.
• the (C) acrylic resin is preferably a high molecular weight polymer.
• the polystyrene-equivalent weight average molecular weight Mw measured by GPC is preferably 50,000 or more and 400,000 or less. More preferably, it is 100,000 or more and 300,000 or less.
• the (C) acrylic resin is more preferable as it has a higher performance as a lubricant from the viewpoint of the effect of reducing the ink drop. That is, it is preferably a copolymer composed of an acrylic monomer having a chemical structure capable of further reducing friction with the die outlet and the like, and a monomer copolymerizable therewith.
• the acrylic monomer having a chemical structure capable of reducing friction is a monomer having an alkyl group having 1 to 20 carbon atoms, preferably alkyl methacrylate or alkyl acrylate.
• alkyl methacrylate or alkyl acrylate examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and the like. It is preferable to use at least one or more of these.
• Examples of the (C) acrylic resin that satisfies such conditions include “Metablene (registered trademark) L-1000” and “Metablene (registered trademark) P-700” manufactured by Mitsubishi Chemical Corporation.
• the resin composition of the present invention may contain (D) a polyolefin wax for the purpose of further enhancing the effect of (C) acrylic resin to suppress the occurrence of the eye damage.
• a polyolefin wax for the purpose of further enhancing the effect of (C) acrylic resin to suppress the occurrence of the eye damage.
• the polyolefin wax that can be used in the present invention include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, and paraffin wax.
• the content of the (D) polyolefin wax is preferably 0.1 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the total of (A) styrene resin and (B) polyester resin. .. Within this range, it is possible to sufficiently exert the effect of enhancing the suppression of the eye damage by the combined use with the (C) acrylic resin, and to suppress the amount of gas generated during processing.
• additives within the range not impairing the object of the present invention for example, plasticizers, spreading agents, solvents, UV absorbers, antioxidants, antioxidants, light stabilizers, stabilizers, antistatic agents, colorants, Dyes and pigments, fillers, anti-coloring agents, reinforcing agents, compatibilizers, crystallization accelerators, flame retardants, flame retarding aids, etc. can be added.
• MBS as a reinforcing agent
• talc as a crystallization accelerator
• liquid paraffin as a spreading agent
• MBS is a copolymer of methyl methacrylate, butadiene, and styrene, and is well compatible with any of (B) polyester resin, (A) styrene resin, (C) acrylic resin, and the resin composition of the present invention. It is preferable because the impact resistance can be efficiently reinforced.
• Talc is preferred because it can promote crystallization of the (B) polyester resin in the present invention and improve the mechanical strength of the resin composition.
• Liquid paraffin is a saturated hydrocarbon purified by removing impurities such as aromatic hydrocarbons and sulfur compounds contained in the lubricating oil fraction of petroleum with sulfuric anhydride or fuming sulfuric acid, and when mixing the resin composition of the present invention.
• impurities such as aromatic hydrocarbons and sulfur compounds contained in the lubricating oil fraction of petroleum with sulfuric anhydride or fuming sulfuric acid, and when mixing the resin composition of the present invention.
• impurities such as aromatic hydrocarbons and sulfur compounds contained in the lubricating oil fraction of petroleum with sulfuric anhydride or fuming sulfuric acid
• the method of adding the above-mentioned additives is not particularly limited, and any known method may be used.
• a method of adding (A) a styrene-based resin or (B) a polyester-based resin in a raw material charging step, a polymerization step, or a finishing step, or a step of mixing a resin composition using an extruder or a molding machine.
• the method of adding in can be applied.
• the method for producing the resin composition of the present invention is not particularly limited, and known mixing techniques can be applied.
• various raw materials are mixed in advance using a mixing device such as a mixer-type mixer, a V-type blender, and a tumbler-type mixer, and the mixture is melt-kneaded to produce a uniform resin composition.
• the melt-kneading device is also not particularly limited, but examples thereof include a Banbury mixer, a kneader, a roll, a single-screw extruder, a special single-screw extruder, and a twin-screw extruder.
• the molding method for obtaining a molded product from the resin composition of the present invention is not particularly limited, and calendar molding, hollow molding, extrusion foam molding, profile extrusion molding, laminate molding, inflation molding, T die film molding, sheet molding, vacuum molding.
• Known molding methods such as extrusion molding methods such as pressure molding and injection molding methods such as injection molding, RIM molding and injection foam molding can be preferably used, but injection molding or sheet molding is preferable.
• the materials used in the examples and comparative examples are as follows. ⁇ material ⁇ (A) Styrene-based resin Rubber-modified impact-resistant polystyrene resin (rubber-like polymer is polybutadiene rubber, reduced viscosity of matrix part is 0.70 dl/g, rubber-like polymer content is 9.2% by mass) (B) Polyester resin Polylactic acid: “REVODE 190” manufactured by Zhejiang Hisun Biomaterials Co., Ltd.

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• Compositions Of Macromolecular Compounds (AREA)

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• 2019
  • 2019-12-20 CN CN201980068616.3A patent/CN112888736B/zh active Active
  • 2019-12-20 JP JP2020563184A patent/JP7426344B2/ja active Active
  • 2019-12-20 WO PCT/JP2019/049983 patent/WO2020137843A1/ja not_active Ceased

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