WO2022045003A1 - Resin composition, molded article and cosmetics container - Google Patents

Resin composition, molded article and cosmetics container Download PDF

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Publication number
WO2022045003A1
WO2022045003A1 PCT/JP2021/030601 JP2021030601W WO2022045003A1 WO 2022045003 A1 WO2022045003 A1 WO 2022045003A1 JP 2021030601 W JP2021030601 W JP 2021030601W WO 2022045003 A1 WO2022045003 A1 WO 2022045003A1
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Prior art keywords
mass
resin
antioxidant
monomer
resin composition
Prior art date
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PCT/JP2021/030601
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French (fr)
Japanese (ja)
Inventor
亘 渡辺
広平 西野
Original Assignee
デンカ株式会社
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Publication date
Application filed by デンカ株式会社 filed Critical デンカ株式会社
Priority to JP2022544546A priority Critical patent/JPWO2022045003A1/ja
Priority to KR1020237010106A priority patent/KR20230058105A/en
Priority to CN202180053442.0A priority patent/CN116096812A/en
Publication of WO2022045003A1 publication Critical patent/WO2022045003A1/en

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Classifications

    • 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
    • C08K5/13—Phenols; Phenolates
    • A—HUMAN NECESSITIES
    • A45—HAND OR TRAVELLING ARTICLES
    • A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
    • A45D33/00—Containers or accessories specially adapted for handling powdery toiletry or cosmetic substances
    • 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
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • 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
    • C08L25/12—Copolymers of styrene with unsaturated nitriles

Definitions

  • the present invention relates to a resin composition containing a copolymer of an aromatic vinyl monomer and a cyano-based monomer, a molded product thereof, and a cosmetic container.
  • Copolymers containing aromatic vinyl monomers and cyano monomers are used in a wide range of fields because they have various properties such as excellent chemical resistance, rigidity, and moldability.
  • a thermoplastic copolymer containing a cyano-based monomer as one component tends to cause hue deterioration due to a high temperature during molding. Therefore, there is a problem that the actual molded product has a low clear feeling and becomes dull.
  • Patent Document 1 a method of using an initiator having a low hydrogen extraction ability during polymerization (Patent Document 1) and an antioxidant having two phenol moieties in the molecule are added at the polymerization stage of a polymerization rate of 60% or more.
  • Patent Document 2 A method of using t-amylperoxyesters containing no aromatic ring when copolymerizing an acrylonitrile monomer and a styrene-based monomer (Patent Document 3) have been proposed. ing.
  • Japanese Unexamined Patent Publication No. 4-146908 Japanese Unexamined Patent Publication No. 4-146907 Japanese Unexamined Patent Publication No. 8-301913
  • an aromatic vinyl monomer having undergone molding processing can have chemical resistance and high transparency and high color tone. It is an object of the present invention to provide a resin containing a copolymer of a cyano-based monomer and a cyano-based monomer.
  • the resin composition according to the present invention contains a resin (A) containing a copolymer of an aromatic vinyl monomer and a cyano-based monomer, and a total of 3 phenol moieties in the molecule. It is a resin composition containing one or more antioxidants (B) and a phosphorus-based antioxidant (C).
  • the total content of the antioxidant (B) and the antioxidant (C) is 0.01 with respect to 100 parts by mass of the resin (A). ⁇ 0.5 parts by mass.
  • the copolymer of the aromatic vinyl monomer and the cyano monomer is the total of the aromatic vinyl monomer and the cyano monomer. Is 100% by mass, it contains 40 to 95% by mass of the aromatic vinyl monomer unit and 5 to 60% by mass of the cyano-based monomer unit.
  • the resin composition according to the present invention is a molded product according to another embodiment, characterized in that it is molded from the resin composition according to any one of (1) to (3). ..
  • the resin composition according to the present invention is a cosmetic container, which is formed from the resin composition according to any one of (1) to (3) in another embodiment. ..
  • a resin having chemical resistance, high transparency and high color tone is provided.
  • This resin composition can be used in cosmetic containers and the like, which require high design.
  • the resin composition of the present invention comprises a resin (A) containing a copolymer of an aromatic vinyl monomer and a cyano-based monomer, and an oxidation having a total of three or more phenol or sulfide moieties in the molecule. It contains an inhibitor (B) and a phosphorus-based antioxidant (C).
  • the resin (A) in the present invention is a resin containing a copolymer of an aromatic vinyl monomer and a cyano-based monomer as a main component.
  • the content of the copolymer of the aromatic vinyl monomer and the cyano-based monomer in 100% by mass of the resin (A) is, for example, 50% by mass or more.
  • the content of the copolymer in the resin (A) is preferably 80% by mass or more, more preferably 80% by mass or more, and further preferably the resin (A) is substantially. It consists only of a copolymer of an aromatic vinyl monomer and a cyano-based monomer.
  • the aromatic vinyl monomer is not particularly limited, but is substituted styrene having a substituent such as styrene, ⁇ -methylstyrene, p-methylstyrene, 3,5-dimethylstyrene, 4-methoxystyrene, 2-hydroxystyrene, ⁇ -bromstyrene, 2 Examples thereof include halogenated styrene such as 4-dichlorostyrene and 1-vinylnaphthalene.
  • the cyano-based monomer is not particularly limited, and examples thereof include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, and ⁇ -ethylacrylonitrile.
  • the antioxidant (B) of the present invention has a total of three or more phenol sites or sulfide sites in the molecule in the basic skeleton. If the number is two or less, the antioxidant capacity is not sufficient, and the resin deteriorates during molding, resulting in deterioration of hue.
  • the antioxidant (B) that can be used in the present invention is specifically 1,3,5, tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5, triazine-. 2,4,6 (1H, 3H, 5H) -trione, 4,4', 4'-(1-methylpropanol-3-iriden) tris (6-tert-butyl-m-cresol), 1, Trisphenols such as 3,5, Tris (3,5-di-tert-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene, pentaerythrityl-tetrakis [3- (3,5-) Tetraphenols such as tert-butyl-4-hydroxyphenyl) propionate], 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, 2 , 4-Bis (octylthio)
  • the phosphorus-based antioxidant (C) of the present invention is, for example, trisnonylphenylphosphite, triphenylphosphite, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis ( 2,4-di-t-butylphenylphosphite), cyclic neopentanetetraylbis (octadecylphosfite), cyclic neopentanetetraylbis (nonylphenylphosphite), tris (mixed, mono and dinonyl) Phenyl) phosphite, 4,4'-isopropylidenediphenolalkyl (C12-C15) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, pheny
  • the total content of the antioxidant (B) and the phosphorus-based antioxidant (C) in the present embodiment is preferably 0.01 to 0.50 parts by mass with respect to 100 parts by mass of the resin (A). , 0.05 to 0.40 parts by mass, more preferably 0.10 to 0.30 parts by mass. Specifically, for example, 0.01, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, or 0.50. It is a part by mass and may be in the range between any two of the numerical values exemplified here. If the total content of the antioxidant (B) and the phosphorus-based antioxidant (C) exceeds 0.50 parts by mass, the heat resistance of the obtained resin composition may decrease. Further, when the total content of the antioxidant (B) and the phosphorus-based antioxidant (C) is less than 0.01 parts by mass, deterioration of the hue of the obtained molded product cannot be suppressed.
  • the mixing ratio of the antioxidant (B) and the phosphorus-based antioxidant (C) is not particularly limited.
  • the mass ratio of the antioxidant (B) to the phosphorus-based antioxidant (C) is preferably 5/1 to 1/5, more preferably 4/1 to 1/4. Specifically, for example, it is 5/1, 4/1, 3/1, 2/1, 1/1, 1/2, 1/3, 1/4, or 1/5, and the numerical values exemplified here. It may be within the range between any two of the above.
  • Examples of the method of adding the antioxidant (B) and the phosphorus-based antioxidant (C) include a method of adding and mixing the resin (A) in the polymerization step, the devolatilization step, and the granulation step, and an extruder or injection during molding. Examples thereof include a method of adding and mixing with a molding machine and the like, and the present invention is not particularly limited.
  • the content ratio of the aromatic vinyl monomer and the cyano-based monomer in the resin (A) can be arbitrarily selected, but the amount of the aromatic vinyl monomer contained in the 100% by mass copolymer is , 40% by mass to 95% by mass, more preferably 50% by mass to 85% by mass, still more preferably 70% by mass to 85% by mass. Specifically, for example, it is 40, 50, 60, 65, 70, 75, 80, 85, 90, or 95% by mass, and may be within the range between any two of the numerical values exemplified here. ..
  • the amount of the cyano-based monomer contained in the 100% by mass of the copolymer is preferably 5% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and further preferably 15% by mass to 70% by mass. %. Specifically, it is, for example, 5, 10, 15, 20, 35, 40, 50, or 60% by mass, and may be within the range between any two of the numerical values exemplified here. If each monomer is out of the above composition range, it is difficult to achieve the appearance, chemical resistance, transparency, mechanical properties, etc. of the molded product, which is the object of the present invention.
  • a suspension polymerization method, a solution polymerization method, a bulk polymerization method or the like can be used as a method for producing the resin (A) containing a copolymer of an aromatic vinyl monomer and a cyano-based monomer in the present invention.
  • a solution polymerization method or a bulk polymerization method is preferably used for the purpose of preventing the dispersant from being mixed into the resin.
  • the resin (A) may be copolymerized with a copolymerizable monomer other than the cyano monomer and the aromatic vinyl monomer as long as the effect of the present invention is not impaired.
  • a copolymerizable monomer other than the cyano monomer and the aromatic vinyl monomer examples include acrylic acid esters such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate and butyl acrylate, and acrylic acid.
  • Examples thereof include unsaturated carboxylic acids such as methacrylic acid, maleic anhydride and itaconic acid or their anhydrides, maleimide compounds such as N-phenylmaleimide and N-cyclohexylmaleimide, and ethyl acrylate and butyl acrylate are particularly preferable. It is also possible to mix and use more than seeds.
  • the content of these monomers is 0% by mass to 20% by mass when the total of the cyano-based monomer, the aromatic vinyl monomer and the monomer copolymerizable with these is 100% by mass. It is preferably 0% by weight to 10% by weight.
  • the resin (A) for example, t-dodecyl mercaptan, n-dodecyl mercaptan, unsaturated dimer of ⁇ -methylstyrene, terpinolene, octyl thioglycolate and the like may be used as the molecular weight modifier.
  • the resin composition of the present invention may contain mineral oil as long as the effects of the present invention are not impaired. It also contains internal lubricants such as stearic acid and ethylene bisstearylamide, and additives such as sulfur-based antioxidants, lactone-based antioxidants, ultraviolet absorbers, hindered amine-based stabilizers, antistatic agents, and external lubricants. It may be.
  • internal lubricants such as stearic acid and ethylene bisstearylamide
  • additives such as sulfur-based antioxidants, lactone-based antioxidants, ultraviolet absorbers, hindered amine-based stabilizers, antistatic agents, and external lubricants. It may be.
  • the ultraviolet absorber has a function of suppressing deterioration and coloring due to ultraviolet rays, and is, for example, benzophenone-based, benzotriazole-based, triazine-based, benzoate-based, salicylate-based, cyanoacrylate-based, oxalic acid anilide-based, and malonic acid ester.
  • ultraviolet absorbers such as those of the system and those of the formamidine system. These can be used alone or in combination of two or more, and a light stabilizer such as hindered amine may be used in combination.
  • the resin composition of the present invention may contain various dyes and pigments as long as the effects of the present invention are not impaired.
  • coumarin fluorescent dye benzopyran fluorescent dye, perylene fluorescent dye, anthracinone fluorescent dye, thioindigo fluorescent dye, xanthene fluorescent dye, xantone fluorescent dye, thioxanthene fluorescent dye, thioxanthone fluorescent dye, thiadin.
  • examples thereof include a fluorescent dye and a diaminostilben fluorescent dye.
  • the content of the above dyeing pigment is preferably 0.00001 to 1 part by mass, preferably 0.00003 to 1 part by mass based on a total of 100 parts by mass of the resin (A), the antioxidant (B), and the antioxidant (C). 0.3 parts by mass is more preferable.
  • a known molding processing technique can be used, and examples thereof include injection molding, extrusion molding, sheet molding, and press molding.
  • the molded product obtained by molding the resin composition according to the present invention can be processed into a cosmetic container that requires particularly high design. Further, the resin composition according to the present invention is preferably used alone or as a mixed resin blended with other resins such as ABS resin and PC resin.
  • the supply liquid supplied to the 50 L reaction vessel is 70 parts by mass of styrene, 15 parts by mass of acrylonitrile, 15 parts by mass of ethylbenzene, 0.02 parts by mass of t-butylperoxyisopropylcarbonate as a polymerization initiator, and n-dodecyl as a chain transfer agent.
  • Mercaptan was prepared to be 0.01 parts by mass. After bubbling this supply liquid with nitrogen gas, it is continuously supplied to the reaction tank at a rate of 10.8 L / hour so that the polymerization temperature can be maintained at 145 ° C. and the filling rate of the reaction liquid in the reaction tank can be maintained at 70 vol%.
  • the reaction solution was continuously withdrawn in the same amount as the supply liquid.
  • the extracted reaction solution was introduced into a volatile matter removing device maintained at a high vacuum of 250 ° C. and 10 mmHg, the unreacted monomer and the organic solvent were degassed and recovered, and the copolymer was recovered as pellets.
  • the supply liquid supplied to the 50 L reaction vessel was 58 parts by mass of styrene, 22 parts by mass of acrylonitrile, 20 parts by mass of ethylbenzene, 0.02 parts by mass of t-butylperoxyisopropylcarbonate as a polymerization initiator, and n-dodecyl as a chain transfer agent.
  • Mercaptan was prepared to be 0.04 parts by mass. After bubbling this supply liquid with nitrogen gas, it is continuously supplied to the reaction tank at a rate of 8 L / hour so that the polymerization temperature can be maintained at 145 ° C. and the filling rate of the reaction liquid in the reaction tank can be maintained at 60 vol%.
  • reaction solution was continuously withdrawn.
  • the extracted reaction solution was introduced into a volatile matter removing device maintained at a high vacuum of 250 ° C. and 10 mmHg, the unreacted monomer and the organic solvent were degassed and recovered, and the copolymer was recovered as pellets.
  • the supply liquid supplied to the reaction vessel of 50 L was 49 parts by mass of styrene, 29 parts by mass of acrylonitrile, 23 parts by mass of ethylbenzene, 0.02 part by mass of t-butylperoxyisopropylcarbonate as a polymerization initiator, and n-dodecyl as a chain transfer agent.
  • Mercaptan was prepared to be 0.12 parts by mass. After bubbling this supply liquid with nitrogen gas, it is continuously supplied to the reaction tank at a rate of 9.8 L / hour so that the polymerization temperature can be maintained at 145 ° C. and the filling rate of the reaction liquid in the reaction tank can be maintained at 80 vol%.
  • the reaction solution was continuously withdrawn in the same amount as the supply liquid.
  • the extracted reaction solution was introduced into a volatile matter removing device maintained at a high vacuum of 250 ° C. and 10 mmHg, the unreacted monomer and the organic solvent were degassed and recovered, and the copolymer was recovered as pellets.
  • this supply liquid After bubbling this supply liquid with nitrogen gas, it is continuously supplied to the reaction tank at a rate of 9.8 L / hour so that the polymerization temperature can be maintained at 145 ° C. and the filling rate of the reaction liquid in the reaction tank can be maintained at 75 vol%.
  • the reaction solution was continuously withdrawn in the same amount as the supply liquid.
  • the extracted reaction solution was introduced into a volatile matter removing device maintained at a high vacuum of 250 ° C. and 10 mmHg, the unreacted monomer and the organic solvent were degassed and recovered, and the copolymer was recovered as pellets.
  • the supply liquid supplied to the 50 L reaction vessel was 84 parts by mass of styrene, 16 parts by mass of ethylbenzene, 0.02 parts by mass of t-butylperoxyisopropyl carbonate as a polymerization initiator, and 0.12 parts of n-dodecyl mercaptan as a chain transfer agent. It was prepared to be parts by mass. After bubbling this supply liquid with nitrogen gas, it is continuously supplied to the reaction tank at a rate of 9.8 L / hour so that the polymerization temperature can be maintained at 145 ° C. and the filling rate of the reaction liquid in the reaction tank can be maintained at 80 vol%.
  • the reaction solution was continuously withdrawn in the same amount as the supply liquid.
  • the extracted reaction solution was introduced into a volatile matter removing device maintained at a high vacuum of 250 ° C. and 10 mmHg, the unreacted monomer and the organic solvent were degassed and recovered, and the copolymer was recovered as pellets.
  • composition analysis in the resin was measured according to JIS K6451-2: 2016.
  • the sample amount was 0.2 g
  • the decomposition temperature was 400 ° C.
  • the titration standard solution was a sulfuric acid standard aqueous solution.
  • B-1 Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010 manufactured by BASF Japan Ltd.)
  • B-2 4,4', 4''- (1-methylpropanol-3-iriden) Tris (6-tert-butyl-m-cresol) (ADEKA CORPORATION ADEKA STAB AO-30)
  • B-3 1,3,5, Tris (3,5-di-tert-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene (Irganox 1330 manufactured by BASF Japan Ltd.)
  • B-4 4,6-bis (octylthiomethyl) -o-cresol (Irganox1520 manufactured by BASF Japan Ltd.)
  • B-5 2,4-bis (octylthio) -6- (4-hydroxy-3,
  • C ⁇ Phosphorus-based antioxidant (C)> The following were used as phosphorus-based antioxidants.
  • C-1 Tris (2,4-di-tert-butylphenyl) phosphite (ADEKA CORPORATION ADEKA STAB 2112)
  • C-2 Tetra-C12-15-alkyl (Propane-2,2-diylbis (4,1-phenylene)) Bis (Phosfite) (ADEKA STAB 1500 manufactured by ADEKA Corporation)
  • a plate-shaped molded product having a thickness of 127 ⁇ 127 ⁇ 3 mm was molded at a molding temperature of 230 ° C. by an injection molding machine (J140AD-180H, manufactured by Nippon Steel Co., Ltd.).
  • J140AD-180H manufactured by Nippon Steel Co., Ltd.
  • a test piece having a thickness of 115 ⁇ 85 ⁇ 3 mm was cut out from the plate-shaped molded product, and the end face was polished by buffing to prepare a plate-shaped molded product having a mirror surface on the end face.
  • the incident light having a size of 20 ⁇ 1.6 mm and a spreading angle of 0 ° has a light path length of 115 mm and 350 nm.
  • the spectral transmittance of about 800 nm was measured, and the YI value at a field of view of 2 ° in the wavelength C light source was calculated according to JIS K7105. Further, the transmittance indicates the total light transmittance in the range of 430 to 700 nm. The results are shown in Tables 1 to 3.
  • the test piece was manufactured by press-molding each pellet at 260 ° C. to a thickness of 4 mm and cutting it into a 50 mm ⁇ 50 mm square in order to eliminate the influence of molding strain. After soaking in each chemical set at 40 ° C. for 14 days, they were classified as follows based on the change in weight and appearance. As the chemicals, a 5% aqueous urea solution and salad oil were used. ⁇ : Almost no effect is observed, ⁇ : Slight cloudiness or discoloration is observed, ⁇ : Slight cracking or crazing occurs, ⁇ : Dissolution or large effect
  • Examples 1 to 14 including (C) had chemical resistance and were excellent in transparency and YI value.
  • Comparative Examples 1 to 5 using an antioxidant having two or less phenol sites in the molecule, Comparative Example 6 not using an antioxidant, and a phosphorus-based antioxidant (C) were not used in combination.
  • the transmittance was low and the YI value was high, resulting in inferior hue.
  • Comparative Example 8 using a resin containing no cyano-based monomer component was excellent in transparency and hue, but the chemical resistance was significantly deteriorated.
  • the resin composition and molded product of the present invention have excellent chemical resistance and hue and transparency, they can be suitably used for applications requiring high design and chemical resistance.
  • Specific examples thereof include cosmetic containers, food containers, and miscellaneous goods such as lighters.

Abstract

The present invention addresses the problem of providing, as a material for cosmetics containers and the like for which especially good design properties are required, a resin that contains: a copolymer of a cyano monomer; and an aromatic vinyl monomer having chemical resistance and having excellent transparency and color tone . The present invention provides a resin composition containing: a resin (A) that includes a copolymer of an aromatic vinyl monomer and a cyano monomer; an antioxidant (B) having a total of three or more phenol moieties within a molecule; and a phosphorous antioxidant (C).

Description

樹脂組成物、成形体及び化粧品容器Resin composition, molded article and cosmetic container
　本発明は芳香族ビニル単量体とシアノ系単量体の共重合体を含有する樹脂組成物、その成形体及び化粧品容器に関するものである。 The present invention relates to a resin composition containing a copolymer of an aromatic vinyl monomer and a cyano-based monomer, a molded product thereof, and a cosmetic container.
　芳香族ビニル単量体とシアノ系単量体を含有する共重合体はその優れた耐薬品性、剛性、成形性などの諸性質を有することから、幅広い分野で使用されている。しかしながら、シアノ系単量体を一成分とする熱可塑性共重合体は、成形加工時の高温により色相劣化を起こしやすい。そのため、実際の成形体のクリア感が低く、くすんでしまうという課題があった。 Copolymers containing aromatic vinyl monomers and cyano monomers are used in a wide range of fields because they have various properties such as excellent chemical resistance, rigidity, and moldability. However, a thermoplastic copolymer containing a cyano-based monomer as one component tends to cause hue deterioration due to a high temperature during molding. Therefore, there is a problem that the actual molded product has a low clear feeling and becomes dull.
　かかる課題を解決すべく、重合時に水素引き抜き能が低い開始剤を使用する方法（特許文献１）やフェノール部位を分子内に二つ有する酸化防止剤を重合率６０％以上の重合段階で添加する方法（特許文献２）、ならびにアクリロニトリル単量体とスチレン系単量体とを共重合する際に、芳香環を含まないｔ－アミルパーオキシエステル類を使用する方法（特許文献３）が提案されている。 In order to solve this problem, a method of using an initiator having a low hydrogen extraction ability during polymerization (Patent Document 1) and an antioxidant having two phenol moieties in the molecule are added at the polymerization stage of a polymerization rate of 60% or more. A method (Patent Document 2) and a method of using t-amylperoxyesters containing no aromatic ring when copolymerizing an acrylonitrile monomer and a styrene-based monomer (Patent Document 3) have been proposed. ing.
特開平４－１４６９０８号公報Japanese Unexamined Patent Publication No. 4-146908 特開平４－１４６９０７号公報Japanese Unexamined Patent Publication No. 4-146907 特開平８－３０１９１３号公報Japanese Unexamined Patent Publication No. 8-301913
　しかし、これらの方法では十分色相を改善できているとはいえず、特に高いデザイン性を求められる化粧品容器などの原料としては、透明性や色調などの点で必ずしも満足すべきレベルの樹脂が得られるとは言いがたい。 However, it cannot be said that these methods can sufficiently improve the hue, and as a raw material for cosmetic containers, which require particularly high design, a resin having a level that is always satisfactory in terms of transparency and color tone can be obtained. It is hard to say that it will be done.
　そこで本発明は、特に高いデザイン性を求められる化粧品容器などの原料として、成形加工を経た後の成形品が耐薬品性をもち高い透明性や高色調を有し得る、芳香族ビニル単量体とシアノ系単量体の共重合体を含有する樹脂を提供することを課題とする。 Therefore, in the present invention, as a raw material for cosmetic containers and the like, which are particularly required to have high designability, an aromatic vinyl monomer having undergone molding processing can have chemical resistance and high transparency and high color tone. It is an object of the present invention to provide a resin containing a copolymer of a cyano-based monomer and a cyano-based monomer.
　本発明者等は、上記の課題を解決すべく鋭意研究を重ねた結果、以下の実施形態が有効であることを見出した。
　（１）本発明に係る樹脂組成物は一実施形態において、芳香族ビニル単量体とシアノ系単量体の共重合体を含有する樹脂（Ａ）と、フェノール部位を分子内に合計で３つ以上有する酸化防止剤（Ｂ）と、リン系の酸化防止剤（Ｃ）とを含有する樹脂組成物である。 As a result of diligent research to solve the above problems, the present inventors have found that the following embodiments are effective.
(1) In one embodiment, the resin composition according to the present invention contains a resin (A) containing a copolymer of an aromatic vinyl monomer and a cyano-based monomer, and a total of 3 phenol moieties in the molecule. It is a resin composition containing one or more antioxidants (B) and a phosphorus-based antioxidant (C).
　（２）本発明に係る樹脂組成物は別の一実施形態において、酸化防止剤（Ｂ）と酸化防止剤（Ｃ）の合計含有量が、樹脂（Ａ）１００質量部に対して０.０１～０.５質量部である。 (2) In another embodiment of the resin composition according to the present invention, the total content of the antioxidant (B) and the antioxidant (C) is 0.01 with respect to 100 parts by mass of the resin (A). ~ 0.5 parts by mass.
　（３）本発明に係る樹脂組成物は別の一実施形態において、芳香族ビニル単量体とシアノ系単量体の共重合体は、芳香族ビニル単量体とシアノ系単量体の合計を１００質量％とした場合に、前記芳香族ビニル単量体単位４０～９５質量％と、前記シアノ系単量体単位５～６０質量％を含有する。 (3) In another embodiment of the resin composition according to the present invention, the copolymer of the aromatic vinyl monomer and the cyano monomer is the total of the aromatic vinyl monomer and the cyano monomer. Is 100% by mass, it contains 40 to 95% by mass of the aromatic vinyl monomer unit and 5 to 60% by mass of the cyano-based monomer unit.
　（４）本発明に係る樹脂組成物は別の一実施形態において、（１）～（３）のいずれか１つに記載の樹脂組成物から成形されてなることを特徴とする成形体である。 (4) The resin composition according to the present invention is a molded product according to another embodiment, characterized in that it is molded from the resin composition according to any one of (1) to (3). ..
　（５）本発明に係る樹脂組成物は別の一実施形態において、（１）～（３）のいずれか１つに記載の樹脂組成物から成形されてなることを特徴とする化粧品容器である。 (5) The resin composition according to the present invention is a cosmetic container, which is formed from the resin composition according to any one of (1) to (3) in another embodiment. ..
　本発明によれば、耐薬品性をもち、かつ高い透明性や高色調を有する樹脂が提供される。本樹脂組成物は高いデザイン性を求められる化粧品容器等に使用することができる。 According to the present invention, a resin having chemical resistance, high transparency and high color tone is provided. This resin composition can be used in cosmetic containers and the like, which require high design.
　本発明の樹脂組成物は、芳香族ビニル単量体とシアノ系単量体の共重合体を含有する樹脂（Ａ）と、にフェノール部位またはスルフィド部位を分子内に合計で３つ以上有する酸化防止剤（Ｂ）とリン系の酸化防止剤（Ｃ）を含有する。
　本発明における樹脂（Ａ）は、芳香族ビニル単量体とシアノ系単量体の共重合体を主成分とする樹脂である。樹脂（Ａ）は、樹脂（Ａ）１００質量％中の芳香族ビニル単量体とシアノ系単量体の共重合体の含有量が、例えば５０質量％以上である。一態様においては、樹脂（Ａ）中の共重合体の含有量は、好ましくは８０質量％以上であり、より好ましくは８０質量％以上であり、さらに好ましくは、樹脂（Ａ）は実質的に芳香族ビニル単量体とシアノ系単量体の共重合体のみからなる。 The resin composition of the present invention comprises a resin (A) containing a copolymer of an aromatic vinyl monomer and a cyano-based monomer, and an oxidation having a total of three or more phenol or sulfide moieties in the molecule. It contains an inhibitor (B) and a phosphorus-based antioxidant (C).
The resin (A) in the present invention is a resin containing a copolymer of an aromatic vinyl monomer and a cyano-based monomer as a main component. In the resin (A), the content of the copolymer of the aromatic vinyl monomer and the cyano-based monomer in 100% by mass of the resin (A) is, for example, 50% by mass or more. In one embodiment, the content of the copolymer in the resin (A) is preferably 80% by mass or more, more preferably 80% by mass or more, and further preferably the resin (A) is substantially. It consists only of a copolymer of an aromatic vinyl monomer and a cyano-based monomer.
　芳香族ビニル単量体としては特に限定されないが、スチレン、αーメチルスチレン、ｐーメチルスチレン、３、５ージメチルスチレン、４ーメトキシスチレン、２ーヒドロキシスチレンなどの置換基を有する置換スチレン、αーブロムスチレン、２、４ージクロロスチレンなどのハロゲン化スチレン、１ービニルナフタレンなどが挙げられる。 The aromatic vinyl monomer is not particularly limited, but is substituted styrene having a substituent such as styrene, α-methylstyrene, p-methylstyrene, 3,5-dimethylstyrene, 4-methoxystyrene, 2-hydroxystyrene, α-bromstyrene, 2 Examples thereof include halogenated styrene such as 4-dichlorostyrene and 1-vinylnaphthalene.
　シアノ系単量体としては特に限定されないが、アクリロニトリル、メタクリロニトリル、αークロルアクリロニトリル、αーエチルアクリロニトリルなどが挙げられる。 The cyano-based monomer is not particularly limited, and examples thereof include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and α-ethylacrylonitrile.
　本発明の酸化防止剤（Ｂ）は、基本骨格内にフェノール部位またはスルフィド部位を分子内に合計で３つ以上有することが重要である。２つ以下であると酸化防止能力が十分でなく、成形時に樹脂の劣化が起きて色相が悪化する。 It is important that the antioxidant (B) of the present invention has a total of three or more phenol sites or sulfide sites in the molecule in the basic skeleton. If the number is two or less, the antioxidant capacity is not sufficient, and the resin deteriorates during molding, resulting in deterioration of hue.
　本発明で使用できる酸化防止剤（Ｂ）は、具体的には、１，３，５，トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）－１，３，５，トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、４，４´，４´´－（１－メチルプロパニル－３－イリデン）トリス（６－ｔｅｒｔ－ブチル－ｍ－クレゾール）、１，３，５，トリス（３，５－ジ－ｔｅｒｔ‐ブチル－４－ヒドロキシフェニルメチル）－２，４，６－トリメチルベンゼン等のトリスフェノール類、ペンタエリスリチル－テトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］等のテトラフェノール類、４，６－ビス（オクチルチオメチル）－ｏ－クレゾール、４，６－ビス（ドデシルチオメチル）－ｏ－クレゾール、２，４－ビス（オクチルチオ）－６－（４－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ブチルアニリノ）－１，３，５，－トリアジン等のビスアルキルチオフェノール類、テトラキス［３－（ドデシルチオ）プロピオン酸］ペンタエリトリトール等のトリスチオアルキル類等が挙げられ、１種単独で又は２種以上を組み合わせて用いてもよい。 The antioxidant (B) that can be used in the present invention is specifically 1,3,5, tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5, triazine-. 2,4,6 (1H, 3H, 5H) -trione, 4,4', 4'-(1-methylpropanol-3-iriden) tris (6-tert-butyl-m-cresol), 1, Trisphenols such as 3,5, Tris (3,5-di-tert-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene, pentaerythrityl-tetrakis [3- (3,5-) Tetraphenols such as tert-butyl-4-hydroxyphenyl) propionate], 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, 2 , 4-Bis (octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine and other bisalkylthiophenols, tetrakis [3- (dodecylthio) propionic acid ] Tristhioalkyls such as pentaerythritol may be mentioned, and one type may be used alone or two or more types may be used in combination.
　本発明のリン系酸化防止剤（Ｃ）は、例えば、トリスノニルフェニルフォスファイト、トリフェニルフォスファイト、トリス（２，４－ジ－ｔ－ブチルフェニル）フォスファイト、サイクリックネオペンタンテトライルビス（２，４－ジ－ｔ－ブチルフェニルフォスファイト）、サイクリックネオペンタンテトライルビス（オクタデシルフォスファイト）、サイクリックネオペンタンテトライルビス（ノニルフェニルフォスファイト）、トリス（ミックスド，モノ及びジノニルフェニル）フォスファイト、４，４'－イソプロピリデンジフェノールアルキル（Ｃ１２～Ｃ１５）フォスファイト、ジフェニルイソオクチルフォスファイト、ジフェニルイソデシルフォスファイト、フェニルジイソデシルフォスファイト、トリスイソデシルフォスファイト、ビス（２，６－ジ－ｔ－ブチル－４－メチルフェニル）ペンタエリスリトールジホスファイト、２，２－メチレンビス（４，６－ジ－ｔ－ブチルフェニル）オクチルホスファイト等が挙げられ、１種単独で又は２種以上を組み合わせて用いることが出来る。 The phosphorus-based antioxidant (C) of the present invention is, for example, trisnonylphenylphosphite, triphenylphosphite, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis ( 2,4-di-t-butylphenylphosphite), cyclic neopentanetetraylbis (octadecylphosfite), cyclic neopentanetetraylbis (nonylphenylphosphite), tris (mixed, mono and dinonyl) Phenyl) phosphite, 4,4'-isopropylidenediphenolalkyl (C12-C15) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, trisisodecylphosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, etc. may be mentioned, and one type alone or 2 More than seeds can be used in combination.
　本実施形態の酸化防止剤（Ｂ）とリン系酸化防止剤（Ｃ）の含有量の合計は、樹脂（Ａ）１００質量部に対して０．０１～０．５０質量部であることが好ましく、０．０５～０．４０質量部であることがより好ましく、０．１０～０．３０質量部であることがさらに好ましい。具体的には例えば、０．０１、０．０５、０．１０、０．１５、０．２０、０．２５、０．３０、０．３５、０．４０、０．４５、又は０．５０質量部であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。酸化防止剤（Ｂ）とリン系酸化防止剤（Ｃ）の含有量の合計が０．５０質量部を超えると得られる樹脂組成物の耐熱性が低下する場合がある。また、酸化防止剤（Ｂ）とリン系酸化防止剤（Ｃ）の含有量の合計が０．０１質量部未満の場合、得られる成形品の色相の悪化を抑えることができなくなる。 The total content of the antioxidant (B) and the phosphorus-based antioxidant (C) in the present embodiment is preferably 0.01 to 0.50 parts by mass with respect to 100 parts by mass of the resin (A). , 0.05 to 0.40 parts by mass, more preferably 0.10 to 0.30 parts by mass. Specifically, for example, 0.01, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, or 0.50. It is a part by mass and may be in the range between any two of the numerical values exemplified here. If the total content of the antioxidant (B) and the phosphorus-based antioxidant (C) exceeds 0.50 parts by mass, the heat resistance of the obtained resin composition may decrease. Further, when the total content of the antioxidant (B) and the phosphorus-based antioxidant (C) is less than 0.01 parts by mass, deterioration of the hue of the obtained molded product cannot be suppressed.
また酸化防止剤（Ｂ）とリン系酸化防止剤（Ｃ）の混合比率は特に限定されるものではない。酸化防止剤（Ｂ）とリン系酸化防止剤（Ｃ）の質量比は、好ましくは５／１～１／５、より好ましくは４／１～１／４である。具体的には例えば、５／１、４／１、３／１、２／１、１／１、１／２、１／３、１／４、又は１／５であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。酸化防止剤（Ｂ）とリン系酸化防止剤（Ｃ）との混合比率を質量比で５／１～１／５にすることにより、得られる成形品の色相の悪化を効率的に抑えることができる。 Further, the mixing ratio of the antioxidant (B) and the phosphorus-based antioxidant (C) is not particularly limited. The mass ratio of the antioxidant (B) to the phosphorus-based antioxidant (C) is preferably 5/1 to 1/5, more preferably 4/1 to 1/4. Specifically, for example, it is 5/1, 4/1, 3/1, 2/1, 1/1, 1/2, 1/3, 1/4, or 1/5, and the numerical values exemplified here. It may be within the range between any two of the above. By setting the mixing ratio of the antioxidant (B) and the phosphorus-based antioxidant (C) to 5/1 to 1/5 by mass ratio, deterioration of the hue of the obtained molded product can be efficiently suppressed. can.
酸化防止剤（Ｂ）とリン系酸化防止剤（Ｃ）の添加方法としては、樹脂（Ａ）の重合工程、脱揮工程、造粒工程で添加混合する方法や成形加工時の押出機や射出成形機などで添加混合する方法などが挙げられ、特に限定されない。 Examples of the method of adding the antioxidant (B) and the phosphorus-based antioxidant (C) include a method of adding and mixing the resin (A) in the polymerization step, the devolatilization step, and the granulation step, and an extruder or injection during molding. Examples thereof include a method of adding and mixing with a molding machine and the like, and the present invention is not particularly limited.
樹脂（Ａ）における芳香族ビニル単量体とシアノ系単量体の含有割合は任意に選択することができるが、１００質量％の共重合体に含有される芳香族ビニル単量体の量は、４０質量％～９５質量％が好ましく、より好ましくは５０質量％～８５質量％、さらに好ましくは７０質量％～８５質量％である。具体的には例えば、４０、５０、６０、６５、７０、７５、８０、８５、９０、又は９５質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。１００質量％の共重合体に含有されるシアノ系単量体の量は、好ましくは５質量％～６０質量％、より好ましくは１５質量％～５０質量％、さらに好ましくは１５質量％～７０質量％である。具体的には例えば、５、１０、１５、２０、３５、４０、５０、又は６０質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。各々の単量体が上記の組成範囲外であると、本発明の目的である成形品の外観及び、耐薬品性、透明性、機械的特性などを達成することが困難である。 The content ratio of the aromatic vinyl monomer and the cyano-based monomer in the resin (A) can be arbitrarily selected, but the amount of the aromatic vinyl monomer contained in the 100% by mass copolymer is , 40% by mass to 95% by mass, more preferably 50% by mass to 85% by mass, still more preferably 70% by mass to 85% by mass. Specifically, for example, it is 40, 50, 60, 65, 70, 75, 80, 85, 90, or 95% by mass, and may be within the range between any two of the numerical values exemplified here. .. The amount of the cyano-based monomer contained in the 100% by mass of the copolymer is preferably 5% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and further preferably 15% by mass to 70% by mass. %. Specifically, it is, for example, 5, 10, 15, 20, 35, 40, 50, or 60% by mass, and may be within the range between any two of the numerical values exemplified here. If each monomer is out of the above composition range, it is difficult to achieve the appearance, chemical resistance, transparency, mechanical properties, etc. of the molded product, which is the object of the present invention.
本発明における芳香族ビニル単量体とシアノ系単量体の共重合体を含有するとする樹脂（Ａ）の製造方法としては、懸濁重合方法、溶液重合法、塊状重合法等を用いることができるが、分散剤などの樹脂中への混入を防ぐ目的から、溶液重合法または塊状重合法が好適に使用される。 As a method for producing the resin (A) containing a copolymer of an aromatic vinyl monomer and a cyano-based monomer in the present invention, a suspension polymerization method, a solution polymerization method, a bulk polymerization method or the like can be used. However, a solution polymerization method or a bulk polymerization method is preferably used for the purpose of preventing the dispersant from being mixed into the resin.
樹脂（Ａ）には、シアノ系単量体及び芳香族ビニル単量体以外の共重合可能な単量体を本発明の効果を阻害しない範囲で共重合させても良い。シアノ系単量体及び芳香族ビニル単量体と共重合可能な他のビニル化合物としては、例えば、メチルメタクリレート、エチルメタクリレート、メチルアクリレート、エチルアクリレート、ブチルアクリレートなどのアクリル酸エステル類、アクリル酸、メタクリル酸、無水マレイン酸、イタコン酸等の不飽和カルボン酸類またはその無水物、Ｎーフェニルマレイミド、Ｎーシクロヘキシルマレイミドなどのマレイミド化合物などが挙げられ、特にエチルアクリレート、ブチルアクリレートが好ましく、これらの２種以上を混合して用いることもできる。
これらの単量体の含有量は、シアノ系単量体、芳香族ビニル単量体及びこれらと共重合可能な単量体の合計を１００質量％とした場合に０重量％～２０重量％、好ましくは０重量％～１０重量％とするとよい。 The resin (A) may be copolymerized with a copolymerizable monomer other than the cyano monomer and the aromatic vinyl monomer as long as the effect of the present invention is not impaired. Examples of other vinyl compounds copolymerizable with the cyano-based monomer and the aromatic vinyl monomer include acrylic acid esters such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate and butyl acrylate, and acrylic acid. Examples thereof include unsaturated carboxylic acids such as methacrylic acid, maleic anhydride and itaconic acid or their anhydrides, maleimide compounds such as N-phenylmaleimide and N-cyclohexylmaleimide, and ethyl acrylate and butyl acrylate are particularly preferable. It is also possible to mix and use more than seeds.
The content of these monomers is 0% by mass to 20% by mass when the total of the cyano-based monomer, the aromatic vinyl monomer and the monomer copolymerizable with these is 100% by mass. It is preferably 0% by weight to 10% by weight.
樹脂（Ａ）の製造においては、分子量調節剤として、例えばｔ－ドデシルメルカプタン、ｎ－ドデシルメルカプタン、α－メチルスチレンの不飽和二量体、テルピノレン、チオグリコール酸オクチル等を使用してもよい。 In the production of the resin (A), for example, t-dodecyl mercaptan, n-dodecyl mercaptan, unsaturated dimer of α-methylstyrene, terpinolene, octyl thioglycolate and the like may be used as the molecular weight modifier.
本発明の樹脂組成物には、本発明の効果を阻害しない範囲でミネラルオイルを含有しても良い。また、ステアリン酸、エチレンビスステアリルアミド等の内部潤滑剤や、イオウ系酸化防止剤、ラクトン系酸化防止剤、紫外線吸収剤、ヒンダードアミン系安定剤、帯電防止剤、外部潤滑剤等の添加剤が含まれていても良い。 The resin composition of the present invention may contain mineral oil as long as the effects of the present invention are not impaired. It also contains internal lubricants such as stearic acid and ethylene bisstearylamide, and additives such as sulfur-based antioxidants, lactone-based antioxidants, ultraviolet absorbers, hindered amine-based stabilizers, antistatic agents, and external lubricants. It may be.
紫外線吸収剤は、紫外線による劣化や着色を抑制する機能を有するものであって、例えば、ベンゾフェノン系、ベンゾトリアゾール系、トリアジン系、ベンゾエート系、サリシレート系、シアノアクリレート系、蓚酸アニリド系、マロン酸エステル系、ホルムアミジン系などの紫外線吸収剤が挙げられる。これらは、単独又は２種以上組み合わせて用いることができ、ヒンダートアミン等の光安定剤を併用してもよい。 The ultraviolet absorber has a function of suppressing deterioration and coloring due to ultraviolet rays, and is, for example, benzophenone-based, benzotriazole-based, triazine-based, benzoate-based, salicylate-based, cyanoacrylate-based, oxalic acid anilide-based, and malonic acid ester. Examples thereof include ultraviolet absorbers such as those of the system and those of the formamidine system. These can be used alone or in combination of two or more, and a light stabilizer such as hindered amine may be used in combination.
本発明の樹脂組成物は多様な意匠性を発現するために本発明の効果を阻害しない範囲で各種の染顔料を含有しても良い。例えば、クマリン系蛍光染料、ベンゾピラン系蛍光染料、ペリレン系蛍光染料、アンスラキノン系蛍光染料、チオインジゴ系蛍光染料、キサンテン系蛍光染料、キサントン系蛍光染料、チオキサンテン系蛍光染料、チオキサントン系蛍光染料、チアジン系蛍光染料、およびジアミノスチルベン系蛍光染料などを挙げることができる。上記の染顔料の含有量は、樹脂（Ａ）、酸化防止剤（Ｂ）、及び酸化防止剤（Ｃ）の合計１００質量部を基準として０．００００１～１質量部が好ましく、０．００００３～０．３質量部がより好ましい。 In order to exhibit various designs, the resin composition of the present invention may contain various dyes and pigments as long as the effects of the present invention are not impaired. For example, coumarin fluorescent dye, benzopyran fluorescent dye, perylene fluorescent dye, anthracinone fluorescent dye, thioindigo fluorescent dye, xanthene fluorescent dye, xantone fluorescent dye, thioxanthene fluorescent dye, thioxanthone fluorescent dye, thiadin. Examples thereof include a fluorescent dye and a diaminostilben fluorescent dye. The content of the above dyeing pigment is preferably 0.00001 to 1 part by mass, preferably 0.00003 to 1 part by mass based on a total of 100 parts by mass of the resin (A), the antioxidant (B), and the antioxidant (C). 0.3 parts by mass is more preferable.
樹脂組成物から成形体を得る方法については、公知の成形加工技術を用いることができ、例えば、射出成形、押出成形、シート成形、プレス成形等が挙げられる。 As a method for obtaining a molded product from the resin composition, a known molding processing technique can be used, and examples thereof include injection molding, extrusion molding, sheet molding, and press molding.
本発明にかかる樹脂組成物を成形して得られる成形体は、特に高いデザイン性を求められる化粧品容器に加工することができる。また、本発明にかかる樹脂組成物は、単独あるいはＡＢＳ樹脂、ＰＣ樹脂等の他の樹脂とのブレンドした混合樹脂として好適に使用される。 The molded product obtained by molding the resin composition according to the present invention can be processed into a cosmetic container that requires particularly high design. Further, the resin composition according to the present invention is preferably used alone or as a mixed resin blended with other resins such as ABS resin and PC resin.
以下、詳細な内容について実施例を用いて説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the detailed contents will be described with reference to Examples, but the present invention is not limited to the following Examples.
＜樹脂（Ａ－１）の製造例＞
５０Ｌの反応槽に供給する供給液を、スチレン７０質量部、アクリロニトリル１５質量部、エチルベンゼン１５質量部、重合開始剤としてｔ－ブチルパーオキシイソプロピルカーボネート０．０２質量部、連鎖移動剤としてｎ－ドデシルメルカプタンを０．０１質量部となるように調製した。この供給液を窒素ガスでバブリングした後、連続的に１０．８Ｌ／時間の速度で反応槽へ供給し、重合温度１４５℃、反応槽内での反応液の充填率が７０ｖｏｌ％を維持できるようにし、供給液量と同量の反応液を連続的に抜き出した。抜き出した反応液は、２５０℃、１０ｍｍＨｇの高真空に保たれた揮発分除去装置へ導入し、未反応単量体、有機溶剤を脱気回収し、共重合体はペレットとして回収した。 <Manufacturing example of resin (A-1)>
The supply liquid supplied to the 50 L reaction vessel is 70 parts by mass of styrene, 15 parts by mass of acrylonitrile, 15 parts by mass of ethylbenzene, 0.02 parts by mass of t-butylperoxyisopropylcarbonate as a polymerization initiator, and n-dodecyl as a chain transfer agent. Mercaptan was prepared to be 0.01 parts by mass. After bubbling this supply liquid with nitrogen gas, it is continuously supplied to the reaction tank at a rate of 10.8 L / hour so that the polymerization temperature can be maintained at 145 ° C. and the filling rate of the reaction liquid in the reaction tank can be maintained at 70 vol%. The reaction solution was continuously withdrawn in the same amount as the supply liquid. The extracted reaction solution was introduced into a volatile matter removing device maintained at a high vacuum of 250 ° C. and 10 mmHg, the unreacted monomer and the organic solvent were degassed and recovered, and the copolymer was recovered as pellets.
＜樹脂（Ａ－２）の製造例＞
５０Ｌの反応槽に供給する供給液を、スチレン５８質量部、アクリロニトリル２２質量部、エチルベンゼン２０質量部、重合開始剤としてｔ－ブチルパーオキシイソプロピルカーボネート０．０２質量部、連鎖移動剤としてｎ－ドデシルメルカプタンを０．０４質量部となるように調製した。この供給液を窒素ガスでバブリングした後、連続的に８Ｌ／時間の速度で反応槽へ供給し、重合温度１４５℃、反応槽内での反応液の充填率が６０ｖｏｌ％を維持できるようにし、供給液量と同量の反応液を連続的に抜き出した。抜き出した反応液は、２５０℃、１０ｍｍＨｇの高真空に保たれた揮発分除去装置へ導入し、未反応単量体、有機溶剤を脱気回収し、共重合体はペレットとして回収した。 <Manufacturing example of resin (A-2)>
The supply liquid supplied to the 50 L reaction vessel was 58 parts by mass of styrene, 22 parts by mass of acrylonitrile, 20 parts by mass of ethylbenzene, 0.02 parts by mass of t-butylperoxyisopropylcarbonate as a polymerization initiator, and n-dodecyl as a chain transfer agent. Mercaptan was prepared to be 0.04 parts by mass. After bubbling this supply liquid with nitrogen gas, it is continuously supplied to the reaction tank at a rate of 8 L / hour so that the polymerization temperature can be maintained at 145 ° C. and the filling rate of the reaction liquid in the reaction tank can be maintained at 60 vol%. The same amount of reaction solution as the supply amount was continuously withdrawn. The extracted reaction solution was introduced into a volatile matter removing device maintained at a high vacuum of 250 ° C. and 10 mmHg, the unreacted monomer and the organic solvent were degassed and recovered, and the copolymer was recovered as pellets.
＜樹脂（Ａ－３）の製造例＞
５０Ｌの反応槽に供給する供給液を、スチレン４９質量部、アクリロニトリル２９質量部、エチルベンゼン２３質量部、重合開始剤としてｔ－ブチルパーオキシイソプロピルカーボネート０．０２質量部、連鎖移動剤としてｎ－ドデシルメルカプタンを０．１２質量部となるように調製した。この供給液を窒素ガスでバブリングした後、連続的に９．８Ｌ／時間の速度で反応槽へ供給し、重合温度１４５℃、反応槽内での反応液の充填率が８０ｖｏｌ％を維持できるようにし、供給液量と同量の反応液を連続的に抜き出した。抜き出した反応液は、２５０℃、１０ｍｍＨｇの高真空に保たれた揮発分除去装置へ導入し、未反応単量体、有機溶剤を脱気回収し、共重合体はペレットとして回収した。 <Manufacturing example of resin (A-3)>
The supply liquid supplied to the reaction vessel of 50 L was 49 parts by mass of styrene, 29 parts by mass of acrylonitrile, 23 parts by mass of ethylbenzene, 0.02 part by mass of t-butylperoxyisopropylcarbonate as a polymerization initiator, and n-dodecyl as a chain transfer agent. Mercaptan was prepared to be 0.12 parts by mass. After bubbling this supply liquid with nitrogen gas, it is continuously supplied to the reaction tank at a rate of 9.8 L / hour so that the polymerization temperature can be maintained at 145 ° C. and the filling rate of the reaction liquid in the reaction tank can be maintained at 80 vol%. The reaction solution was continuously withdrawn in the same amount as the supply liquid. The extracted reaction solution was introduced into a volatile matter removing device maintained at a high vacuum of 250 ° C. and 10 mmHg, the unreacted monomer and the organic solvent were degassed and recovered, and the copolymer was recovered as pellets.
＜樹脂（Ａ－４）の製造例＞
スチレン７０質量部、アクリロニトリル９質量部、エチルベンゼン２１質量部、重合開始剤としてｔ－ブチルパーオキシイソプロピルカーボネート０．０２質量部、連鎖移動剤としてｎ－ドデシルメルカプタンを０．１２質量部となるように調製した。この供給液を窒素ガスでバブリングした後、連続的に９．８Ｌ／時間の速度で反応槽へ供給し、重合温度１４５℃、反応槽内での反応液の充填率が７５ｖｏｌ％を維持できるようにし、供給液量と同量の反応液を連続的に抜き出した。抜き出した反応液は、２５０℃、１０ｍｍＨｇの高真空に保たれた揮発分除去装置へ導入し、未反応単量体、有機溶剤を脱気回収し、共重合体はペレットとして回収した。 <Manufacturing example of resin (A-4)>
70 parts by mass of styrene, 9 parts by mass of acrylonitrile, 21 parts by mass of ethylbenzene, 0.02 parts by mass of t-butylperoxyisopropyl carbonate as a polymerization initiator, and 0.12 parts by mass of n-dodecyl mercaptan as a chain transfer agent. Prepared. After bubbling this supply liquid with nitrogen gas, it is continuously supplied to the reaction tank at a rate of 9.8 L / hour so that the polymerization temperature can be maintained at 145 ° C. and the filling rate of the reaction liquid in the reaction tank can be maintained at 75 vol%. The reaction solution was continuously withdrawn in the same amount as the supply liquid. The extracted reaction solution was introduced into a volatile matter removing device maintained at a high vacuum of 250 ° C. and 10 mmHg, the unreacted monomer and the organic solvent were degassed and recovered, and the copolymer was recovered as pellets.
＜樹脂（Ａ－５）の製造例＞
５０Ｌの反応槽に供給する供給液を、スチレン８４質量部、エチルベンゼン１６質量部、重合開始剤としてｔ－ブチルパーオキシイソプロピルカーボネート０．０２質量部、連鎖移動剤としてｎ－ドデシルメルカプタンを０．１２質量部となるように調製した。この供給液を窒素ガスでバブリングした後、連続的に９．８Ｌ／時間の速度で反応槽へ供給し、重合温度１４５℃、反応槽内での反応液の充填率が８０ｖｏｌ％を維持できるようにし、供給液量と同量の反応液を連続的に抜き出した。抜き出した反応液は、２５０℃、１０ｍｍＨｇの高真空に保たれた揮発分除去装置へ導入し、未反応単量体、有機溶剤を脱気回収し、共重合体はペレットとして回収した。 <Manufacturing example of resin (A-5)>
The supply liquid supplied to the 50 L reaction vessel was 84 parts by mass of styrene, 16 parts by mass of ethylbenzene, 0.02 parts by mass of t-butylperoxyisopropyl carbonate as a polymerization initiator, and 0.12 parts of n-dodecyl mercaptan as a chain transfer agent. It was prepared to be parts by mass. After bubbling this supply liquid with nitrogen gas, it is continuously supplied to the reaction tank at a rate of 9.8 L / hour so that the polymerization temperature can be maintained at 145 ° C. and the filling rate of the reaction liquid in the reaction tank can be maintained at 80 vol%. The reaction solution was continuously withdrawn in the same amount as the supply liquid. The extracted reaction solution was introduced into a volatile matter removing device maintained at a high vacuum of 250 ° C. and 10 mmHg, the unreacted monomer and the organic solvent were degassed and recovered, and the copolymer was recovered as pellets.
樹脂中の組成分析は、ＪＩＳ　Ｋ６４５１－２：２０１６に準拠して測定した。尚、試料量は０．２ｇ、分解温度は４００℃、滴定標準溶液は硫酸標準水溶液を用いた。 The composition analysis in the resin was measured according to JIS K6451-2: 2016. The sample amount was 0.2 g, the decomposition temperature was 400 ° C., and the titration standard solution was a sulfuric acid standard aqueous solution.
＜酸化防止剤（Ｂ）＞
酸化防止剤（Ｂ）として、以下を用いた。
Ｂ－１：ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］（ＢＡＳＦジャパン株式会社製　Ｉｒｇａｎｏｘ１０１０）
Ｂ－２：４，４'，４''－（１－メチルプロパニル－３－イリデン）トリス（６－ｔｅｒｔ－ブチル－ｍ－クレゾール）（株式会社ＡＤＥＫＡ製　アデカスタブＡＯ－３０）
Ｂ－３：１，３，５，トリス（３，５－ジ－ｔｅｒｔ‐ブチル－４－ヒドロキシフェニルメチル）－２，４，６－トリメチルベンゼン（ＢＡＳＦジャパン株式会社製　Ｉｒｇａｎｏｘ１３３０）
Ｂ－４：４，６－ビス（オクチルチオメチル）－ｏ－クレゾール（ＢＡＳＦジャパン株式会社製　Ｉｒｇａｎｏｘ１５２０）
Ｂ－５：２，４－ビス（オクチルチオ）－６－（４－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ブチルアニリノ）－１，３，５，－トリアジン（ＢＡＳＦジャパン株式会社製　Ｉｒｇａｎｏｘ５６５）
Ｂ－６：エチレンビス（オキシエチレン）ビス〔３－（５－ｔｅｒｔ－ブチル－４－ヒド
ロキシ－ｍ－トリル）プロピオネート〕（ＢＡＳＦジャパン株式会社製　Ｉｒｇａｎｏｘ　２４５）
Ｂ－７：アクリル酸２－［１－（２－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ペンチルフェニル）エチル］－４，６－ジ－ｔｅｒｔ－ペンチルフェニル（住友化学株式会社製　Ｓｕｍｉｌｉｚｅｒ　ＧＳ）
Ｂ－８： ｎ－オクタデシル－３－（４'－ヒドロキシ－３'，５'－ジ－ｔ－ブチルフェニル）プロピオネート（ＢＡＳＦジャパン株式会社製　Ｉｒｇａｎｏｘ　１０７６） <Antioxidant (B)>
The following was used as the antioxidant (B).
B-1: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010 manufactured by BASF Japan Ltd.)
B-2: 4,4', 4''- (1-methylpropanol-3-iriden) Tris (6-tert-butyl-m-cresol) (ADEKA CORPORATION ADEKA STAB AO-30)
B-3: 1,3,5, Tris (3,5-di-tert-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene (Irganox 1330 manufactured by BASF Japan Ltd.)
B-4: 4,6-bis (octylthiomethyl) -o-cresol (Irganox1520 manufactured by BASF Japan Ltd.)
B-5: 2,4-bis (octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine (Irganox565 manufactured by BASF Japan Ltd.)
B-6: Ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (Irganox 245 manufactured by BASF Japan Ltd.)
B-7: 2- [1- (2-Hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl (Sumilizer GS manufactured by Sumitomo Chemical Co., Ltd.)
B-8: n-octadecyl-3- (4'-hydroxy-3', 5'-di-t-butylphenyl) propionate (Irganox 1076 manufactured by BASF Japan Ltd.)
＜リン系酸化防止剤（Ｃ）＞
リン系酸化防止剤として、以下を用いた。
Ｃ－１：トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）フォスファイト（株式会社ＡＤＥＫＡ製　アデカスタブ２１１２）
Ｃ－２：テトラ－Ｃ１２－１５－アルキル（プロパン－２，２－ジイルビス（４，１－フェニレン））ビス（フォスファイト）（株式会社ＡＤＥＫＡ製　アデカスタブ１５００） <Phosphorus-based antioxidant (C)>
The following were used as phosphorus-based antioxidants.
C-1: Tris (2,4-di-tert-butylphenyl) phosphite (ADEKA CORPORATION ADEKA STAB 2112)
C-2: Tetra-C12-15-alkyl (Propane-2,2-diylbis (4,1-phenylene)) Bis (Phosfite) (ADEKA STAB 1500 manufactured by ADEKA Corporation)
＜樹脂組成物＞
実施例１～１４、比較例１～８
　樹脂Ａ－１～Ａ－５と、酸化防止剤（Ｂ）とリン系酸化防止剤（Ｃ）とを表１～３に示した配合割合でブレンドした後、単軸押出機（IKG株式会社製　ＭＳ－４０）を用いて、押出しペレット化した。このペレットを使用し、射出成形機により試験片を作成して、各物性値の測定を行った。結果を表１～３に示す。 <Resin composition>
Examples 1 to 14, Comparative Examples 1 to 8
After blending the resins A-1 to A-5, the antioxidant (B) and the phosphorus-based antioxidant (C) in the blending ratios shown in Tables 1 to 3, a single-screw extruder (manufactured by IKG Co., Ltd.) It was extruded and pelletized using MS-40). Using this pellet, a test piece was prepared by an injection molding machine, and each physical property value was measured. The results are shown in Tables 1 to 3.
（色相・透過率）
　得られたペレットを用いて射出成形機（Ｊ１４０ＡＤ－１８０Ｈ、株式会社日本鉄鋼所製）により、１２７×１２７×３ｍｍ厚みの板状成形品を成形温度２３０℃で成形した。板状成形品から１１５×８５×３ｍｍ厚みの試験片を切り出し、端面をバフ研磨によって研磨し、端面に鏡面を有する板状成形品を作成した。研磨後の板状成形品について、日本分光株式会社製の紫外線可視分光光度計Ｖ－６７０を用いて、大きさ２０×１．６ｍｍ、広がり角度０°の入射光において、光路長１１５ｍｍでの３５０ｎｍ～８００ｎｍの分光透過率を測定し、波長Ｃ光源における、視野２°でのＹＩ値をＪＩＳ　Ｋ７１０５に倣い算出した。また、透過率は４３０～７００ｎｍの範囲の全光線透過率を示す。結果を表１～３に示す。 (Hue / Transmittance)
Using the obtained pellets, a plate-shaped molded product having a thickness of 127 × 127 × 3 mm was molded at a molding temperature of 230 ° C. by an injection molding machine (J140AD-180H, manufactured by Nippon Steel Co., Ltd.). A test piece having a thickness of 115 × 85 × 3 mm was cut out from the plate-shaped molded product, and the end face was polished by buffing to prepare a plate-shaped molded product having a mirror surface on the end face. For the polished plate-shaped molded product, using an ultraviolet visible spectrophotometer V-670 manufactured by JASCO Corporation, the incident light having a size of 20 × 1.6 mm and a spreading angle of 0 ° has a light path length of 115 mm and 350 nm. The spectral transmittance of about 800 nm was measured, and the YI value at a field of view of 2 ° in the wavelength C light source was calculated according to JIS K7105. Further, the transmittance indicates the total light transmittance in the range of 430 to 700 nm. The results are shown in Tables 1 to 3.
（耐薬品性）
　試験片は成形ひずみの影響を排除するため、２６０℃にて各ペレットを厚さ４ｍｍになるようプレス成形して、５０ｍｍ×５０ｍｍ角に切り出して製造した。４０℃に設定した各薬品に１４日間浸漬した後、重量変化と外観変化から次のように分類した。薬品は５％尿素水溶液、サラダ油を用いた。
◎ ： 影響は殆ど認められない、○ ： 僅かに曇りあるいは変色が認められる、△ ： 僅かなクラックあるいはクレージングが発生する、× ： 溶解あるいは影響が大きい (chemical resistance)
The test piece was manufactured by press-molding each pellet at 260 ° C. to a thickness of 4 mm and cutting it into a 50 mm × 50 mm square in order to eliminate the influence of molding strain. After soaking in each chemical set at 40 ° C. for 14 days, they were classified as follows based on the change in weight and appearance. As the chemicals, a 5% aqueous urea solution and salad oil were used.
◎: Almost no effect is observed, ○: Slight cloudiness or discoloration is observed, △: Slight cracking or crazing occurs, ×: Dissolution or large effect
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　芳香族ビニル単量体とシアノ系単量体の共重合体を含有するとする樹脂（Ａ）とフェノール部位を分子内に合計で３つ以上有する酸化防止剤（Ｂ）とリン系の酸化防止剤（Ｃ）を含む実施例１～１４は耐薬品性を有し、透明性とYI値に優れていた。一方、フェノール部位が分子内に２つ以下である酸化防止剤を用いた比較例１～５、酸化防止剤を使用しなかった比較例６、リン系の酸化防止剤（Ｃ）を併用しなかった比較例７は透過率が低くかつYI値が高い結果となり、色相に劣る結果となった。シアノ系単量体成分を含まない樹脂を用いた比較例８は透明性、色相は優れていたが、耐薬品性が非常に悪化した。 A resin (A) containing a copolymer of an aromatic vinyl monomer and a cyano-based monomer, an antioxidant (B) having a total of three or more phenol moieties in the molecule, and a phosphorus-based antioxidant. Examples 1 to 14 including (C) had chemical resistance and were excellent in transparency and YI value. On the other hand, Comparative Examples 1 to 5 using an antioxidant having two or less phenol sites in the molecule, Comparative Example 6 not using an antioxidant, and a phosphorus-based antioxidant (C) were not used in combination. In Comparative Example 7, the transmittance was low and the YI value was high, resulting in inferior hue. Comparative Example 8 using a resin containing no cyano-based monomer component was excellent in transparency and hue, but the chemical resistance was significantly deteriorated.
　本発明の樹脂組成物および成形品は、耐薬品性に優れ色相および透明性に優れることから、高いデザイン性と耐薬品性が要求される用途に好適に用いることができる。具体的には、化粧品容器や食品容器、ライター等の雑貨等が挙げられる。 Since the resin composition and molded product of the present invention have excellent chemical resistance and hue and transparency, they can be suitably used for applications requiring high design and chemical resistance. Specific examples thereof include cosmetic containers, food containers, and miscellaneous goods such as lighters.

Claims (5)

  1. 　芳香族ビニル単量体とシアノ系単量体の共重合体を含有する樹脂（Ａ）と、フェノール部位を分子内に合計で３つ以上有する酸化防止剤（Ｂ）と、リン系の酸化防止剤（Ｃ）とを含有する樹脂組成物。 A resin (A) containing a copolymer of an aromatic vinyl monomer and a cyano-based monomer, an antioxidant (B) having a total of three or more phenol moieties in the molecule, and a phosphorus-based antioxidant. A resin composition containing the agent (C).
  2. 　前記酸化防止剤（Ｂ）と前記酸化防止剤（Ｃ）の合計含有量が、前記樹脂（Ａ）１００質量部に対して０.０１～０.５質量部である請求項１に記載の樹脂組成物。 The resin according to claim 1, wherein the total content of the antioxidant (B) and the antioxidant (C) is 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the resin (A). Composition.
  3. 　前記芳香族ビニル単量体とシアノ系単量体の共重合体は、芳香族ビニル単量体とシアノ系単量体の合計を１００質量％とした場合に、前記芳香族ビニル単量体単位４０～９５質量％と、前記シアノ系単量体単位５～６０質量％を含有する、請求項１または請求項２に記載の樹脂組成物。 The copolymer of the aromatic vinyl monomer and the cyano-based monomer is a unit of the aromatic vinyl monomer when the total of the aromatic vinyl monomer and the cyano-based monomer is 100% by mass. The resin composition according to claim 1 or 2, which contains 40 to 95% by mass and 5 to 60% by mass of the cyano-based monomer unit.
  4. 　請求項１～３のいずれか１項に記載の樹脂組成物から成形されてなることを特徴とする成形体。 A molded body characterized by being molded from the resin composition according to any one of claims 1 to 3.
  5. 　請求項１～３いずれか１項に記載の樹脂組成物から成形されてなることを特徴とする化粧品容器。 A cosmetic container characterized by being molded from the resin composition according to any one of claims 1 to 3.
PCT/JP2021/030601 2020-08-28 2021-08-20 Resin composition, molded article and cosmetics container WO2022045003A1 (en)

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