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.

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• 2021
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