WO2010082613A1 - ゴム変性熱可塑性樹脂組成物、その射出成形体およびそれを用いた洗濯機の蓋 - Google Patents
ゴム変性熱可塑性樹脂組成物、その射出成形体およびそれを用いた洗濯機の蓋 Download PDFInfo
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- WO2010082613A1 WO2010082613A1 PCT/JP2010/050375 JP2010050375W WO2010082613A1 WO 2010082613 A1 WO2010082613 A1 WO 2010082613A1 JP 2010050375 W JP2010050375 W JP 2010050375W WO 2010082613 A1 WO2010082613 A1 WO 2010082613A1
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
- C08F212/10—Styrene with nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F37/00—Details specific to washing machines covered by groups D06F21/00 - D06F25/00
- D06F37/26—Casings; Tubs
- D06F37/28—Doors; Security means therefor
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00
- D06F39/12—Casings; Tubs
- D06F39/14—Doors or covers; Securing means therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention relates to a rubber-modified thermoplastic resin composition, an injection-molded body thereof, and a lid of a washing machine using the same.
- ABS resin is widely used in home appliances, electrical / electronic equipment parts, OA equipment, pachinko parts, etc. because of its excellent impact resistance, mechanical properties, and molding processability.
- transparent ABS resin is used (Patent Document 1).
- such transparent ABS resin is not sufficiently resistant to organic solvents such as alcohol, detergents, etc., and there is a problem that cracks and cracks may occur depending on the application and use environment, which impairs commercial value. There is a need to improve sex.
- Patent Documents 2 to 4 propose resin compositions comprising a styrene-acrylonitrile-methyl methacrylate copolymer and a graft copolymer.
- Patent Document 5 proposes a resin composition comprising a copolymer of alkyl acrylate having 1 to 4 carbon atoms and methyl methacrylate, a styrene-acrylonitrile copolymer, and a graft copolymer.
- Patent Document 6 proposes a resin composition comprising an acrylic resin, an ABS resin, and a copolymer of vinyl cyanide and aromatic vinyl.
- Patent Documents 2 to 4 have a problem that a resin composition comprising a copolymer of styrene-acrylonitrile-methyl methacrylate and a graft copolymer has a poor hue as it becomes high nitrile. It was.
- Patent Document 5 a resin composition comprising a copolymer of alkyl acrylate having 1 to 4 carbon atoms and methyl methacrylate, a styrene-acrylonitrile copolymer and a graft copolymer has poor transparency, Further, since alkyl acrylate is copolymerized to improve thermal stability, there is a problem that heat resistance is low.
- Patent Document 6 an acrylic resin, ABS resin, and a resin composition comprising a copolymer of vinyl cyanide and aromatic vinyl had a problem in transparency as in Patent Document 5.
- the present inventors have determined that a specific styrene-methacrylic acid ester copolymer, a specific styrene-vinyl cyanide copolymer, and a specific graft copolymer are in specific conditions.
- the rubber-modified thermoplastic resin composition contained in a specific composition is generally in a trade-off relationship with each other, and it is difficult to satisfy at the same time, chemical resistance, transparency, hue It was found that heat resistance and impact resistance are excellent in a well-balanced manner.
- a modified thermoplastic resin composition is provided.
- the component (A) is composed of 1 to 15% by mass of styrene monomer units and 100% by mass of styrene monomer units and methacrylic acid ester monomer units.
- the component (B) is composed of 80 to 90% by mass of styrene monomer units and cyanide when the total mass of styrene monomer units and vinyl cyanide monomer units is 100% by mass.
- This is a styrene-vinyl cyanide copolymer containing vinyl halide monomer units in the range of 10 to 20% by mass.
- the component (C) is formed by copolymerizing a rubbery elastic body with a styrene monomer, a methacrylic acid ester monomer, and a vinyl cyanide monomer.
- the molded product having a thickness of 2 mm is a graft copolymer in which the total light transmittance is 85% or more.
- this (A) component is 15 to 54% by mass
- this (B) component is 20 to 20% by mass. 63% by mass
- the component (C) is contained in the range of 10 to 50% by mass.
- the difference between the refractive index of the mixture of the component (A) and the component (B) and the refractive index of the component (C) is 0.005 or less.
- the vinyl cyanide monomer unit in the mixture of these components (A) and (B) is 6 to 15 when the total mass of the components (A) and (B) is 100% by mass. It is in the range of mass%.
- the specific styrene-methacrylic acid ester copolymer, the specific styrene-vinyl cyanide copolymer, and the specific graft copolymer are Because it is contained in a specific composition, it is generally considered that it is difficult to satisfy at the same time because it is in a trade-off relationship with each other, in terms of chemical resistance, transparency, hue, heat resistance, and impact resistance. A rubber-modified thermoplastic resin composition excellent in balance can be obtained.
- an injection molded product obtained by injection molding the above rubber-modified thermoplastic resin composition. Since the rubber-modified thermoplastic resin composition having a good balance of chemical resistance, transparency, hue, heat resistance, and impact resistance is used, injection molding is performed by injection molding the rubber-modified thermoplastic resin composition. Similarly, the body is well balanced in chemical resistance, transparency, hue, heat resistance and impact resistance.
- a lid of a washing machine using the above injection molded body as a member Since the above-mentioned injection molded article having excellent balance in chemical resistance, transparency, hue, heat resistance and impact resistance is used, the lid of a washing machine using the injection molded article as a member is also chemically resistant, Excellent balance in transparency, hue, heat resistance and impact resistance.
- a rubber modified product containing a styrene-methacrylic acid ester copolymer (A), a styrene-vinyl cyanide copolymer (B), and a graft copolymer (C).
- a thermoplastic resin composition is provided. Since the rubber-modified thermoplastic resin composition of the present embodiment contains these component (A), component (B), and component (C) so as to satisfy the specific conditions and compounding composition described later, Have a good balance of chemical resistance, transparency, hue, heat resistance and impact resistance, which are said to be in a trade-off relationship and difficult to satisfy at the same time.
- Component (A) Styrene-methacrylic acid ester copolymer
- the above component (A) is a styrene-methacrylic acid ester copolymer comprising a styrene monomer unit and a methacrylic acid ester monomer unit. It is a coalescence.
- the structure of the styrene-methacrylic acid ester copolymer is not particularly limited, and a copolymer having an arbitrary structure including a styrene monomer unit and a methacrylic acid ester monomer unit can be used.
- copolymers are roughly classified into four types of structures: random copolymers, alternating copolymers, periodic copolymers, and block copolymers.
- One type of block copolymer is a graft system.
- a copolymer a copolymer having a branched structure in which different types of branched polymer chains are bonded to a main polymer chain
- a copolymer having any structure may be used.
- the styrene monomer unit used in the component (A) includes styrene, ⁇ -methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, ethylstyrene, pt-butylstyrene. Chlorostyrene, bromostyrene and the like can be mentioned, but from the viewpoint of kneadability and stability against thermal decomposition, styrene and ⁇ -methylstyrene are preferable, and styrene is particularly preferable. These styrenic monomers may be used alone or in combination of two or more. About these styrene-type monomer units, it can manufacture using the raw material which consists of a corresponding monomer or contains, for example.
- methacrylic acid ester monomer units used in the component (A) include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate. From the viewpoint of imparting heat resistance to the resin, It is preferable to use methyl methacrylate. These methacrylic acid ester monomers may be used alone or in combination of two or more. These methacrylic acid ester-based monomer units can be produced using, for example, a raw material comprising or including a corresponding monomer.
- the styrene monomer unit when the total mass of the styrene monomer unit and the methacrylic acid ester monomer unit is 100% by mass, the styrene monomer unit is 1%. It is preferable that the methacrylic acid ester monomer unit is contained in the range of 15 to 15% by mass and 85 to 99% by mass. Similarly, it is more preferable that the styrene monomer unit is contained in the range of 2 to 13% by mass and the methacrylic acid ester monomer unit is contained in the range of 87 to 98% by mass.
- the styrene monomer unit is 15% by mass or less, the smaller the styrene monomer unit, the more transparent the rubber-modified thermoplastic resin composition containing this styrene-methacrylic acid ester copolymer. This is because the property is improved.
- the styrene monomer unit is 1% by mass or more, the more styrene monomer units, the more the heat of the rubber-modified thermoplastic resin composition containing this styrene-methacrylic acid ester copolymer. This is because stability is excellent and transparency and hue are improved.
- the weight average molecular weight (Mw) of the styrene-methacrylic acid ester copolymer as the component (A) is preferably 70,000 to 100,000, and preferably 80,000 to 90,000. Is particularly preferred.
- Mw weight average molecular weight
- the chemical resistance of the rubber-modified thermoplastic resin composition containing the styrene-methacrylate copolymer is improved.
- the melt mass flow rate (MFR) of the rubber-modified thermoplastic resin composition containing the styrene-methacrylic acid ester copolymer can be maintained high.
- the moldability can be maintained well.
- the weight average molecular weight here was measured by the following gel permeation chromatography (GPC) method.
- Component (B) Styrene-vinyl cyanide copolymer
- the above component (B) is a styrene-vinyl cyanide copolymer comprising a styrene monomer unit and a vinyl cyanide monomer unit. It is a coalescence.
- the structure of the styrene-vinyl cyanide copolymer is not particularly limited, and a copolymer having an arbitrary structure including a styrene monomer unit and a vinyl cyanide monomer unit can be used. That is, the copolymers are roughly classified into four types of structures: random copolymers, alternating copolymers, periodic copolymers, and block copolymers.
- block copolymer is a graft system. Although there is a copolymer (a copolymer having a branched structure in which different types of branched polymer chains are bonded to a main polymer chain), a copolymer having any structure may be used.
- the styrene monomer unit used in the component (B) includes styrene, ⁇ -methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, ethylstyrene, pt-butylstyrene. Chlorostyrene, bromostyrene and the like can be mentioned, but from the viewpoint of kneadability and stability against thermal decomposition, styrene and ⁇ -methylstyrene are preferable, and styrene is particularly preferable. These styrenic monomers may be used alone or in combination of two or more. These styrenic monomer monomer units can be produced using, for example, a raw material comprising or including a corresponding monomer.
- Examples of the vinyl cyanide monomer unit used in the above component (B) include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, etc., and chemical resistance imparting and styrene-methacrylate copolymer From the viewpoint of compatibility with acrylonitrile, acrylonitrile is preferred. These vinyl cyanide monomers may be used alone or in combination of two or more. These vinyl cyanide monomer units can be produced using, for example, a raw material comprising or including a corresponding monomer.
- the styrene-vinyl cyanide copolymer that is the component (B) has a styrene content when the total mass of the styrene monomer unit and the vinyl cyanide monomer unit is 100% by mass. It is preferable that the monomer unit is contained in the range of 80 to 90% by mass and the vinyl cyanide monomer unit in the range of 10 to 20% by mass. Similarly, it is more preferable that the styrene monomer unit is contained in the range of 80 to 88% by mass and the vinyl cyanide monomer unit is contained in the range of 12 to 20% by mass.
- the styrene monomer unit is contained in the range of 80 to 84% by mass and the vinyl cyanide monomer unit is contained in the range of 16 to 20% by mass. This is because if the vinyl cyanide monomer unit is 20% by mass or less, the smaller the vinyl cyanide monomer unit, the smaller the rubber-modified thermoplastic resin composition containing this styrene-vinyl cyanide copolymer. This is because the transparency of the material is improved. Further, when the vinyl cyanide monomer unit is 10% by mass or more, the more vinyl cyanide monomer units, the more the rubber-modified thermoplastic resin composition containing this styrene-vinyl cyanide copolymer. This is because the chemical resistance is improved.
- the weight average molecular weight (Mw) of the styrene-vinyl cyanide copolymer as the component (B) is preferably 100,000 to 190,000, and 160,000 to 180,000. It is particularly preferred. If the weight average molecular weight of the styrene-vinyl cyanide copolymer is 100,000 or 160,000 or more, the impact resistance of the rubber-modified thermoplastic resin composition containing the styrene-vinyl cyanide copolymer If the weight average molecular weight of the styrene-vinyl cyanide copolymer is 190,000 or 180,000 or less, the rubber modification containing the styrene-vinyl cyanide copolymer can be maintained. The moldability of the thermoplastic resin composition can be maintained well.
- Component (C) Graft copolymer
- the component (C) includes a rubber-like elastic body, a styrene monomer, a methacrylic acid ester monomer, and a vinyl cyanide monomer. Is a graft copolymer.
- the structure of the graft copolymer is not particularly limited, and a rubber-like elastic body is copolymerized with a styrene monomer, a methacrylate ester monomer, and a vinyl cyanide monomer.
- Any graft copolymer can be used. That is, it may be a graft copolymer having a branched structure in which different types of branched polymer chains are bonded to a general polymer chain serving as a trunk.
- acrylic rubbers such as ethyl acrylate and butyl acrylate, ethylene- ⁇ -olefin-polyene copolymers, ethylene- ⁇ -olefin copolymers, silicones Rubber, silicone-acrylic rubber copolymer,
- the ratio of styrene and butadiene is not particularly limited when a styrene-butadiene copolymer is used as the rubber-like elastic body used in the component (C), but the total mass of styrene and butadiene is 100% by mass.
- the styrene content is preferably 15 to 50% by mass
- the butadiene content is preferably 50 to 85% by mass
- the styrene content is 20 to 45% by mass
- the butadiene content is 55 to 80% by mass. More preferred is a butadiene copolymer.
- the styrene-butadiene copolymer used in the component (C) When the difference between the refractive index of the mixture of the component (A) and the component (B) and the refractive index of the component (C) is 0.005 or less, the styrene-butadiene copolymer used in the component (C) When the styrene content in the polymer is 20% by mass or more, the refractive index of the rubber-like elastic material containing a styrene-butadiene copolymer as a main component becomes high, so that the rubber-modified thermoplastic resin composition The blending ratio of the styrene-vinyl cyanide copolymer (B) can be increased, and the chemical resistance is improved. Further, when the styrene content is 45% by mass or less, the properties as an elastic body are further improved, so that the impact strength of the rubber-modified thermoplastic resin composition is improved.
- styrenic monomer used in the above component (C) examples include styrene, ⁇ -methylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, ethylstyrene, pt-butylstyrene, Chlorostyrene, bromostyrene and the like can be mentioned. From the viewpoint of compatibility and kneadability between the component (A) and the component (B), styrene and ⁇ -methylstyrene are preferable. Styrene is preferred. These styrenic monomers may be used alone or in combination of two or more.
- methacrylic acid ester monomer used in the component (C) examples include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
- the component (A) and the component (B) From the viewpoint of compatibility and heat resistance, it is preferable to use methyl methacrylate.
- These methacrylic acid ester monomers may be used alone or in combination of two or more.
- Examples of the vinyl cyanide monomer used in the component (C) include acrylonitrile, methacrylonitrile, etaacrylonitrile, fumaronitrile, and the like.
- the phase of the component (A) and the component (B) From the viewpoint of imparting solubility and chemical resistance, acrylonitrile is preferred.
- These vinyl cyanide monomers may be used alone or in combination of two or more.
- the graft copolymer as the component (C) preferably has a total light transmittance of 85% or more of a 2 mm-thick molded product obtained by press molding the graft copolymer, in particular 88. More preferably, it is% or less. If the total light transmittance of this press-molded body is 85% or 88% or more, the transparency of the resin composition as a material for molding the press-molded body is also improved.
- a graft copolymer having a total light transmittance of 85% or 88% or more in the press-molded product no complicated preparation is required.
- the refractive index of the rubber-like elastic material and the styrene-based copolymer are not required. It is easily obtained by adjusting the graft branch composition so that the difference from the refractive index of the graft branch formed by copolymerizing the monomer, methacrylate ester-based monomer and vinyl cyanide-based monomer is as small as possible. be able to.
- said (C) component in the range which does not impair the effect of the rubber-modified thermoplastic resin composition of this embodiment, ethyl acrylate, methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, etc. It is also possible to graft a rubber-like elastic body using other copolymerizable vinyl monomers such as acrylic acid esters and methacrylic acid esters.
- the volume-dispersed particle size of the graft copolymer is 0.25 to 0.80 ⁇ m.
- the rubber-modified thermoplastic resin composition containing this graft copolymer In order to obtain good transparency and impact resistance, it is particularly preferably 0.30 to 0.70 ⁇ m. If the volume average particle diameter is 0.25 ⁇ m or 0.30 ⁇ m or more, the impact resistance is excellent, and if it is 0.80 ⁇ m or less, the transparency can be maintained well, which is preferable.
- the volume average particle diameter is a volume-based median diameter measured by a light scattering type particle size distribution measuring apparatus in which a vinyl copolymer is dispersed in N, N-dimethylformamide (DMF).
- the total mass of the component (A), the component (B) and the component (C) is 100% by mass.
- the component (A) styrene-methacrylic ester copolymer
- the component (B) styrene-vinyl cyanide copolymer
- the above component (A) (styrene-methacrylate copolymer) Is 20 to 40% by mass
- the component (B) styrene-vinyl cyanide copolymer
- the component (C) (graft copolymer) is 15 to 45% by mass. It is preferable that it is contained within.
- the rubber-modified thermoplastic resin composition of the present embodiment a mixture of the component (A) (styrene-methacrylic acid ester copolymer) and the component (B) (styrene-vinyl cyanide copolymer).
- the difference between the refractive index of the component (C) (graft copolymer) is preferably 0.005 or less, particularly preferably 0.003 or less. When this refractive index difference is 0.005 or 0.003 or less, the transparency of the resulting rubber-modified thermoplastic resin composition can be maintained well.
- the refractive index referred to here is a molded product having a thickness of 2 mm by press molding from a mixture of the component (A) and the component (B) or a resin composition containing the component (C) as a main component. Measured using an Abbe refractometer.
- the rubber-modified thermoplastic resin composition of the present embodiment a mixture of the component (A) (styrene-methacrylic ester copolymer) and the component (B) (styrene-vinyl cyanide copolymer).
- the content of the vinyl cyanide monomer unit in the content is preferably in the range of 6 to 15% by mass when the total mass of the component (A) and the component (B) is 100% by mass. If the content of the vinyl cyanide monomer unit is 6% by mass or more, the chemical resistance of the resulting rubber-modified thermoplastic resin composition can be maintained satisfactorily. If the content of is 15% by mass or less, the yellowness can be suppressed from becoming strong, so that the hue can be maintained well.
- the method for producing the combined body (B) is not particularly limited, and any known polymerization method such as a bulk polymerization method, a suspension polymerization method, a bulk-suspension polymerization method, a solution polymerization method, and an emulsion polymerization method can be used.
- any known polymerization method such as a bulk polymerization method, a suspension polymerization method, a bulk-suspension polymerization method, a solution polymerization method, and an emulsion polymerization method can be used.
- the copolymers of the above components (A) and (B) are polymerized by continuous bulk polymerization.
- the method for producing the above graft copolymer (C) constituting the rubber-modified thermoplastic resin composition of the present embodiment is not particularly limited, and is also an emulsion polymerization method, bulk polymerization method, bulk-suspension method. Any known polymerization method such as a polymerization method or a solution polymerization method can be used, and among these, an emulsion polymerization method can be suitably employed from the viewpoint of transparency and appearance of an injection-molded product. In any of the production methods, a part of the styrene-methacrylic acid ester copolymer (A) constituting the continuous phase may be formed simultaneously with the production of the graft copolymer (C). In addition, any of a batch polymerization method and a continuous polymerization method can be used.
- styrene-methacrylic acid ester copolymer (A), styrene-vinyl cyanide copolymer (B), and graft copolymer (C) are all polymerized using azobis as a polymerization initiator.
- Azo compounds such as butyronitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxide, dicumylperoxide
- Organic peroxides such as oxide and ethyl-3,3-di- (t-butylperoxy) butyrate can be used.
- t-dodecyl mercaptan, n-dodecyl mercaptan, 4-methyl-2,4-diphenylpentene-1 may be added as a molecular weight adjusting agent, and diisobutyl adipate, butyl benzyl phthalate, or the like may be added as a plasticizer. .
- the mixing method is not particularly limited. For example, after premixing with a known mixing apparatus such as a Henschel mixer or a tumbler mixer, the mixture is melt-kneaded using an extruder such as a single screw extruder or a twin screw extruder. By performing the above, uniform mixing can be performed.
- the rubber-modified thermoplastic resin composition of the present embodiment includes a styrene / methacrylic acid ester copolymer (A), a styrene / vinyl cyanide copolymer (B), and a graft copolymer (C).
- arbitrary well-known additives can be mix
- plasticizers, lubricants, silicone oils and the like can be blended in order to improve fluidity and releasability.
- a light stabilizer and a ultraviolet absorber can be mix
- Other examples include antioxidants, antistatic agents, colorants, pigments, dyes, lubricants, antiblocking agents, foaming agents, foaming aids, crosslinking agents, and crosslinking aids.
- each raw material such as styrene-methacrylic acid ester copolymer (A), styrene-vinyl cyanide copolymer (B), and graft copolymer (C) is previously homogenized with a tumbler or Henschel mixer.
- a method in which the mixture is fed to a single-screw extruder or a twin-screw extruder, melt-kneaded, and adjusted as pellets.
- the rubber-modified styrenic resin composition of the present embodiment thus obtained can be processed into various molded bodies and put to practical use by methods such as injection molding, compression molding and extrusion molding.
- the rubber-modified styrenic resin composition of the form is injection molded by injection-molding this rubber-modified styrenic resin composition in order to satisfy the chemical resistance, transparency, hue, heat resistance, and impact resistance properties in a well-balanced manner.
- the body is extremely excellent in practice.
- the injection-molded product of the present embodiment can be obtained by molding the rubber-modified thermoplastic resin composition into a predetermined shape by injection molding.
- the injection-molded product of this embodiment is particularly effective when applied to containers and container lids that are required to satisfy chemical resistance, transparency, hue, heat resistance, and impact resistance in a well-balanced manner. .
- the raw material for obtaining this injection-molded body may be made of the above-mentioned rubber-modified thermoplastic resin composition, and the shape and the like are not particularly limited, but the handling property and moldability during injection molding are good. In order to do so, it is preferable to have a pellet shape.
- the temperature of injection molding of the rubber-modified thermoplastic resin composition is preferably in the range of, for example, 180 to 280 ° C. from the viewpoint of moldability and hue. If this injection temperature is 180 ° C. or higher, the fluidity of the rubber-modified thermoplastic resin composition is increased and the mold can be filled well, so that the moldability is improved. Moreover, if this injection temperature is 280 ° C. or lower, it is possible to suppress the occurrence of burns in the injection-molded product.
- the lid of the washing machine of the present embodiment is a lid of a washing machine using the above injection molded body as a member.
- the washing machine here generally means a machine that performs washing semi-automatically or fully automatically. However, it is not intended to exclude a manual washing machine that manually rotates the washing tub. Conventionally, opaque parts have generally been used for lids of washing machines. However, due to the recent increase in demand for design, a material having transparency and excellent hue is required for the lid. In addition, the lid of the washing machine is frequently exposed to the chemical solution due to the splashing of the detergent solution from the inside of the washing tub, and is susceptible to impacts caused by rotation of the washing tub and opening / closing of the lid by the user.
- the lid of the washing machine is required to satisfy the chemical resistance, transparency, hue, heat resistance, and impact resistance characteristics in a well-balanced manner.
- the injection-molded product satisfies the chemical resistance, transparency, hue, heat resistance, and impact resistance properties in a well-balanced manner, and thus is suitable as a member for such a transparent lid.
- the lid of the washing machine of the present embodiment does not need to be made of the above-described injection-molded body as a whole, for example, a transparent viewing window provided so that a user can look inside the washing tub of the washing machine. It may be used as a member.
- an injection-molded body that satisfies the above-mentioned properties of chemical resistance, transparency, hue, heat resistance, and impact resistance can be used only in a necessary range. Manufacturing costs can be reduced.
- the rubber-modified thermoplastic resin composition includes a styrene-methacrylic acid ester copolymer (A), a styrene-vinyl cyanide copolymer (B), and a graft copolymer. (C) is included, but it is not intended to exclude the inclusion of other types of resins or copolymers.
- polystyrene, MS resin, AS resin, ABS resin, acrylic resin, polycarbonate, and the like can be used as long as the object of the present invention is not impaired. It may be included as a polymer.
- Resin composition of styrene copolymer, vinyl cyanide content: FT-NMR (FX-90Q manufactured by JEOL Ltd.) was prepared as a measurement data by dissolving the copolymer in deuterated chloroform to prepare a 2% solution. 13 C was used and calculated from the peak areas of styrene, methyl methacrylate and acrylonitrile.
- the composition of the styrene-methacrylic acid ester copolymer grafted on the rubber-like elastic body is the same as that of the ungrafted styrene-methacrylic acid ester copolymer. Therefore, the measured value was taken as the composition of the styrene-methacrylic ester copolymer grafted on the rubber-like polymer.
- Refractive index of copolymer A molded product having a thickness of 2 mm was produced by press molding and measured using an Abbe refractometer (DR-M2) manufactured by Atago Co., Ltd.
- Refractive index of copolymer A molded product having a thickness of 2 mm was produced by press molding, and measured using an Abbe refractometer (DR-M2) manufactured by Atago Co., Ltd.
- Total light transmittance / HAZE Measured in accordance with ASTM D-1003 using a Nippon Denshoku Industries HAZE meter (NDH-2000). If the total light transmittance is 88% or more and HAZE is 7% or less, it can be judged that the transparency is good.
- Hue The b value was measured by a transmission method using a color difference meter ( ⁇ -80) manufactured by Nippon Denshoku. If the b value is 5 or less, it can be determined that the hue is excellent.
- MFR Measured under the conditions of a temperature of 220 ° C. and a load of 10 kg according to JIS K6874 using a sample pellet.
- Charpy impact strength A test piece having a size of 12.7 ⁇ 64 ⁇ 6.4 mm was formed at a cylinder temperature of 220 ° C. using Toshiba Machine Co., Ltd. (IS-80CNV). Using this test piece, measurement was performed in accordance with ISO 179-2. If the Charpy impact strength is 5 kJ / m 2 or more, it can be determined that the impact resistance is good.
- Vicat softening point A test piece having a size of 12.7 ⁇ 64 ⁇ 6.4 mm was molded at a cylinder temperature of 220 ° C. using an injection molding machine (IS-80CNV) manufactured by Toshiba Machine Co., Ltd. Using this test piece, measurement was performed under a load of 49.0 N in accordance with JIS K7206. If the Vicat softening point is 100 ° C. or higher, it can be determined that the heat resistance is good.
- volume average rubber particle diameter of the graft copolymer measured using a Beckman Coulter Coalter Multisizer (LS230). The volume average particle size here is measured with a light scattering particle size distribution analyzer by dissolving the graft copolymer (C) and the rubber-modified thermoplastic resin composition in N, N-dimethylformamide (DMF). The volume-based median diameter.
- this polymerization solution was supplied to a tower type plug flow type continuous reaction vessel adjusted so as to have a gradient of 125 ° C. to 144 ° C. in the flow direction, and polymerized.
- the conversion rate at the outlet of the column type plug flow type continuous reaction vessel was controlled to 75 to 78%.
- this polymerization solution was heated to 230 ° C. with a preheater, it was introduced into a flash-type devolatilization tank depressurized to 1.3 kPa, and unreacted monomers were removed at a tank temperature of 235 ° C.
- the resin at 232 ° C. was extracted with a gear pump, and extruded and cut into strands to obtain pellet-shaped styrene-methacrylic acid ester copolymer (a-1).
- Styrene-methacrylate copolymer (a-2) The same procedure as in (a-1) was carried out except that a monomer solution consisting of 79.8% by weight of methyl methacrylate, 2.2% by weight of styrene and 18.0% by weight of ethylbenzene was used. An ester copolymer (a-2) was obtained.
- Styrene-methacrylic acid ester copolymer (a-3) The same procedure as in (a-1) was conducted except that a monomer solution consisting of 70.0% by mass of methyl methacrylate, 18.0% by mass of styrene, and 12.0% by mass of ethylbenzene was used. An ester copolymer (a-3) was obtained.
- Styrene-methacrylate copolymer (a-4) A styrene-methacrylic acid ester copolymer (a-4) was obtained in the same manner as (a-1) except that the amount of n-dodecyl mercaptan was changed to 0.45 parts by mass.
- Styrene-methacrylic acid ester copolymer (a-5) A styrene-methacrylic acid ester copolymer (a-5) was obtained in the same manner as in (a-1) except that the amount of n-dodecyl mercaptan was changed to 0.20 parts by mass.
- Polymethyl methacrylate (a-6) As polymethyl methacrylate, Kuraray Parapet G was used.
- Styrene-methacrylic acid ester copolymer (a-7) A monomer mixture of 52 kg of styrene, 38 kg of methyl methacrylate and 10 kg of acrylonitrile, 80 g of benzoyl peroxide as a polymerization initiator and 300 g of t-dodecyl mercaptan as a chain transfer agent were added to a 200 L autoclave at a temperature of 95 ° C. while stirring. After heating for 2 hours at a temperature of 130 ° C., the suspension polymerization was stopped by cooling. After completion of the reaction, washing, dehydration and drying were performed to obtain a bead-like styrene-methacrylic acid ester copolymer (a-7).
- Styrene-methacrylic acid ester copolymer (a-8) Styrene-methacrylic acid was carried out in the same manner as in (a-1) except that a monomer solution consisting of 43.0% by mass of methyl methacrylate, 45.0% by mass of styrene and 12.0% by mass of ethylbenzene was used. An ester copolymer (a-8) was obtained.
- compositions of the styrene-methacrylic acid ester copolymers (a-1) to (a-8) described so far are summarized in Table 1 below.
- reaction liquid was continuously withdrawn from the complete mixing type reactor, supplied to a tower type plug flow type continuous reaction tank adjusted so as to have a gradient of 130 ° C. to 160 ° C. in the flow direction, and polymerized. While this polymerization solution was heated to 230 ° C. with a preheater, it was introduced into a flash-type devolatilization tank depressurized to 1.0 kPa, and unreacted monomers were removed at a tank temperature of 235 ° C. The resin was extracted with a gear pump and extruded and cut into strands to obtain pellet-shaped styrene-vinyl cyanide copolymer (b-1).
- Styrene-vinyl cyanide copolymer (b-2) A styrene-acrylonitrile copolymer (b-2) was obtained in the same manner as (b-1) except that 70 parts by mass of styrene and 30 parts by mass of acrylonitrile were used.
- Styrene-vinyl cyanide copolymer (b-3) A styrene-acrylonitrile copolymer (b-3) was obtained in the same manner as (b-1) except that 88 parts by mass of styrene and 12 parts by mass of acrylonitrile were used.
- Styrene-vinyl cyanide copolymer (b-4) A styrene-acrylonitrile copolymer (b-4) was obtained in the same manner as (b-1) except that 92 parts by mass of styrene and 8 parts by mass of acrylonitrile were used.
- Styrene-vinyl cyanide copolymer (b-5) Except that n-dodecyl mercaptan was changed to 0.035 parts by mass, the same procedure as in (b-1) was carried out, A styrene-acrylonitrile copolymer (b-5) was obtained.
- Styrene-vinyl cyanide copolymer (b-6) Except that n-dodecyl mercaptan was changed to 0.04 parts by mass, the same procedure as in (b-1) was carried out, A styrene-acrylonitrile copolymer (b-6) was obtained.
- Styrene-vinyl cyanide copolymer (b-7) Except that the amount of n-dodecyl mercaptan was changed to 0.015 part by mass, the same procedure as in (b-1) was performed, A styrene-acrylonitrile copolymer (b-7) was obtained.
- compositions of the styrene-vinyl cyanide copolymers (b-1) to (b-7) described so far are summarized in Table 2 below.
- Graft copolymer production method Graft copolymer (c-1) Styrene-butadiene latex (styrene content 40% by mass, rubber particle diameter 0.3 ⁇ m) 36 kg in terms of solid content is weighed and transferred to an autoclave with a volume of 200 L equipped with a stirrer, and the water content is combined with the water content in polybutadiene latex. Pure water was added to 100 kg, and the temperature was raised to 50 ° C. in a nitrogen atmosphere while stirring.
- the temperature was raised to 70 ° C., 24 g of diisopropylbenzene hydroperoxide was further added, and the mixture was left for 2 hours to complete the polymerization.
- Antioxidant is added to the obtained emulsion, the solid content is diluted to 15% by mass with pure water, the temperature is raised to 70 ° C., dilute sulfuric acid is added with vigorous stirring, and salting out is performed.
- the mixture was heated to 95 ° C. for solidification, then dehydrated, washed with water, and dried to obtain a powdered graft copolymer (c-1).
- the obtained graft copolymer had a volume average particle size of 0.35 ⁇ m.
- Graft copolymer (c-2) The same procedure as in (c-1) was conducted except that 1.2 kg of acrylonitrile, 12.7 kg of styrene, and 10.1 kg of methyl methacrylate were added to 36 kg of styrene-butadiene latex to obtain a graft copolymer (c-2). .
- the obtained graft copolymer had a volume average particle size of 0.35 ⁇ m.
- Graft copolymer (c-3) A graft copolymer (c-3) was obtained in the same manner as (c-1) except that 2.8 kg of acrylonitrile, 11.6 kg of styrene, and 9.6 kg of methyl methacrylate were added to 36 kg of styrene-butadiene latex. .
- the obtained graft copolymer had a volume average particle size of 0.35 ⁇ m.
- Graft copolymer (c-4) A graft copolymer (c-4) was obtained in the same manner as in (c-1) except that 9.6 kg of styrene and 14.4 kg of methyl methacrylate were added to 30 kg of styrene-butadiene latex. The obtained graft copolymer had a volume average particle size of 0.35 ⁇ m.
- Graft copolymer (c-5) A graft copolymer (c-5) was obtained in the same manner as (c-1) except that a styrene-butadiene latex having a rubber particle diameter of 0.2 ⁇ m was used. The obtained graft copolymer had a volume average particle size of 0.23 ⁇ m.
- Graft copolymer (c-6) A graft copolymer (c-6) was obtained in the same manner as (c-1) except that a styrene-butadiene latex having a rubber particle diameter of 0.6 ⁇ m was used. The obtained graft copolymer had a volume average particle size of 0.65 ⁇ m.
- Graft copolymer (c-7) A graft copolymer (c-7) was obtained in the same manner as in (c-1) except that a styrene-butadiene latex having a rubber particle diameter of 0.8 ⁇ m was used. The obtained graft copolymer had a volume average particle size of 0.82 ⁇ m.
- Graft copolymer (c-8) The same procedure as in (c-1) was conducted except that a styrene-butadiene latex having a styrene content of 25% by mass was used, and 9.6 kg of styrene and 14.4 kg of methyl methacrylate were added to 36 kg of the styrene-butadiene latex. A graft copolymer (c-8) was obtained. The obtained graft copolymer had a volume average particle size of 0.35 ⁇ m.
- Graft copolymer (c-9) The same procedure as in (c-1) was carried out except that 13.4 kg of styrene, 9.4 kg of methyl methacrylate and 1.2 kg of n-butyl acrylate were added to 30 kg of styrene-butadiene latex, and the graft copolymer (c-9) ) The obtained graft copolymer had a volume average particle size of 0.35 ⁇ m.
- compositions of the graft copolymers (c-1) to (c-7) described so far are summarized in Table 3 below.
- Examples 1 to 15 and Comparative Examples 1 to 13 Styrene-methacrylic acid ester copolymers (a-1) to (a-7), styrene-vinyl cyanide copolymers (b-1) to (b-7), grafts obtained by the above method
- a Henschel mixer at the blending ratios shown in Tables 4 to 6
- a twin-screw extruder (TEM35B manufactured by Toshiba Machine Co., Ltd., cylinder temperature 220 ° C.) was used.
- the resulting mixture was melt-kneaded to produce pellets to obtain a rubber-modified thermoplastic resin composition.
- the pellet was then injection molded to obtain a molded body.
- the obtained molded products were evaluated for transparency and hue, and are shown in Tables 4-6.
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Abstract
Description
第一に、特許文献2~4では、スチレン-アクリロニトリル-メタクリル酸メチルの共重合体とグラフト系共重合体からなる樹脂組成物は、高ニトリルになるに伴い色相が悪くなるという問題を有していた。
本願明細書において、「~」という記号は「以上」及び「以下」を意味し、「~」で示された上限値及び下限値をそれぞれ含むものとする。例えば、「A~B」なる記載は、A以上でありB以下であることを意味する。また、「を含有する」には、「から実質的になる」および「からなる」が含まれるものとする。
本実施形態によれば、スチレン-メタクリル酸エステル系共重合体(A)と、スチレン-シアン化ビニル系共重合体(B)と、グラフト系共重合体(C)と、を含有するゴム変性熱可塑性樹脂組成物が提供される。本実施形態のゴム変性熱可塑性樹脂組成物は、これらの成分(A)、成分(B)および成分(C)を、後述する特定の条件および配合組成を満たすように含有するため、一般的には互いにトレードオフの関係にあって同時に満足させることが困難であるとされている、耐薬品性、透明性、色相、耐熱性、耐衝撃性にバランスよく優れる。
上記の(A)成分は、スチレン系単量体単位およびメタクリル酸エステル系単量体単位を含むスチレン-メタクリル酸エステル系共重合体である。このスチレン-メタクリル酸エステル系共重合体の構造は、特に限定されず、スチレン系単量体単位およびメタクリル酸エステル系単量体単位を含む任意の構造の共重合体を用いることができる。すなわち、共重合体には、大きく分類して、ランダム共重合体、交互共重合体、周期的共重合体、ブロック共重合体の4種類の構造があり、ブロック共重合体の一種にグラフト系共重合体(幹となる高分子鎖に、異種の枝高分子鎖が結合した枝分かれ構造の共重合体)があるが、いずれの構造の共重合体であってもよい。
カラム:PL Gel MIXED-Bを直列3本
温度:40℃
検出:示差屈折計
溶媒:THF(テトラヒドロフラン)
濃度:2質量%
検量線:標準ポリスチレン(PS)(PL社製)を用いて作成し、重量平均分子量(Mw)はPS換算値で表した。
上記の(B)成分は、スチレン系単量体単位およびシアン化ビニル系単量体単位を含むスチレン-シアン化ビニル系共重合体である。このスチレン-シアン化ビニル系共重合体の構造は、特に限定されず、スチレン系単量体単位およびシアン化ビニル系単量体単位を含む任意の構造の共重合体を用いることができる。すなわち、共重合体には、大きく分類して、ランダム共重合体、交互共重合体、周期的共重合体、ブロック共重合体の4種類の構造があり、ブロック共重合体の一種にグラフト系共重合体(幹となる高分子鎖に、異種の枝高分子鎖が結合した枝分かれ構造の共重合体)があるが、いずれの構造の共重合体であってもよい。
上記の(C)成分は、ゴム状弾性体に、スチレン系単量体と、メタクリル酸エステル系単量体と、シアン化ビニル系単量体とを共重合してなるグラフト系共重合体である。このグラフト系共重合体の構造は、特に限定されず、ゴム状弾性体に、スチレン系単量体と、メタクリル酸エステル系単量体と、シアン化ビニル系単量体とを共重合してなる任意のグラフト系共重合体を用いることができる。すなわち、一般的な幹となる高分子鎖に、異種の枝高分子鎖が結合した枝分かれ構造のグラフト系共重合体であればよい。
本実施形態のゴム変性熱可塑性樹脂組成物では、上記(A)成分、(B)成分および(C)成分の合計質量を100質量%とした場合に、耐薬品性、透明性、耐熱性、耐衝撃性に優れるゴム変性熱可塑性樹脂組成物を得るためには、上記(A)成分(スチレン-メタクリル酸エステル系共重合体)は15~54質量%、上記(B)成分(スチレン-シアン化ビニル系共重合体)は20~63質量%、上記(C)成分(グラフト系共重合体)は10~50質量%の範囲内で含有されていることが好ましい。
本実施形態のゴム変性熱可塑性樹脂組成物を構成する上記のスチレン-メタクリル酸エステル系共重合体(A)およびスチレン-シアン化ビニル系共重合体(B)の製造方法は、特に限定されず、塊状重合法、懸濁重合法、塊状-懸濁重合法、溶液重合法、乳化重合法等の任意の公知の重合法を用いることができるが、耐熱性とより良好な色相と透明性を得るためには上記の(A)成分および(B)成分の各共重合体が連続塊状重合によって重合されたものであることが好ましい。
本実施形態の射出成形体は、上記のゴム変性熱可塑性樹脂組成物を、射出成形によって所定形状に成形することによって得ることができる。本実施形態の射出成形体はとくに、耐薬品性、透明性、色相、耐熱性、耐衝撃性の特性をバランスよく満たすことを求められる容器や容器の蓋材に適用するのが効果的である。
本実施形態の洗濯機の蓋は、上記の射出成形体を部材として用いた洗濯機の蓋である。なお、ここでいう洗濯機は、一般的には洗濯を半自動または全自動で行う機械を意味する。もっとも、洗濯槽の回転を手動で行う手動式洗濯機を排除する趣旨ではない。従来、洗濯機の蓋には、一般的には不透明な部品が使用されてきた。しかしながら、近年のデザイン性に対する要求の高まりから、蓋に透明性および優れた色相を有する材料が求められている。また、洗濯機の蓋は、洗濯槽内からの洗剤溶液の跳ね返りなどによって頻繁に薬品溶液にさらされ、洗濯槽の回転および使用者による蓋の開閉にともなう衝撃を受けやすく、さらに洗濯機内部の機械駆動部からの発熱および使用者がお湯を用いて洗濯をする場合には洗剤溶液の高温にさらされる場合もある。そのため、洗濯機の蓋には、耐薬品性、透明性、色相、耐熱性、耐衝撃性の特性をバランスよく満たすことが求められる。これに対して、上記の射出成形体は、耐薬品性、透明性、色相、耐熱性、耐衝撃性の特性をバランスよく満たすため、このような透明な蓋の部材として適している。
本実施例において用いたスチレン-メタクリル酸エステル系共重合体、スチレン-シアン化ビニル系共重合体、グラフト系共重合体およびゴム変性熱可塑性樹脂組成物を構成する各種測定値および実施した各物性値の測定方法を以下に説明する。
ここでいう体積平均粒子径とは、N,N-ジメチルホルムアミド(DMF)にグラフト系共重合体(C)及び、ゴム変性熱可塑性樹脂組成物を溶解させて光散乱式粒度分布測定装置で測定した体積基準のメジアン径である。
a:1/4楕円法治具の長軸(mm)
b:1/4楕円法治具の短軸(mm)
t:試験片厚み(mm)
X:クラック発生点(mm)
である。
(a)スチレン-メタクリル酸エステル系共重合体の製造方法
スチレン-メタクリル酸エステル系共重合体(a-1)
攪拌翼を備えた容積約20Lの完全混合型連続反応槽、容積約11Lの塔式プラグフロー型連続反応槽、予熱器を備えたフラッシュ型脱揮槽を直列に接続して構成した。メタクリル酸メチル79.2質量%、スチレン8.8質量%、エチルベンゼン12.0質量%で構成する溶液に対し、t-ブチルパーオキシイソプロピルモノカーボネート0.0073質量部、n-ドデシルメルカプタン0.32質量部を混合し原料溶液とした。この原料溶液を毎時3.9kgで温度125℃に保った完全混合型連続反応槽に供給し、重合した。完全混合型連続反応槽出口における転化率は55~58%に制御した。さらにこの重合溶液を流れの方向に向かって125℃から144℃の勾配がつくように調整した塔式プラグフロー型連続反応槽に供給し、重合した。塔式プラグフロー型連続反応槽出口における転化率を75~78%に制御した。この重合溶液を予熱器で230℃に加温しながら、1.3kPaに減圧したフラッシュ型脱揮槽に導入し、槽内温度235℃にて未反応単量体を除去した。232℃の樹脂をギアポンプで抜き出し、ストランド状に押出し切断することにより、ペレット形状のスチレン-メタクリル酸エステル系共重合体(a-1)を得た。
メタクリル酸メチル79.8質量%、スチレン2.2質量%、エチルベンゼン18.0質量%で構成する単量体溶液を用いた以外は、(a-1)と同様に実施し、スチレン-メタクリル酸エステル系共重合体(a-2)を得た。
メタクリル酸メチル70.0質量%、スチレン18.0質量%、エチルベンゼン12.0質量%で構成する単量体溶液を用いた以外は、(a-1)と同様に実施し、スチレン-メタクリル酸エステル系共重合体(a-3)を得た。
n-ドデシルメルカプタンの量を0.45質量部にした以外は、(a-1)と同様に実施し、スチレン-メタクリル酸エステル系共重合体(a-4)を得た。
n-ドデシルメルカプタンの量を0.20質量部にした以外は、(a-1)と同様に実施し、スチレン-メタクリル酸エステル系共重合体(a-5)を得た。
ポリメチルメタクリレートとして、株式会社クラレのパラペットGを用いた。
容量200Lのオートクレーブにスチレン52kg、メチルメタクリレート38kg及びアクリロニトリル10kgの単量体混合物、重合開始剤としてベンゾイルパーオキサイド80g、連鎖移動剤としてt-ドデシルメルカプタン300gを添加し、攪拌しながら温度95℃で6時間、さらに温度130℃で2時間加熱した後、冷却して懸濁重合を停止した。反応終了後、洗浄、脱水、乾燥しビーズ状のスチレン-メタクリル酸エステル系共重合体(a-7)を得た。
メタクリル酸メチル43.0質量%、スチレン45.0質量%、エチルベンゼン12.0質量%で構成する単量体溶液を用いた以外は、(a-1)と同様に実施し、スチレン-メタクリル酸エステル系共重合体(a-8)を得た。
スチレン-シアン化ビニル系共重合体(b-1)
撹拌機を備えた容積約20リットルの完全混合型連続反応槽、容積約40Lの塔式プラグフロー型連続反応槽、予熱器を備えたフラッシュ型脱揮槽を直列に接続して構成した。スチレン81質量部、アクリロニトリル19質量部、エチルベンゼン10質量部で構成する溶液に対し、t-ブチルパーオキシイソプロピルモノカーボネート0.02質量部とn-ドデシルメルカプタン0.02質量部を混合し原料溶液とした。この原料溶液を毎時6.0kgで温度130℃に制御した完全混合型連続反応槽に供給し、重合した。なお、完全混合型反応器の撹拌数は180rpmで実施した。さらに完全混合型反応器より反応液を連続的に抜き出し、流れの方向に向かって温度130℃から160℃の勾配がつくように調整した塔式プラグフロー型連続反応槽に供給し、重合した。この重合溶液を予熱器で230℃に加温しながら、1.0kPaに減圧したフラッシュ型脱揮槽に導入し、槽内温度235℃にて未反応単量体を除去した。この樹脂をギアポンプで抜き出し、ストランド状に押出し切断することによりペレット形状のスチレン-シアン化ビニル系共重合体(b-1)を得た。
スチレン70質量部、アクリロニトリル30質量部とした以外は、(b-1)と同様に行い、スチレン-アクリロニトリル系共重合体(b-2)を得た。
スチレン88質量部、アクリロニトリル12質量部とした以外は、(b-1)と同様に行い、スチレン-アクリロニトリル系共重合体(b-3)を得た。
スチレン92質量部、アクリロニトリル8質量部とした以外は、(b-1)と同様に行い、スチレン-アクリロニトリル系共重合体(b-4)を得た。
n-ドデシルメルカプタンを0.035質量部とした以外は、(b-1)と同様に行い、
スチレン-アクリロニトリル系共重合体(b-5)を得た。
n-ドデシルメルカプタンを0.04質量部とした以外は、(b-1)と同様に行い、
スチレン-アクリロニトリル系共重合体(b-6)を得た。
n-ドデシルメルカプタンを0.015質量部とした以外は、(b-1)と同様に行い、
スチレン-アクリロニトリル系共重合体(b-7)を得た。
グラフト系共重合体(c-1)
スチレン-ブタジエンラテックス(スチレン含有量40質量%、ゴム粒子径0.3μm)固形分換算で36kg計量して攪拌機を備えた容積200Lのオートクレーブに移し、水分量がポリブタジエンラテックス中の水分量とあわせて100kgになるよう純水を加え、攪拌しながら窒素雰囲気下で温度50℃に昇温した。ここに硫酸第一鉄1.8g、エチレンジアミンテトラ酢酸ナトリウム3.6g、ロンガリット108gを純水2kgに溶解したものを加え、スチレン13.2kg、メチルメタクリレート10.8kg、t-ドデシルメルカプタン240gからなる混合物と、ジイソプロピルベンゼンハイドロパーオキサイド48g、オレイン酸カリウム450gを純水8kgに分散した溶解液とを別々に6時間かけて連続添加した。添加終了後、温度を70℃に昇温し、さらにジイソプロピルベンゼンハイドロパーオキサイド24g添加した後2時間放置して重合を終了させた。得られた乳化液に酸化防止剤を加え、純水で固形分を15質量%に希釈した後に温度70℃に昇温し、烈しく攪拌しながら希硫酸を加えて塩析を行い、その後温度を95℃に昇温して凝固させ、次に脱水、水洗、乾燥して粉末状のグラフト系共重合体(c-1)を得た。
得られたグラフト系共重合体の体積平均粒子径は0.35μmであった。
スチレン-ブタジエンラテックス36kgにアクリロニトリル1.2kg、スチレン12.7kg、メチルメタクリレート10.1kgを添加した以外は(c-1)と同様に実施し、グラフト系共重合体(c-2)を得た。
得られたグラフト系共重合体の体積平均粒子径は0.35μmであった。
スチレン-ブタジエンラテックス36kgにアクリロニトリル2.8kg、スチレン11.6kg、メチルメタクリレート9.6kgを添加した以外は(c-1)と同様に実施し、グラフト系共重合体(c-3)を得た。
得られたグラフト系共重合体の体積平均粒子径は0.35μmであった。
スチレン-ブタジエンラテックス30kgにスチレン9.6kg、メチルメタクリレート14.4kgを添加した以外は(c-1)と同様に実施し、グラフト系共重合体(c-4)を得た。
得られたグラフト系共重合体の体積平均粒子径は0.35μmであった。
ゴム粒子径0.2μmのスチレン-ブタジエンラテックスを用いた以外は(c-1)と同様に実施し、グラフト系共重合体(c-5)を得た。
得られたグラフト系共重合体の体積平均粒子径は0.23μmであった。
ゴム粒子径0.6μmのスチレン-ブタジエンラテックスを用いた以外は(c-1)と同様に実施し、グラフト系共重合体(c-6)を得た。
得られたグラフト系共重合体の体積平均粒子径は0.65μmであった。
ゴム粒子径0.8μmのスチレン-ブタジエンラテックスを用いた以外は(c-1)と同様に実施し、グラフト系共重合体(c-7)を得た。
得られたグラフト系共重合体の体積平均粒子径は0.82μmであった。
スチレン-ブタジエンラテックスとしてスチレン含有量が25質量%のものを用い、そのスチレン-ブタジエンラテックス36kgにスチレン9.6kg、メチルメタクリレート14.4kgを添加した以外は(c-1)と同様に実施し、グラフト系共重合体(c-8)を得た。
得られたグラフト系共重合体の体積平均粒子径は0.35μmであった。
スチレン-ブタジエンラテックス30kgにスチレン13.4kg、メチルメタクリレート9.4kg、n-ブチルアクリレート1.2kg、を添加した以外は(c-1)と同様に実施し、グラフト系共重合体(c-9)を得た。
得られたグラフト系共重合体の体積平均粒子径は0.35μmであった。
上記の方法で得られたスチレン-メタクリル酸エステル系共重合体(a-1)~(a-7)、スチレン-シアン化ビニル系共重合体(b-1)~(b-7)、グラフト系共重合体(c-1)~(c-11)を表4~6に示す配合割合にてヘンシェルミキサーで混合した後、二軸押出機(東芝機械社製TEM35B、シリンダー温度220℃)を用いて溶融混練してペレットを作成しゴム変性熱可塑性樹脂組成物を得た。次いでこのペレットを射出成形し、成形体を得た。得られた成形体の透明性、色相を評価し、表4~6に示した。
上記の表4~6に示されるように、実施例1~17のゴム変性熱可塑性樹脂組成物はいずれも耐薬品性、透明性、色相、耐熱性、耐衝撃性にバランスよく優れることが明らかである。これに対して、比較例1~10のゴム変性熱可塑性樹脂組成物の少なくとも1つ以上の特性が実施例1~17に比べて劣っているため、耐薬品性、透明性、色相、耐熱性、耐衝撃性をバランスよく実現できていなかった。
b 1/4楕円法治具の短軸
X クラック発生点
Claims (7)
- スチレン系単量体単位およびメタクリル酸エステル系単量体単位の合計質量を100質量%とした場合に、スチレン系単量体単位が1~15質量%、メタクリル酸エステル系単量体単位が85~99質量%の範囲内で含まれているスチレン-メタクリル酸エステル系共重合体(A)と、
スチレン系単量体単位およびシアン化ビニル系単量体単位の合計質量を100質量%とした場合に、スチレン系単量体単位が80~90質量%、シアン化ビニル系単量体単位が10~20質量%の範囲内で含まれているスチレン-シアン化ビニル系共重合体(B)と、
ゴム状弾性体に、スチレン系単量体と、メタクリル酸エステル系単量体と、シアン化ビニル系単量体とを共重合してなり、かつプレス成形した場合の厚み2mmの成形体の全光線透過率が85%以上であるグラフト系共重合体(C)とを含有し、
スチレン-メタクリル酸エステル系共重合体(A)、スチレン-シアン化ビニル系共重合体(B)およびグラフト系共重合体(C)成分の合計質量を100質量%とした場合に、スチレン-メタクリル酸エステル系共重合体(A)が15~54質量%、スチレン-シアン化ビニル系共重合体(B)が20~63質量%、グラフト系共重合体(C)が10~50質量%の範囲内で含有されており、
スチレン-メタクリル酸エステル系共重合体(A)およびスチレン-シアン化ビニル系共重合体(B)の混合物の屈折率と、グラフト系共重合体(C)の屈折率との差が0.005以下であり、
スチレン-メタクリル酸エステル系共重合体(A)およびスチレン-シアン化ビニル系共重合体(B)成分の合計質量を100質量%とした場合に、スチレン-メタクリル酸エステル系共重合体(A)およびスチレン-シアン化ビニル系共重合体(B)の混合物中のシアン化ビニル系単量体単位が6~15質量%の範囲内である、
ゴム変性熱可塑性樹脂組成物。 - スチレン-メタクリル酸エステル系共重合体(A)の重量平均分子量が70,000~100,000の範囲内であり、スチレン-シアン化ビニル系共重合体(B)の分子量が100,000~190,000の範囲内である、請求項1に記載のゴム変性熱可塑性樹脂組成物。
- グラフト系共重合体(C)の体積平均粒子径が0.25~0.80μmの範囲内である、請求項1または2記載のゴム変性熱可塑性樹脂組成物。
- スチレン-メタクリル酸エステル系共重合体(A)の製造方法が連続塊状重合である、請求項1乃至3いずれかに記載のゴム変性熱可塑性樹脂組成物。
- スチレン-シアン化ビニル系共重合体(B)の製造方法が連続塊状重合である、請求項1乃至4いずれかに記載のゴム変性熱可塑性樹脂組成物。
- 請求項1乃至5いずれかに記載のゴム変性熱可塑性樹脂組成物を射出成形してなる射出成形体。
- 請求項6に記載の射出成形体を部材として用いた洗濯機の蓋。
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JP2012046648A (ja) * | 2010-08-27 | 2012-03-08 | Nippon A&L Inc | 熱可塑性樹脂組成物及び樹脂成形品 |
JP2012251015A (ja) * | 2011-05-31 | 2012-12-20 | Techno Polymer Co Ltd | 熱可塑性樹脂組成物およびそれを用いてなる成形品 |
WO2022202557A1 (ja) * | 2021-03-23 | 2022-09-29 | デンカ株式会社 | 熱可塑性樹脂組成物およびその製造方法 |
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