Classifications

• • 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
• • 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
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
  • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/12—Copolymers of styrene with unsaturated nitriles
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/30—Applications used for thermoforming
• • 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
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • 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
• • 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
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

• the present invention relates to a thermoplastic resin composition that has excellent heat resistance, impact resistance, and fluidity as moldability, and can provide molded products with excellent paintability and durability.
• the present invention also relates to a thermoplastic resin molded article using this thermoplastic resin composition.
• the present invention also relates to a painted part made of this thermoplastic resin molded product.
• Rubber-reinforced styrene resins represented by ABS resins, have excellent impact resistance, mechanical strength, and chemical resistance, so they are used in office-related equipment, information and communication equipment, electronic and electrical equipment, home appliances, It is used in a wide range of fields, including interior and exterior parts of automobiles, exterior parts of motorcycles, interior parts of railway vehicles, and building materials.
• ABS resin specific gravity 1.07
• polycarbonate resin specific gravity 1.14 to 1.17
• Patent Documents 1 and 2 propose thermoplastic resin compositions with excellent heat resistance and paintability.
• Patent Document 1 discloses a maleimide-based heat-resistant and paint-resistant thermoplastic resin composition.
• the thermoplastic resin composition of Patent Document 1 has problems such as insufficient paintability (flanks) at areas where stress is applied such as the surface of a molded product; gas generation during molding; and insufficient durability. There is.
• Patent Document 2 discloses a heat-resistant and paint-resistant thermoplastic resin composition containing two or more types of copolymers.
• the thermoplastic resin composition of Patent Document 2 also has insufficient paintability (armpit) at areas where stress is applied, such as the surface of a molded product; insufficient heat resistance; insufficient durability; There are problems like this.
• An object of the present invention is to provide a thermoplastic resin composition that has excellent heat resistance, impact resistance, and fluidity, and also has excellent paintability and durability of the resulting thermoplastic resin molded product.
• the present inventor has developed a method that contains a specific rubber-containing graft copolymer (A), a vinyl cyanide-maleimide copolymer (B), and a vinyl cyanide-aromatic vinyl copolymer (C) in a predetermined ratio. It has been found that a thermoplastic resin composition in which the total content of maleimide monomer units is within a predetermined range can solve the above problems.
• the present invention facilitates:
• thermoplastic resin composition comprising a total of 100 parts by mass of The content of maleimide monomer units in the thermoplastic resin composition is determined by the rubber-containing graft copolymer (A), the vinyl cyanide-maleimide copolymer (B), and the vinyl cyanide-aromatic vinyl copolymer.
• the other vinyl monomer (b3) is selected from aromatic vinyl monomers, unsaturated carboxylic acid ester monomers, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and unsaturated amides.
• thermoplastic resin molded article obtained by molding the thermoplastic resin composition according to any one of [1] to [4].
• thermoplastic resin composition that is excellent in heat resistance, impact resistance, and fluidity, and also has excellent paintability and durability of the resulting thermoplastic resin molded product.
• Molded products made from the thermoplastic resin composition of the present invention have excellent heat resistance, impact resistance, paintability, and durability, and therefore are suitable for use in office-related equipment, information/communication equipment, electronic/electrical equipment, home appliances, automobiles, etc. It can be applied to a wide range of fields such as interior and exterior parts of cars, exterior parts of motorcycles, interior parts of railway vehicles, and building materials.
• the thermoplastic resin molded article of the present invention is suitably used for vehicle applications.
• thermoplastic resin composition includes: A rubber-containing graft copolymer obtained by graft polymerizing a vinyl monomer mixture (a2) containing a vinyl cyanide monomer and an aromatic vinyl monomer in the presence of a rubbery polymer (a1).
• A) (hereinafter sometimes referred to as "component (A)") 10 to 50 parts by mass; Vinyl cyanide monomer (b1) 5 to 30% by mass, maleimide monomer (b2) 20 to 60% by mass, and other vinyl monomer copolymerizable with these (b3) 10 to 75%.
• Vinyl cyanide-maleimide copolymer (B) (hereinafter referred to as "component (B)") obtained by copolymerizing % by mass (however, the total of (b1), (b2), and (b3) is 100% by mass) ) 5 to 90 parts by mass
• a vinyl cyanide-aromatic vinyl copolymer (C) obtained by copolymerizing a vinyl monomer mixture (c1) containing a vinyl cyanide monomer and an aromatic vinyl monomer (hereinafter referred to as " A thermoplastic resin composition containing a total of 100 parts by mass of 0 to 45 parts by mass (sometimes referred to as "component (C)"),
• the content of maleimide monomer units in the thermoplastic resin composition is determined by the rubber-containing graft copolymer (A), the vinyl cyanide-maleimide copolymer (B), and the vinyl cyanide-aromatic vinyl copolymer. It is characterized in that the proportion is 10 to 45 parts by mass based on
• the rubber-containing graft copolymer (A) is obtained by graft polymerizing a vinyl monomer mixture (a2) in the presence of a rubbery polymer (a1).
• the rubbery polymer (a1) (hereinafter sometimes referred to as "component (a1)") constituting the rubber-containing graft copolymer (A) is not particularly limited, but diene-based rubbers, acrylic-based Examples include rubber and ethylene rubber.
• These rubbery polymers may be used alone or in a mixture of two or more.
• polybutadiene, polybutyl acrylate, and poly(butadiene-styrene) are preferably used from the viewpoint of improving the impact resistance of the thermoplastic resin composition of the present invention.
• the volume average particle diameter of the rubbery polymer (a1) is preferably 50 to 500 nm, more preferably from the viewpoint of impact resistance, moldability, fluidity, and appearance of the thermoplastic resin composition obtained.
• the wavelength is 180 to 440 nm, more preferably 280 to 380 nm.
• the volume average particle diameter of the rubbery polymer (a1) is a value measured by the method described in the Examples section below.
• the vinyl monomer mixture (a2) (hereinafter sometimes referred to as "component (a2)") is a vinyl monomer mixture containing at least an aromatic vinyl monomer and a vinyl cyanide monomer. It is a mixture.
• aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene, and o,p-dichlorostyrene. These may be used alone or in combination of two or more.
• vinyl cyanide monomers examples include acrylonitrile, methaacrylonitrile, ethacrylonitrile, and the like, with acrylonitrile being particularly preferred.
• vinyl cyanide monomers only one type may be used, or two or more types may be used in combination.
• the vinyl monomer mixture (a2) contains, in addition to aromatic vinyl monomers and vinyl cyanide monomers, other vinyl monomers copolymerizable with these in a range of 0 to 30% by mass. may be included.
• Other vinyl monomers that can be copolymerized with these include unsaturated carboxylic acid ester monomers such as methyl (meth)acrylate, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, etc. Examples include one or more of maleimide monomers, unsaturated dicarboxylic acids such as maleic acid, unsaturated dicarboxylic anhydrides such as maleic anhydride, and unsaturated amides such as acrylamide, but are not limited to these.
• (Meth)acrylic acid refers to one or both of acrylic acid and methacrylic acid.
• the rubber-containing graft copolymer (A) is obtained by graft polymerizing 25 to 80% by mass of a vinyl monomer mixture (a2) in the presence of 20 to 75% by mass of a rubbery polymer (a1). It is preferable that there be. However, the total amount of the rubbery polymer (a1) and the vinyl monomer mixture (a2) is 100% by mass.
• the resulting thermoplastic resin composition tends to have poor impact resistance. If the rubbery polymer (a1) exceeds 75% by mass and the vinyl monomer mixture (a2) exceeds 25% by mass, impact resistance and moldability tend to decrease.
• the proportion of the rubbery polymer (a1) is preferably 30 to 70% by mass, more preferably 40 to 65% by mass, and the proportion of the vinyl monomer mixture (a2) is preferably 30 to 70% by mass, More preferably, it is 35 to 60% by mass.
• the rubber-containing graft copolymer (A) does not require that the entire amount of the vinyl monomer mixture (a2) be grafted, and usually one obtained as a mixture with a non-grafted copolymer is used. do. Although this mixture is originally a composition, it is included in the rubber-containing graft copolymer (A) in the present invention.
• grafting rate of the rubber-containing graft copolymer (A) is preferably 10 to 150% by mass, more preferably 15 to 100% by mass, and even more preferably 20 to 60% by mass. be.
• the graft ratio of the rubber-containing graft copolymer (A) is measured by the method described in the Examples section below.
• the composition of the non-grafted copolymer in the rubber-containing graft copolymer (A) falls within the range of the blending ratio of the monomer components.
• the weight average molecular weight (Mw) of the ungrafted copolymer is preferably 20,000 to 400,000, more preferably 30,000 to 200,000, even more preferably 40,000 to 100,000. be.
• the molecular weight distribution (Mw/Mn) of the ungrafted copolymer is preferably 1.5 to 4.0, more preferably 1.7 to 3.6, and even more preferably 1.8 to 3.2. .
• Mw mass average molecular weight
• Mw/Mn molecular weight distribution
• the mass average molecular weight and molecular weight distribution of the non-grafted copolymer can be measured as polystyrene equivalent values by GPC. The details are as described in the Examples section below.
• ⁇ Graft polymerization method> There are no particular limitations on the method of graft polymerization of the rubber-containing graft copolymer (A), and the rubber-containing graft copolymer (A) can be prepared using known emulsion polymerization methods, suspension polymerization methods, continuous bulk polymerization methods, and continuous solution polymerization methods. It can be produced by any method such as a polymerization method.
• the rubber-containing graft copolymer (A) is preferably produced by an emulsion polymerization method or a bulk polymerization method.
• the rubber-containing graft copolymer (A) is most preferably produced by an emulsion polymerization method because it is easy to adjust the emulsifier content and water content in the rubber-containing graft copolymer (A).
• the rubber-containing graft copolymer (A) may be used by blending a plurality of separately produced rubber-containing graft copolymers with different rubber particle sizes or compositions.
• the content of component (A) in a total of 100 parts by mass of components (A) to (C) is 10 to 50 parts by mass, preferably 20 to 40 parts by mass. , more preferably 25 to 35 parts by weight, still more preferably 26 to 34 parts by weight. If the content of component (A) is at least the above-mentioned lower limit, impact resistance and paintability will be good, and if it is below the above-mentioned upper limit, moldability and heat resistance will be good.
• the content of the rubbery polymer (a1) in 100% by mass of the thermoplastic resin composition of the present invention is preferably 10 to 30% by mass, more preferably 12 to 28% by mass, even more preferably 15 to 25% by mass. Mass%. If the content of the rubbery polymer (a1) is at least the above-mentioned lower limit, the impact resistance will be good, and if it is below the above-mentioned upper limit, the moldability and gloss will be good.
• the vinyl cyanide-maleimide copolymer (B) contains 5 to 30% by mass of vinyl cyanide monomer (b1) (hereinafter sometimes referred to as “component (b1)”) and maleimide monomer. (b2) (hereinafter sometimes referred to as “component (b2)”) and other vinyl monomer (b3) copolymerizable with these (hereinafter referred to as "component (b3)”). )”) 10 to 75% by mass (however, the total of component (b1), component (b2), and component (b3) is 100% by mass). Vinyl cyanide-maleimide system. It is a copolymer.
• Examples of the vinyl cyanide monomer (b1) include acrylonitrile, methacrylonitrile, and ethacrylonitrile, with acrylonitrile being particularly preferred.
• the vinyl cyanide monomers may be used alone or in combination of two or more.
• maleimide monomer (b2) examples include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and the like. Among these, N-cyclohexylmaleimide and N-phenylmaleimide are preferred, and N-phenylmaleimide is particularly preferred.
• the maleimide monomers may be used alone or in combination of two or more.
• vinyl monomers (b3) copolymerizable with component (b1) and component (b2) include aromatic vinyl monomers and unsaturated carboxylic acid ester monomers such as methyl (meth)acrylate.
• aromatic vinyl monomers such as maleic acid, unsaturated dicarboxylic anhydrides such as maleic anhydride, or unsaturated amides such as acrylamide, but are not limited to these. do not have.
• aromatic vinyl monomers are preferred.
• aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene, and o,p-dichlorostyrene. These may be used alone or in combination of two or more.
• the proportion of each monomer in 100% by mass of the raw vinyl monomer mixture used for producing the vinyl cyanide-maleimide copolymer (B) is determined based on the heat resistance, paintability, and From the viewpoint of durability, 5 to 30% by mass of vinyl cyanide monomer (b1), 20 to 60% by mass of maleimide monomer (b2), and other vinyl monomers copolymerizable with these. (b3) 10 to 75% by mass (however, the total of component (b1), component (b2), and component (b3) is 100% by mass), preferably vinyl cyanide monomer (b1) 6 to 28% by mass.
• vinyl cyanide monomer (b3) polymer (b1) 7 to 25% by mass, maleimide monomer (b2) 30 to 57% by mass, and other vinyl monomer (b3) copolymerizable with these 18 to 63% by mass, More preferably vinyl cyanide monomer (b1) 8 to 22% by mass, maleimide monomer (b2) 40 to 55% by mass, and other vinyl monomer copolymerizable with these (b3) 23 to 52% by mass, most preferably vinyl cyanide monomer (b1) 9 to 19% by mass, maleimide monomer (b2) 41 to 53% by mass, and other copolymerizable with these.
• the vinyl monomer (b3) is 28 to 50% by mass.
• the weight average molecular weight (Mw) of the vinyl cyanide-maleimide copolymer (B) is preferably 50,000 to 300,000, more preferably 80,000 to 200,000.
• the mass average molecular weight of the vinyl cyanide-maleimide copolymer (B) can be measured as a polystyrene equivalent value by GPC. The details are as described in the Examples section below.
• vinyl cyanide-maleimide copolymer (B) Only one type of vinyl cyanide-maleimide copolymer (B) may be used, or two or more types having different monomer compositions, molecular weights, etc. may be used as a mixture.
• the content of component (B) in a total of 100 parts by mass of components (A) to (C) is 5 to 90 parts by mass, preferably 20 to 70 parts by mass. , more preferably 40 to 60 parts by weight, still more preferably 42 to 58 parts by weight. If the content of component (B) is at least the above-mentioned lower limit, it will be excellent in heat resistance, paintability, and durability, and if it is below the above-mentioned upper limit, it will be excellent in fluidity and impact resistance.
• the vinyl cyanide-aromatic vinyl copolymer (C) is a copolymer obtained by copolymerizing a vinyl monomer mixture containing a vinyl cyanide monomer and an aromatic vinyl monomer. .
• vinyl cyanide monomers examples include acrylonitrile, methaacrylonitrile, ethacrylonitrile, and the like, with acrylonitrile being particularly preferred.
• the vinyl cyanide monomers may be used alone or in combination of two or more.
• aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene, and o,p-dichlorostyrene. These may be used alone or in combination of two or more.
• the ratio of vinyl cyanide monomer and aromatic vinyl monomer in 100% by mass of vinyl monomer mixture (c1) is determined from the viewpoint of moldability and paintability of the resulting thermoplastic resin composition.
• vinyl cyanide monomer/aromatic vinyl monomer 20 to 40% by mass/60 to 80% by mass, more preferably 22 to 38% by mass/62 to 78% by mass, even more preferably 24% by mass -35% by weight/65-76% by weight, most preferably 25-29% by weight/71-75% by weight.
• the vinyl monomer mixture (c1) contains, in addition to the vinyl cyanide monomer and the aromatic vinyl monomer, 0 to 30% by mass of other vinyl monomer units copolymerizable with these. It may be included within the range.
• Other vinyl monomers that can be copolymerized with these include unsaturated carboxylic acid ester monomers such as methyl (meth)acrylate, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, etc. Examples include one or more of maleimide monomers, unsaturated dicarboxylic acids such as maleic acid, unsaturated dicarboxylic anhydrides such as maleic anhydride, or unsaturated amides such as acrylamide, but are not limited to these. It's not something you can do. Among these, methyl (meth)acrylate, N-phenylmaleimide, and maleic anhydride are preferred.
• the weight average molecular weight (Mw) of the vinyl cyanide-aromatic vinyl copolymer (C) is preferably 50,000 to 300,000, more preferably 65,000 to 200,000, and even more preferably 80. ,000 to 150,000.
• the molecular weight distribution (Mw/Mn) of the vinyl cyanide-aromatic vinyl copolymer (C) is preferably 1.3 to 2.8, more preferably 1.8 to 2.6, even more preferably 1. 7 to 2.4.
• the mass average molecular weight and molecular weight distribution of the vinyl cyanide-aromatic vinyl copolymer (C) can be measured as polystyrene equivalent values by GPC. The details are as described in the Examples section below.
• vinyl cyanide-aromatic vinyl copolymer (C) Only one type of vinyl cyanide-aromatic vinyl copolymer (C) may be used, or two or more types having different monomer compositions, molecular weights, etc. may be used as a mixture.
• the content of component (C) in a total of 100 parts by mass of components (A) to (C) is 0 to 45 parts by mass, preferably 10 to 40 parts by mass. , more preferably 15 to 25 parts by weight, still more preferably 16 to 24 parts by weight.
• Component (C) is used as necessary to adjust fluidity, heat resistance, and impact resistance. If the content of component (C) is at least the above-mentioned lower limit, fluidity and heat resistance can be adjusted, and when it is below the above-mentioned upper limit, heat resistance and impact resistance can be adjusted.
• component (B) and component (C) are preferably produced by a suspension polymerization method, a continuous bulk polymerization method, or a continuous solution polymerization method other than the emulsion polymerization method.
• the content of the maleimide monomer unit in the thermoplastic resin composition of the present invention is the ratio to 100 parts by mass of component (A), component (B), and component (C) (hereinafter, this ratio is simply referred to as " The maleimide monomer unit content (sometimes referred to as “maleimide monomer unit content”) is 10 to 45 parts by mass. If the maleimide monomer unit content is at least the above-mentioned lower limit, the thermoplastic resin composition of the present invention can exhibit heat resistance and durability, and when it is below the above-mentioned upper limit, the fluidity and impact resistance can be improved. can be expressed.
• the maleimide monomer unit content of the thermoplastic resin composition of the present invention is preferably 13 to 30 parts by mass, more preferably 16 to 28 parts by mass, even more preferably 18 to 26 parts by mass, and particularly preferably 20 to 28 parts by mass. It is 24 parts by mass.
• the maleimide monomer unit is a structural unit derived from the maleimide monomer used as a raw material for each copolymer and is contained in the copolymer, and is Not limited to the monomer (b2), but also the vinyl monomer mixture (a2) of the rubber-containing graft copolymer (A) and the vinyl monomer of the vinyl cyanide-aromatic vinyl copolymer (C). It also includes those contained in the thermoplastic resin composition as constituent units of the rubber-containing graft copolymer (A) and the vinyl cyanide-aromatic vinyl copolymer (C), which are contained in the mixture (c1). It will be done. Furthermore, when maleimide monomer units are included in the other resin components described below, the maleimide monomer units are also totaled as maleimide monomer units in the thermoplastic resin composition.
• the content of maleimide monomer units in the thermoplastic resin composition can be confirmed by measuring the content of nitrogen elements and oxygen elements by elemental analysis.
• the content of maleimide monomer units in the thermoplastic resin composition can also be calculated as the content of maleimide monomers in the raw materials for producing each copolymer constituting the thermoplastic resin composition.
• the content of maleimide monomer in component (B) is measured using an elemental analyzer, and the proportion of component (B) that makes the total of components (A) to (C) 100 parts by mass is determined.
• the maleimide monomer unit content in the thermoplastic resin composition was calculated from
• thermoplastic resin composition of the present invention contains an olefin resin (D) (hereinafter sometimes referred to as "component (D)"). ).
• Examples of the olefin resin (D) include polyolefin resins (d1) and/or modified polyolefin resins (d2).
• the polyolefin resin (d1) (hereinafter sometimes referred to as "component (d1)") is preferably an unmodified ( co)polymer.
• a particularly preferred component (d1) is a polyolefin resin comprising at least one structural unit derived from an ⁇ -olefin having 2 to 10 carbon atoms.
• Examples of the ⁇ -olefin include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methylhexene-1, and the like.
• ethylene, propylene, butene-1, 3-methylbutene-1 and 4-methylpentene-1 are preferred, and propylene is particularly preferred.
• Examples of the component (d1) include polyethylene, polypropylene, ethylene/propylene copolymer, polybutene-1, ethylene/butene-1 copolymer, and the like. Among these, polyethylene, polypropylene, and propylene/ethylene copolymer are preferred. From the viewpoint of the appearance and mechanical strength of the thermoplastic resin molded product obtained, polypropylene resins containing 85% by mass or more of propylene units based on the total structural units, that is, polypropylene and ethylene-propylene copolymers are more preferred. Examples of the ethylene/propylene copolymer include random copolymers, block copolymers, etc., and random copolymers are particularly preferred.
• the above component (d1) may be crystalline or amorphous. Preferably, it has a crystallinity of 20% or more as determined by X-ray diffraction at room temperature.
• the molecular weight of the component (d1) is not particularly limited, but from the viewpoint of the appearance and mechanical strength of the obtained thermoplastic resin molded product, the melt mass flow rate (hereinafter also referred to as "MFR") according to JIS K7210 is as follows: At a temperature of 190° C. and a load of 2.16 kg, it is preferably 0.1 to 50 g/10 minutes, more preferably 0.5 to 30 g/10 minutes, and those having molecular weights corresponding to each value are preferred.
• component (d1) Commercially available products can also be used as component (d1).
• polypropylene with the trade names "Novatec FY6” and “Novatec FY4" both manufactured by Nippon Polypropylene Co., Ltd.
• Novatec FY6 trade names
• Novatec FY4 both manufactured by Nippon Polypropylene Co., Ltd.
• the number of components (d1) contained in the thermoplastic resin composition of the present invention may be one, or two or more.
• the modified polyolefin resin (d2) (hereinafter sometimes referred to as "component (d2)") is an acid-modified polyolefin resin, such as acrylic acid, methacrylic acid, maleic acid, or fumaric acid. , unsaturated carboxylic acids such as maleic anhydride, itaconic anhydride, etc., modified products obtained by grafting with siloxane, etc. can be used. Particularly preferred as component (d2) is maleic anhydride-modified polyolefin resin.
• the acid value of the modified polyolefin resin (d2) according to JIS K0070 is preferably 20 to 70 mgKOH/g.
• the melt viscosity of the modified polyolefin resin (d2) at 160° C. is preferably 1,000 to 20,0000 mPa ⁇ s, more preferably 2,000 to 12,0000 mPa ⁇ s.
• component (d2) Commercially available products can also be used as component (d2).
• the product names "UMEX 1001" and “UMEX 1010” both manufactured by Sanyo Chemical Industries, Ltd.) can be suitably used.
• thermoplastic resin composition of the present invention may contain only one type of component (d2), or may contain two or more types.
• thermoplastic resin composition of the present invention contains an olefin resin (D)
• the content of the polyolefin resin (d1) and/or modified polyolefin resin (d2) as the olefin resin (D) is the same as that of the component (A).
• the content of the polyolefin resin (d1) and/or modified polyolefin resin (d2) as the olefin resin (D) is the same as that of the component (A).
• component (A) preferably from 0.1 to 15 parts by weight, more preferably from 0.3 to 10 parts by weight, even more preferably from 0.5 to 10 parts by weight, based on a total of 100 parts by weight of component (B) and component (C). 5 parts by weight, particularly preferably 0.8 to 3 parts by weight.
• the paintability of the molded product made from the thermoplastic resin composition of the present invention can be improved, and if it is below the above-mentioned upper limit, better heat resistance can be achieved. It can improve durability, durability, and appearance.
• thermoplastic resin composition of the present invention contains, in addition to the above components (A), (B), and (C), an ethylene/(meth)acrylic acid ester/carbon monoxide copolymer (E) (hereinafter referred to as may be referred to as "component (E)").
• the ethylene/(meth)acrylic ester/carbon monoxide copolymer (E) is a copolymer obtained by copolymerizing at least ethylene, (meth)acrylic ester, and carbon monoxide.
• Component (E) may be a random copolymer or a block copolymer, but is preferably a random copolymer.
• Component (E) may be obtained by further copolymerizing other monomers copolymerizable with these.
• the (meth)acrylic ester in the ethylene/(meth)acrylic ester/carbon monoxide copolymer (E) is preferably an ester of (meth)acrylic acid and an alcohol having 1 to 8 carbon atoms.
• an ester of (meth)acrylic acid and an alcohol having 1 to 8 carbon atoms For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-(meth)acrylate.
• Examples include butyl, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, and the like. Two or more types of these may be used. Among these, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, (meth)acrylate Preferred are t-butyl and isobutyl (meth)acrylate.
• the glass transition temperature of the ethylene/(meth)acrylic acid ester/carbon monoxide copolymer (E) is preferably -60°C to -20°C, particularly preferably -48°C to -35°C.
• the melting point of the ethylene/(meth)acrylic acid ester/carbon monoxide copolymer (E) is preferably in the range of 30°C to 80°C. When the glass transition temperature and melting point are within this range, the paintability of the coating under environmental factors (for example, summer and winter) is excellent.
• component (E) Commercially available products can also be used as component (E).
• the trade name "Elvaloy HP661” manufactured by DuPont Mitsui Polychemicals
• thermoplastic resin composition of the present invention may contain only one type of component (E), or may contain two or more types.
• thermoplastic resin composition of the present invention contains an ethylene/(meth)acrylic ester/carbon monoxide copolymer (E), the ethylene/(meth)acrylic ester/carbon monoxide copolymer (E)
• the content is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, based on a total of 100 parts by mass of component (A), component (B), and component (C). , more preferably 0.5 to 5 parts by weight, particularly preferably 0.8 to 3 parts by weight.
• the content of the ethylene/(meth)acrylic acid ester/carbon monoxide copolymer (E) is at least the above lower limit, it is possible to further improve the paintability of the molded article made of the thermoplastic resin composition of the present invention. If it is below the above upper limit, better heat resistance, durability, and appearance can be achieved.
• the total content of component (D) and component (E) in the thermoplastic resin composition of the present invention is 100 parts by mass of component (A), component (B), and component (C).
• the amount is preferably 0.2 to 15 parts by weight, more preferably 0.6 to 10 parts by weight, even more preferably 1 to 6 parts by weight, particularly preferably 1.5 to 4 parts by weight, and most preferably It is 1.8 to 3 parts by mass.
• thermoplastic resin composition of the present invention Various additives can be added to the thermoplastic resin composition of the present invention for the purpose of improving the performance as a molding resin within a range that does not impair the purpose of the present invention.
• antioxidants such as hindered phenols, sulfur-containing organic compounds, and phosphorus-containing organic compounds
• heat stabilizers such as phenols and acrylates
• monostearyl acid phosphate and distearyl acid Transesterification inhibitors such as phosphate mixtures
• Transesterification inhibitors such as phosphate mixtures
• UV absorbers such as benzotriazole, benzophenone, and salicylates
• various stabilizers such as organic nickel and hindered amine light stabilizers
• metal salts of higher fatty acids such as benzotriazole, benzophenone, and salicylates.
• lubricants such as higher fatty acid amides
• plasticizers such as phthalates and phosphoric esters
• halogen-containing compounds such as polybromodiphenyl ether, tetrabromobisphenol-A, brominated epoxy oligomers, and brominated polycarbonate oligomers
• phosphorus phosphorus
• Flame retardants and flame retardant aids such as antimony trioxide, carbon black, pigments and dyes, etc. can be added.
• the thermoplastic resin composition of the present invention may contain other resins other than the above-mentioned components (A) to (E), such as a fluororesin, an impact modifier, and a mass average molecular weight, to the extent that the object of the present invention is not impaired. It may contain one or more kinds of AS resins having a molecular weight of 500,000 or more. In this case, the amount of other resins is preferably 10 parts by mass or less based on the total of 100 parts by mass of components (A) to (E) and other resins.
• thermoplastic resin composition of the present invention comprises the above-mentioned components (A) and (B), or components (A) to (C), or components (A) to (C) and component (D) and/or component ( E) Furthermore, the above-mentioned additives and other resins used as necessary can be produced by various methods such as melt-kneading with a Banbury mixer, a roll, and a single-screw or multi-screw extruder.
• thermoplastic resin molded product The thermoplastic resin molded article of the present invention is obtained by molding the thermoplastic resin composition of the present invention by a known molding method.
• the molding method include injection molding, press molding, extrusion molding, vacuum molding, blow molding, and the like.
• thermoplastic resin molded product of the present invention obtained by molding the thermoplastic resin composition of the present invention has excellent paintability, high heat resistance, and excellent appearance, and has a lower specific gravity and lighter weight than alloy materials such as polycarbonate. Moreover, it exhibits excellent durability against fatigue failure due to vibrations, etc.
• the thermoplastic resin molded article of the present invention can be used for electrical/electronic parts, automobile parts, mechanical mechanism parts, OA equipment, housing parts for home appliances, general miscellaneous goods, housing construction materials, and the like.
• the thermoplastic resin molded article of the present invention can be particularly suitably used as a lightweight material for spoilers of automobile parts.
• the thermoplastic resin molded article of the present invention is useful as a painted part whose surface is coated because of its excellent paintability.
• the volume average particle diameter of the rubbery polymer (a1) was measured according to (1) below.
• the grafting rate of the rubber-containing graft copolymer (A) was measured according to (2) below.
• Mass average molecular weight (Mw) and its molecular weight distribution ( Mw/Mn) was measured according to (3) below.
• volume average particle diameter The volume average particle diameter in the latex of the rubbery polymer (a1) was measured at room temperature using "Microtrack UPA150" (trade name) manufactured by HONEYWELL. The unit is nm. It is known that there is no substantial difference between the latex particle size of the rubbery polymer (a1) and the rubber particle size of the rubbery polymer (a1) in a resin composition using the same. The former corresponds to the latter.
• n is about 1 g [weighing: m (g)] of the rubber-containing graft copolymer (A) after adding it to 20 mL of acetone and shaking it with a shaker for 2 hours at a temperature of 25°C.
• L is the mass (g) of the rubbery polymer (a1) contained in the rubber-containing graft copolymer (A).
• the mass of the rubbery polymer (a1) can be determined by a method of calculating from a polymerization recipe and a polymerization conversion rate, a method of calculating from an infrared absorption spectrum, or the like.
• Mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) The mass average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) were measured using GPC (GPC: “GPC/V2000” manufactured by Waters, column: “Shodex AT-G + AT-806MS” manufactured by Showa Denko K.K.), It was determined by measuring in terms of polystyrene using o-dichlorobenzene (145°C) as a solvent.
• the acetone-soluble content with the above-mentioned grafting rate was dropped into methanol to precipitate the polymer component, and then the solid content was filtered out and dried in a vacuum dryer for 24 hours.
• the dried product was used for GPC measurement.
• component (B) was dissolved in acetone, the polymer component was precipitated in methanol, and the resultant product was dried in a vacuum dryer for 24 hours and used for the GPC measurement.
• Nitrogen element (N) and oxygen element (O) were measured using the following elemental analyzer for component (B) prepared in the same manner as the sample for GPC measurement. .
• the content of maleimide monomer units in component (B) was determined from the ratio of nitrogen element (N) and oxygen element (O) present in component (B).
• the content of the vinyl cyanide monomer was also determined from the amount of the remaining nitrogen element (N).
• the average residence time was reduced to 2 hours while keeping the temperature inside the polymerization vessel constant at 110°C.
• the polymerization reaction solution was continuously drawn out using a gear pump provided at the bottom of the polymerization reactor, and then the polymerization reaction solution was kept in a heat exchanger maintained at 150° C. for about 20 minutes. Thereafter, it was introduced into a two-vent type twin-screw extruder with a cylinder temperature of 230° C., and the volatile components were devolatilized under atmospheric pressure at the first vent section and reduced pressure of 2.67 kPaabs at the second vent section.
• the obtained vinyl cyanide-aromatic vinyl copolymer (C1) had a mass average molecular weight (Mw) of 96,000 and a molecular weight distribution (Mw/Mn) of 2.1.
• ⁇ Olefin resin (d2)> Maleic anhydride-modified polypropylene "Umex 1010" (trade name) manufactured by Sanyo Chemical Co., Ltd. (melt viscosity at 160°C: 6000 mPa ⁇ s, acid value according to JIS K0070: 52 mgKOH/g (catalog value)) was used. .
• the maleimide monomer unit content of the obtained thermoplastic resin composition (I) was calculated as the maleimide monomer content in the manufacturing raw material of each copolymer, and the values are shown in Tables 1 to 4. show. The following tests were conducted using the thermoplastic resin composition (I), and the results are shown in Tables 1 to 4.
• test piece (a) For each pelletized thermoplastic resin composition (I), a test piece (a) of 150 mm x 70 mm x 3 mm was injection molded using an injection molding machine "IS-100GN" (model name) manufactured by Toshiba Machine. The resin temperature during injection molding was 260°C and 220°C, the mold temperature was 5°C, and the injection speed was 25 mm/s. The test piece in which the resin temperature during injection molding was 260°C is referred to as "test piece (a-1)", and the test piece in which the resin temperature during injection molding was 220 °C is referred to as "test piece (a-2)". .
• ⁇ Paintability evaluation armpit evaluation> Test pieces (a-1) and (a-2) were painted according to the following procedure, and the surface was visually observed for the occurrence of underarm coating defects, and the paintability was evaluated based on the following evaluation criteria. I judged it. (1) Conditioning Test pieces (a-1) and (a-2) were left in a constant temperature bath adjusted to 5° C. for 12 hours or more to condition them. (2) Painting: Apply 80 parts of acrylic resin paint base, 85 parts of synthetic resin paint thinner, and 10 parts of hardening agent to the surfaces of test pieces (a-1) and (a-2) (the side without ejector pin marks). The sample was sprayed with a coating material (film thickness: 20 to 30 ⁇ m) and left at 23° C. for 5 minutes. (3) Drying Then, it was dried at 80°C for 30 minutes to obtain a painted test piece.
• a coating material film thickness: 20 to 30 ⁇ m
• test piece (b) Using an injection molding machine (manufactured by Shibaura Kikai Co., Ltd., product name "IS55FP-1.5A"), the thermoplastic resin composition (I) in the form of pellets was molded under the conditions of a cylinder temperature of 220 to 250 °C and a mold temperature of 60 °C. was injection molded to obtain a test piece (b) measuring 80 mm in length, 10 mm in width, and 4 mm in thickness. Test piece (b) was used for measuring Charpy impact strength and deflection temperature under load.
• HDT load deflection temperature
• MVR melt volume rate
• Comparative Examples 1 to 4 since component (B) did not contain acrylonitrile, the paintability was poor, especially at 220° C. where molding stress strain occurs. Furthermore, the fatigue properties at high temperatures tended to be inferior compared to Examples 1 to 4.
• Comparative Examples 5 and 6 by adding component (D) to component (B) which does not contain acrylonitrile, the paintability tends to be improved, but the fatigue properties are inferior to Comparative Examples 1 to 4. There is a tendency.
• Comparative Example 7 the amount of acrylonitrile as component (B) was higher than the specified range of the present invention, so the fluidity was poor and the fatigue properties also tended to be poor.
• Comparative Examples 8, 9, and 10 had a maleimide monomer unit content lower than the specified range of the present invention, and therefore had greatly inferior heat resistance, and was particularly inferior in vibration fatigue tests under high temperature conditions.
• Reference Examples 1 and 2 were cases in which components (D) and (E) were blended in excess, and the impact resistance, heat resistance, and molded appearance were poor.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=87935013

Family Applications (1)

Country Status (4)

Citations (4)

• 2022
  • 2022-03-10 JP JP2022037315A patent/JP2023132149A/ja active Pending
• 2023
  • 2023-03-02 CN CN202380017602.5A patent/CN118591590A/zh active Pending
  • 2023-03-02 WO PCT/JP2023/007842 patent/WO2023171531A1/ja not_active Ceased
  • 2023-03-02 US US18/712,849 patent/US20240352243A1/en active Pending

Patent Citations (4)

Also Published As

Similar Documents

Legal Events