JP5775401B2 - Thermoplastic resin composition and molded article - Google Patents

Description

  The present invention relates to a thermoplastic resin composition and a molded article excellent in the balance of impact resistance, heat resistance, molding processability, molded appearance and flame retardancy.

In recent years, the use of plant-derived materials is being studied in the face of concerns over global warming and the depletion of petroleum resources. This is because, by using plant-derived materials, the amount of oil used can be suppressed, and when the combustion treatment is performed after the use, the balance of carbon dioxide (CO ₂ ) in the atmosphere hardly changes. This is because it is based on the concept of carbon neutral. In addition, biomass plastics that use biomass, which is a biological organic resource, have attracted attention in recent years because they can reduce the environmental burden. Among them, polylactic acid-based resins are widely used from the viewpoints of low heat of combustion at the time of combustion and cost when mass-produced, and their applications are being further expanded. And the use of the resin composition which made the content rate of biomass plastics 25 mass% or more is recommended, and the identification indication of "biomass plastic" is permitted by Japan Bioplastics Association.

When a thermoplastic resin composition containing a polylactic acid-based resin is used to form molding materials, packaging materials, protective materials, etc. for various resin products, the polylactic acid-based resin becomes an existing petroleum resin. Compared with mechanical strength and durability, especially inferior in impact resistance and moist heat resistance (hydrolysis resistance), a composition using a polylactic acid resin and another thermoplastic resin in combination Is used.
However, many other thermoplastic resins are incompatible with aliphatic polyester resins such as polylactic acid resins. For example, when an ABS resin is used, a (meth) acrylic resin is usually used. And other resins or polymers are blended as compatibilizers.

Patent Document 1 discloses a thermoplastic resin composition containing a polylactic acid resin, an ABS resin, and a hard (co) polymer containing a (meth) acrylic resin component.
Patent Document 2 discloses a thermoplastic resin composition containing a polylactic acid resin, an ABS resin, and a hard copolymer obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound.
Patent Document 3 discloses a thermoplastic resin composition containing a biodegradable resin such as polylactic acid, an ABS resin, and a (meth) acrylic acid ester (co) polymer.

In addition, when a thermoplastic resin composition containing a polylactic acid resin requires heat resistance, a polycarbonate resin can be used as another thermoplastic resin. Patent Document 4 discloses an aromatic polycarbonate resin, In addition, there is disclosed a molded product having a pearly luster comprising a resin composition containing a copolymer obtained by using polylactic acid and / or lactic acid and other hydroxycarboxylic acid.
Furthermore, in resin members such as automobiles, electronic devices, home appliances, building materials, daily miscellaneous goods, etc., for heat generating elements or resin members arranged near the heat generating members, or resin members that receive sunlight, etc. Flame resistance may be required. As a molding material for such a resin member, an aromatic polycarbonate resin, a copolymer of polylactic acid and / or lactic acid and other hydroxycarboxylic acid, a core of a rubber component, and a shell formed using a vinyl compound, There is known a composition containing an impact modifier such as a core-shell type graft copolymer including a flame retardant and a flame retardant (see Patent Document 5).

JP 2006-137908 A JP 2006-161024 A JP 2007-2111206 JP-A-7-109413 JP-A-2005-48067

  An object of the present invention is to provide a molded article in which formation of pearly luster and the like on the surface is suppressed, and a thermoplastic resin composition having an excellent balance of impact resistance, heat resistance, molding processability, molding appearance and flame retardancy, and It is to provide a molded product.

The present invention is as follows.
1. [A] A rubbery polymer-reinforced graft resin obtained by polymerizing a polymerizable unsaturated monomer in the presence of an aliphatic polyester resin, [B] a polycarbonate resin, and [C] a rubbery polymer. And [D] a polymer obtained by polymerizing a polymerizable unsaturated monomer (excluding the rubber polymer reinforced graft resin [C]), and a (meth) acrylic acid ester compound. A polymer containing a (co) polymer having the derived structural unit (d1), and [E] a phosphorus-based flame retardant, and the components [A], [B], [C] and [D] When the total amount is 100% by mass, the content of the component [A] is 25 to 42 % by mass, the content of the component [B] is 22 to 48% by mass, and the component [C] the content of] is 8-14 wt%, the content of the component (D) is 14 to 38% by mass The content of rubbery polymer derived from the component [C] is 3 to 10 wt%, the content of structural units (d1) derived from the component [D] is 10 to 22 wt%, Value obtained by dividing the content of the component [A] by the content of the structural unit (d1) constituting the component [D] (content of the component [A]) / (content of the structural unit (d1)) Is 1.5 to 3.0, and the value obtained by dividing the content of the component [B] by the content of the structural unit (d1) constituting the component [D] (content of the component [B]) / (Content of structural unit (d1)) is 1.5 to 4.0, and the total amount of the above components [A], [B], [C] and [D] is 100 parts by mass. The thermoplastic resin composition, wherein the content of the component [E] is 10 to 25 parts by mass.
2. 2. The thermoplastic resin composition as described in 1 above, wherein the rubbery polymer is a diene rubber.
3. 3. The thermoplastic resin composition according to 1 or 2 above, wherein the component [E] is a phosphate ester.
4). A molded article obtained by using the thermoplastic resin composition according to any one of 1 to 3 above.

According to the thermoplastic resin composition of the present invention, the formation of pearly luster and the like on the surface is suppressed, and the appearance is good, and impact resistance, heat resistance, molding processability, molding appearance and flame retardancy are improved. A molded product having an excellent balance can be obtained. And this thermoplastic resin composition is used for members such as vehicles, ships, electronic devices, home appliances, building materials, daily goods, sports goods, stationery, etc., impact resistance, heat resistance, molded appearance, flame retardancy, etc. It is suitable for forming molded products that require properties.
Moreover, since plant-derived resin can be used as a raw material for component [A], the obtained molded article is preferably used as a resin molded article having a low environmental load.

The present invention will be described in detail below.
In this specification, “(meth) acryl” refers to acryl and methacryl, “(meth) acrylate” refers to acrylate and methacrylate, “(meth) acryloyl group” refers to acryloyl group or methacryloyl group, “Polymer” means homopolymers and copolymers.

The thermoplastic resin composition of the present invention is obtained by polymerizing a polymerizable unsaturated monomer in the presence of [A] an aliphatic polyester-based resin, [B] a polycarbonate resin, and [C] a rubbery polymer. A polymer obtained by polymerizing the obtained rubbery polymer reinforced graft resin and [D] a polymerizable unsaturated monomer (excluding the above-mentioned component [C]), comprising (meth) acrylic A polymer containing a (co) polymer having a structural unit (d1) derived from an acid ester compound, and [E] a phosphorus-based flame retardant, and the components [A], [B], [C] And when the total amount of [D] is 100% by mass, the content of the component [A] is 25 to 42 % by mass, the content of the component [B] is 22 to 48% by mass, the content of the component [C] is 8-14 wt%, the content of the component (D) is 14 to 38 mass , And the content of the rubber polymer derived from the component [C] is 3 to 10 wt%, the content of structural units (d1) derived from the component [D] is 10 to 22 wt% Yes, value obtained by dividing the content of component [A] by the content of structural unit (d1) constituting component [D] (content of component [A]) / (content of structural unit (d1)) The amount is 1.5 to 3.0, and the value obtained by dividing the content of the component [B] by the content of the structural unit (d1) constituting the component [D] (content of the component [B] Amount) / (content of structural unit (d1)) is 1.5 to 4.0, and the total amount of the above components [A], [B], [C] and [D] is 100 parts by mass. In this case, the content of the component [E] is 10 to 25 parts by mass.

  The component [A] is an aliphatic polyester resin, and conventionally known resins can be used alone or in combination of two or more. Specific examples of the component [A] include polylactic acid resin, polybutylene succinate, polybutylene succinate / adipate, polyethylene succinate, polyglycolic acid, polycaprolactone, polyhydroxybutyric acid, polyhydroxyvaleric acid, hydroxybutyric acid, Examples thereof include hydroxyvaleric acid copolymers. Of these, polylactic acid resins, polybutylene succinates, polybutylene succinate adipates and polyethylene succinates are preferred, and polylactic acid resins and polybutylene succinates are more preferred. A polylactic acid resin whose raw material is derived from plants is particularly preferred.

The polylactic acid-based resin is not particularly limited as long as the main structural unit is an L-lactic acid unit and / or a D-lactic acid unit. The (total) content of these lactic acid units is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, still more preferably 99 to 100 mol%.
When the polylactic acid-based resin contains other structural units, specific examples thereof include dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones and the like having two or more functional groups capable of forming an ester bond. Examples include derived structural units.

Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid.
Examples of the polyhydric alcohol include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol. And aromatic polyhydric alcohols such as compounds in which ethylene oxide is added to bisphenol.
Hydroxycarboxylic acids include glycolic acid, 2-hydroxycaproic acid, 6-hydroxycarboxylic acid, 2-hydroxy-2-methylcaproic acid, 2-hydroxy-2-ethylcaproic acid, 2-hydroxybutyric acid, 2-hydroxy- 2-methylbutyric acid, 2-hydroxy-2-ethylbutyric acid, 4-hydroxybutyric acid, 2-hydroxyvaleric acid, 5-hydroxyvaleric acid, 2-hydroxyheptanoic acid, 2-hydroxy-2-ethylheptanoic acid, 2-hydroxy Examples include octanoic acid, 7-hydroxyheptanoic acid, 2-hydroxy-2-methyloctanoic acid, 2-hydroxy-2-methylpropionic acid, and 3-hydroxypropionic acid.
Examples of the lactone include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, and δ-valerolactone.

  The molecular weight and molecular weight distribution of the polylactic acid resin are not particularly limited as long as the composition has moldability. The lower limit of the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 10,000, more preferably 50,000, and still more preferably 100,000. However, the upper limit is usually 400,000. The lower limit value of MFR (temperature 190 ° C., load 10 kg) corresponding to Mw is preferably 3 g / 10 minutes, more preferably 5 g / 10 minutes, still more preferably 7 g / 10 minutes, and the upper limit value is Usually, it is 100 g / 10 minutes.

  In the composition of the present invention, the component [A] may be included singly or in combination of two or more.

  The component [B] is not particularly limited as long as it is a polycarbonate resin having a carbonate bond in the main chain, and may be an aromatic polycarbonate or an aliphatic polycarbonate. Moreover, you may use combining these. In the present invention, an aromatic polycarbonate is preferable from the viewpoint of impact resistance, heat resistance, flame retardancy, and the like. In addition, this component [B] may have a terminal modified with an R—CO— group or an R′—O—CO— group (R and R ′ each represents an organic group). Good.

  Examples of the aromatic polycarbonate include those obtained by melting a transesterification (transesterification reaction) of an aromatic dihydroxy compound and a carbonic acid diester, those obtained by an interfacial polycondensation method using phosgene, and pyridine and phosgene. What was obtained by the pyridine method using a reaction product etc. can be used.

  The aromatic dihydroxy compound may be any compound having two hydroxyl groups in the molecule, such as dihydroxybenzene such as hydroquinone and resorcinol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane ( Hereinafter, referred to as “bisphenol A”), 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane, 2,2-bis ( -Hydroxyphenyl) pentane, 1,1-bis (p-hydroxyphenyl) cyclohexane, 1,1-bis (p-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (p-hydroxyphenyl) -3, 3,5-trimethylcyclohexane, 1,1-bis (p-hydroxyphenyl) -1-phenylethane, 9,9-bis (p-hydroxyphenyl) fluorene, 9,9-bis (p-hydroxy-3-methyl) Phenyl) fluorene, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropylidene) diphenol, bis (p-hydroxyphenyl) oxide, bis (p-hydroxy) Phenyl) ketone, bis (p-hydroxyphenyl) ether, bis (p-hydroxy) Phenyl) ester, bis (p-hydroxyphenyl) sulfide, bis (p-hydroxy-3-methylphenyl) sulfide, bis (p-hydroxyphenyl) sulfone, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, Examples thereof include bis (p-hydroxyphenyl) sulfoxide. These can be used alone or in combination of two or more.

  Of the aromatic hydroxy compounds, compounds having a hydrocarbon group between two benzene rings are preferred. In this compound, the hydrocarbon group may be a halogen-substituted hydrocarbon group. Further, the benzene ring may be one in which a hydrogen atom contained in the benzene ring is substituted with a halogen atom. Therefore, the above compounds include bisphenol A, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2 -Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis ( p-hydroxyphenyl) ethane, 2,2-bis (p-hydroxyphenyl) butane and the like. Of these, bisphenol A is particularly preferred.

  Examples of the carbonic acid diester used for obtaining the aromatic polycarbonate by transesterification include dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, diphenyl carbonate, and ditolyl carbonate. These can be used alone or in combination of two or more.

  The viscosity average molecular weight (Mv) of the component [B] is preferably 15,000 to 40,000, more preferably 17,000 to 30,000, still more preferably 18,000 to 28,000, and particularly preferably 18. , 2,000 to 22,000. As the viscosity average molecular weight (Mv) increases, the impact resistance increases, but the fluidity is not sufficient and the molding processability tends to be inferior. In addition, as long as the viscosity average molecular weight (Mv) as a whole falls within the above range, two or more kinds of polycarbonate resins having different viscosity average molecular weights (Mv) may be used in combination.

  In the composition of the present invention, the component [B] may be included singly or in combination of two or more.

The component [C] is a resin composition (hereinafter referred to as “rubber reinforced resin”) obtained by polymerizing a polymerizable unsaturated monomer (hereinafter referred to as “graft polymerization”) in the presence of a rubbery polymer. The rubbery polymer reinforced graft resin (hereinafter referred to as “graft resin”). This graft resin is a resin in which a (co) polymer containing a structural unit derived from a polymerizable unsaturated monomer is grafted to a rubbery polymer. And a (co) polymer portion containing a structural unit derived from a monomer.
The rubber-reinforced resin obtained by graft polymerization is usually a (co) polymer not grafted to a rubbery polymer (hereinafter referred to as “ungrafted polymer”) in addition to the rubbery polymer-reinforced graft resin. .)including. The composition of this ungrafted polymer depends on the type of polymerizable unsaturated monomer used.

  The rubbery polymer may be a homopolymer or a copolymer as long as it is rubbery at 25 ° C., but may be a diene polymer (hereinafter referred to as “diene rubber”). ) And a non-diene polymer (hereinafter referred to as “non-diene rubber”). Further, the rubbery polymer may be a crosslinked polymer or a non-crosslinked polymer. These can be used alone or in combination of two or more.

  Examples of the diene rubber include homopolymers such as polybutadiene, polyisoprene, and polychloroprene; styrene / butadiene copolymers, styrene / butadiene / styrene copolymers, acrylonitrile / butadiene copolymers, and acrylonitrile / styrene / butadiene copolymers. Styrene / butadiene copolymer rubbers such as styrene / isoprene copolymers, styrene / isoprene / styrene copolymers, styrene / isoprene copolymer rubbers such as acrylonitrile / styrene / isoprene copolymers, natural rubber, etc. Is mentioned. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is less than 50%). The diene rubber can be used singly or in combination of two or more.

  Examples of the non-diene rubber include an ethylene / α-olefin copolymer rubber containing an ethylene unit and a unit composed of an α-olefin having 3 or more carbon atoms; a urethane rubber; an acrylic rubber; a silicone rubber; -Acrylic IPN rubbers: Polymers obtained by hydrogenating (co) polymers containing units composed of conjugated diene compounds. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is 50% or more). The non-diene rubber can be used alone or in combination of two or more.

  In the present invention, the component [C] is preferably a graft resin obtained using a diene rubber as the rubber polymer.

  The polymerizable unsaturated monomer is preferably a vinyl monomer. As this vinyl monomer, aromatic vinyl compound, vinyl cyanide compound, (meth) acrylic ester compound, maleimide compound, unsaturated acid anhydride, carboxyl group-containing unsaturated compound, hydroxyl group-containing unsaturated compound And oxazoline group-containing unsaturated compounds. These can be used alone or in combination of two or more.

  The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. However, it shall not have a substituent such as a functional group. Examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene and the like. These compounds can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.

  Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile and the like. These compounds can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.

The (meth) acrylic acid ester compound is not particularly limited as long as it is a compound having a (meth) acryloyl group. However, carboxylic acid is not included. Examples thereof include compounds in which the ester moiety contains a hydrocarbon group, and compounds in which the ester moiety contains a hydroxyalkyl group. These compounds can be used alone or in combination of two or more.
Examples of the (meth) acrylic acid ester compound in which the ester portion contains a hydrocarbon group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like.
Moreover, as a compound in which an ester part contains a hydroxyalkyl group, (meth) acrylic acid 2-hydroxymethyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3 -Hydroxypropyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, And compounds obtained by adding ε-caprolactone to 2-hydroxyethyl (meth) acrylate.

  As described above, since the rubber-reinforced resin obtained by graft polymerization usually contains an ungrafted polymer, when the polymerizable unsaturated monomer contains a (meth) acrylate compound, This ungrafted polymer means a structural unit derived from a (meth) acrylic acid ester compound (meaning the same structural unit as the structural unit (d1) contained in the component [D], hereinafter referred to as “(meth) acrylic structure”). Unit ").).

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methyl). Phenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N-benzylmaleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. These compounds can be used alone or in combination of two or more.

Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These compounds can be used alone or in combination of two or more.
Examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and the like. These compounds can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing unsaturated compound include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, and p-hydroxy-α-methyl. Styrene, 2-hydroxymethyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinyl Naphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenylnaphthalene, 8-hydroxymethyl-1-isopropenylnaphthalene, p-vinylbenzyl alcohol 3 Hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, and the like. These compounds can be used alone or in combination of two or more.

In the present invention, the polymerizable unsaturated monomer preferably contains an aromatic vinyl compound, and more preferably contains an aromatic vinyl compound and a vinyl cyanide compound.
The lower limit of the content of the aromatic vinyl compound contained in the polymerizable unsaturated monomer is preferably 40% by mass, more preferably 50% by mass, and still more preferably 60% by mass. The upper limit is usually 100% by mass.
When the polymerizable unsaturated monomer contains an aromatic vinyl compound and a vinyl cyanide compound, the lower limit of the total amount is preferably 70% by mass, more preferably 80% by mass, and still more preferably 95%. % By mass. The upper limit is usually 100% by mass. The ratio of aromatic vinyl compound and vinyl cyanide compound is 100% by mass when both are combined. Molding processability, chemical resistance, hydrolysis resistance, impact resistance, rigidity, dimensional stability, molded appearance From the viewpoint of properties, etc., preferably 40 to 95% by mass and 5 to 60% by mass, more preferably 50 to 90% by mass and 10 to 50% by mass, and still more preferably 60 to 85% by mass and 15 to 40% by mass, respectively. %.

As the component [C], preferred graft resins are as follows. Among these, aspects (1) and (3) are particularly preferable from the viewpoint of the balance of impact resistance, heat resistance, molding processability, molding appearance, and flame retardancy.
(1) Graft resin obtained by polymerizing a polymerizable unsaturated monomer comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of a diene rubber. (2) In the presence of a diene rubber, Graft resin obtained by polymerizing a polymerizable unsaturated monomer comprising an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound (3) In the presence of a diene rubber, an aromatic vinyl compound, a vinyl cyanide compound And a graft resin obtained by polymerizing a polymerizable unsaturated monomer comprising a (meth) acrylic acid ester compound

In the above aspect (3), the content of the (meth) acrylic structural unit in the component [C] is not particularly limited. However, aromatic vinyl compounds, vinyl cyanide compounds and (meth) acrylic acid ester compounds in the presence of diene rubber from the viewpoint of balance of impact resistance, heat resistance, molding processability, molding appearance and flame retardancy Is a graft resin obtained by polymerizing a polymerizable unsaturated monomer containing, wherein the upper limit of the content of the structural unit ((meth) acrylic structural unit) derived from the (meth) acrylic ester compound is An 80% by mass rubber-reinforced graft resin is preferred. The upper limit of the content of the (meth) acrylic structural unit is more preferably 70% by mass, still more preferably 60% by mass, and particularly preferably 50% by mass.
In the present invention, as the component [C], any of the graft resins of the above aspect (3) and having different (meth) acrylic structural unit contents may be used in combination. .

  The method for producing the component [C] is not particularly limited, and a known method can be applied. As a polymerization method, emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these can be used.

  When the component [C] is produced, the polymerization may be started by supplying the polymerizable unsaturated monomers all at once in the reaction system in the presence of the total amount of the rubbery polymer. Alternatively, the polymerization may be performed while continuously feeding. Further, in the presence or absence of a part of the rubbery polymer, polymerization may be started by batch supply of polymerizable unsaturated monomers, or may be divided or continuously supplied. Good. At this time, the remainder of the rubbery polymer may be supplied in a batch, divided or continuously in the middle of the reaction.

  When performing emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water, and the like are used.

  Examples of the polymerization initiator include organic peroxides, azo compounds, inorganic peroxides, and redox polymerization initiators.

  Examples of the organic peroxide include tert-butyl hydroperoxide, tert-amyl-tert-butyl peroxide, tert-butyl-tert-hexyl peroxide, tert-amyl-tert-hexyl peroxide, di (tert-hexyl). ) Peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- Bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydropa Oxide, 1,3-bis (tert-butylperoxy) -m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert-butyl kumi Ruperoxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxylaurate, tert-butylperoxymonocarbonate, bis (tert-butylcyclohexyl) peroxy Examples include dicarbonate, tert-butyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, and the like.

  Examples of the azo compound include 2,2′-azobis (isobutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), azocumene, and 2,2′-azobis (2-methylbutyronitrile). 2,2′-azobisdimethylvaleronitrile, 4,4′-azobis (4-cyanovaleric acid), 2- (tert-butylazo) -2-cyanopropane, 2,2′-azobis (2,4,4) 4-trimethylpentane), 2,2′-azobis (2-methylpropane), dimethyl 2,2′-azobis (2-methylpropionate) and the like.

Examples of the inorganic peroxide include potassium persulfate, sodium persulfate, and ammonium persulfate.
Further, as a redox type polymerization initiator, sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate and the like are used as reducing agents, potassium peroxodisulfate, hydrogen peroxide, cumene hydroperoxide, What used tert-butyl hydroperoxide etc. as the oxidizing agent can be used.

The usage-amount of the said polymerization initiator is 0.05-10 mass% normally with respect to the whole quantity of the said polymerizable unsaturated monomer.
The polymerization initiator can be supplied to the reaction system all at once or continuously.

  Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; Examples include α-methylstyrene dimers. These can be used alone or in combination of two or more.

The amount of the chain transfer agent used is usually 0.01 to 5% by mass with respect to the total amount of the polymerizable unsaturated monomer.
The chain transfer agent can be supplied to the reaction system all at once or continuously.

  Examples of the emulsifier include anionic surfactants and nonionic surfactants. Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates, aliphatic phosphates, etc. Is mentioned. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used alone or in combination of two or more.

  The usage-amount of the said emulsifier is 0.1-10 mass% normally with respect to the whole quantity of the said polymerizable unsaturated monomer.

  Emulsion polymerization can be carried out under known conditions depending on the type of polymerizable unsaturated monomer, polymerization initiator and the like. The latex obtained by this emulsion polymerization is usually subjected to coagulation of the resin component with a coagulant to form a powder or the like. Thereafter, it is purified by washing with water, etc., dried and collected. For coagulation, conventionally known coagulants are used, and inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid are used. In the present invention, if a salt is present in the composition, it may cause hydrolysis of component [B]. Therefore, it is preferable to use an inorganic acid and an organic acid as a coagulant.

  When the component [C] is produced by solution polymerization, bulk polymerization, and bulk-suspension polymerization, known methods can be applied.

  When the component [C] and the ungrafted polymer are separated from the rubber reinforced resin containing the component [C] obtained as described above, for example, 10 g of the rubber reinforced resin is added to 100 to 200 ml of acetone (rubber If the polymer is an acrylic rubber, use acetonitrile) and shake it at 25 ° C for 2 to 3 hours using a shaker etc. to separate the insoluble and soluble components produced. The method of recovery is applied. The acetone-soluble component (acetonitrile-soluble component) corresponds to the ungrafted polymer and is included in component [D].

  The graft ratio in the component [C] is preferably 10 to 200%, more preferably 15 to 150%, and still more preferably 20 from the viewpoints of molding processability, impact resistance of molded products, molded appearance, and the like. ~ 100%. If this graft ratio is too low, the impact resistance and molded appearance of the molded product may be lowered. On the other hand, if the graft ratio is too high, moldability may not be sufficient.

The graft ratio can be determined by the following formula.
Graft rate (%) = {(S−T) / T} × 100
In the formula, S represents 1 gram of rubber-reinforced resin obtained by graft polymerization in 20 ml of acetone (acetonitrile is used when the rubbery polymer is an acrylic rubber), and is shaken using a shaker. (Temperature 25 ° C., 2 hours) Then, using a centrifuge, the mixture is centrifuged (temperature 5 ° C., rotation speed 23,000 rpm, 1 hour), insoluble matter corresponding to component [C] It is the mass (g) of the insoluble matter obtained by separating the soluble component corresponding to the coalescence, and T is the mass (g) of the rubbery polymer contained in 1 gram of the rubber reinforced resin. The mass of the rubbery polymer can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.

  The graft ratio is, for example, the type and amount of polymerization initiator used in the production of component [C], the type and amount of chain transfer agent, the supply method and supply time of the polymerizable unsaturated monomer, polymerization Temperature etc. can be adjusted by selecting suitably.

  The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component (or acetonitrile-soluble component) of the rubber-reinforced resin is preferably from 0.1 to 1. from the viewpoint of molding processability and impact resistance. It is 0 dl / g, More preferably, it is 0.15-0.9 dl / g, More preferably, it is 0.2-0.8 dl / g. If this intrinsic viscosity [η] is too low, the impact resistance of the molded product may be lowered. On the other hand, if the intrinsic viscosity [η] is too high, the moldability may not be sufficient.

Here, the intrinsic viscosity [η] can be obtained, for example, in the following manner.
When determining the graft ratio in the component [C], the acetone-soluble component (or acetonitrile-soluble component) recovered after centrifuging the mixture containing the rubber-reinforced resin and acetone or acetonitrile using a centrifuge ) Is dissolved in methyl ethyl ketone, five different concentrations are prepared, and the reduced viscosity of each concentration is measured at 30 ° C. using an Ubbelohde viscosity tube, whereby the intrinsic viscosity [η] is obtained.

  The intrinsic viscosity [η] is used when producing the component [C], by adjusting the type and amount of polymerization initiator, chain transfer agent, emulsifier, solvent, etc., and further adjusting the polymerization time, polymerization temperature, etc. Can be controlled.

  In the composition of the present invention, the component [C] may be included singly or in combination of two or more.

The component [D] is a polymer not containing the component [C] obtained by polymerizing a polymerizable unsaturated monomer, and is a structural unit derived from a (meth) acrylic acid ester compound (d1 ) Having a (co) polymer (hereinafter referred to as “polymer (DX)”). The component [D] may be only the polymer (DX), does not contain the polymer (DX) and the structural unit (d1), and is a structural unit different from the structural unit (d1) (hereinafter referred to as the structural unit (D1)). Or a combination with another (co) polymer (hereinafter referred to as “polymer (DY)”) composed of “structural unit (d2)”. None of these polymer (DX) and polymer (DY) contains the component [C].
The polymer (DX) contained in the component [D] may be only one type or two or more types. The polymer (DY) contained in the component [D] may also be only one type or two or more types.

  The content of the structural unit (d1) constituting the component [D] is preferably from the viewpoint of molding appearance when the total amount of all structural units constituting the component [D] is 100% by mass. Is 25-100 mass%, More preferably, it is 30-90 mass%, More preferably, it is 35-85 mass%. The type of the structural unit (d1) constituting the component [D] may be the same as or different from the (meth) acrylic structural unit contained in the graft part constituting the component [C]. Good.

The polymer (DX) may be a (co) polymer consisting only of the structural unit (d1), or other polymerizable with the structural unit (d1) and the (meth) acrylate compound. It may be a copolymer containing a structural unit derived from an unsaturated monomer (hereinafter referred to as “structural unit (d3)”).
The content of the structural unit (d1) contained in the polymer (DX) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and still more preferably, from the viewpoint of the appearance of the obtained molded product. It is 65-100 mass%.

  About the (meth) acrylic acid ester compound which forms the said structural unit (d1), the exemplary compound of the (meth) acrylic acid ester compound which can be used as a polymerizable unsaturated monomer used for formation of the said component [C] Applies. The structural unit (d1) constituting the polymer (DX) may be only one type or two or more types.

As said (meth) acrylic acid ester compound, the ester part contains the (meth) acrylic acid ester compound (henceforth "monomer (dm1)") whose carbon number is a C1-C4 hydrocarbon group. Preferably, it may be a combination of this monomer (dm1) and a (meth) acrylic acid ester compound whose ester moiety is a hydrocarbon group having 5 or more carbon atoms. As the monomer (dm1), methyl methacrylate, methyl acrylate, and n-butyl acrylate are preferable.
The proportion of the monomer (dm1) contained in the (meth) acrylic acid ester compound is preferably 55 to 100% by mass, more preferably 65 to 100% by mass, particularly from the viewpoint of the appearance of the obtained molded product. Preferably it is 80-100 mass%.

  Examples of the polymerizable unsaturated monomer forming the structural unit (d3) include aromatic vinyl compounds, vinyl cyanide compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, and hydroxyl group-containing unsaturated monomers. Examples include saturated compounds, oxazoline group-containing unsaturated compounds, α-olefins, chlorine-containing unsaturated compounds (such as vinyl chloride and vinylidene chloride), and fluorine-containing unsaturated compounds. These can be used alone or in combination of two or more.

  Examples of the polymer (DX) include polymethyl methacrylate, methyl methacrylate / methyl acrylate copolymer, methyl methacrylate / butyl methacrylate copolymer, methyl methacrylate / styrene copolymer, acrylonitrile / styrene / methacrylic acid. Examples include acid methyl copolymers. These (co) polymers may be used alone or in combination of two or more.

  On the other hand, the polymer (DY) is a (co) polymer consisting only of the structural unit (d2). Examples of the polymerizable unsaturated monomer that forms the structural unit (d2) include aromatic vinyl compounds, vinyl cyanide compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, and hydroxyl group-containing unsaturated monomers. Examples thereof include saturated compounds and oxazoline group-containing unsaturated compounds. Of these, aromatic vinyl compounds and vinyl cyanide compounds are preferred. Moreover, these polymerizable unsaturated monomers can be used individually by 1 type or in combination of 2 or more types.

  Examples of the polymer (DY) include styrene / acrylonitrile copolymers, α-methylstyrene / acrylonitrile copolymers, styrene / acrylonitrile / N-phenylmaleimide copolymers, and the like. These copolymers may be used alone or in combination of two or more.

  When the said component [D] consists of a polymer (DX) and a polymer (DY), the content rate of these polymers is not specifically limited. From the viewpoint of impact resistance, heat resistance and molding appearance, the content ratio of the polymer (DX) and the polymer (DY) is preferably 20 to 100 masses when the total of both is 100 mass%. % And 0 to 80% by mass, more preferably 30 to 100% by mass and 0 to 70% by mass.

The component [D] according to the present invention is preferably a (co) polymer whose content of the structural unit (d1) is 60 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 100% by mass. (D1) and a copolymer (D2) in which the content of the structural unit (d1) is 0 to 40% by mass, more preferably 0 to 20% by mass, and particularly preferably 0% by mass. The content ratios of the copolymer (D1) and the copolymer (D2) are preferably 10 to 100% by mass and more preferably 0 to 90% by mass, respectively, when the total amount of both is 100% by mass. Is 25 to 100% by mass and 0 to 75% by mass, more preferably 35 to 100% by mass and 0 to 65% by mass, and particularly preferably 50 to 100% by mass and 0 to 50% by mass. And the sum (total amount) of the content of the structural unit (d1) constituting the (co) polymer (D1) and the content of the structural unit (d1) constituting the copolymer (D2) is The total amount of all structural units constituting the polymer [D] (contents of all structural units constituting the (co) polymer (D1) and the copolymer (D2)) When the sum of the contents of all structural units is 100% by mass, a more preferable ratio is 30 to 95% by mass from the viewpoint of impact resistance, flame retardancy, and appearance of the obtained molded product. Preferably it is 35-95 mass%, Most preferably, it is 35-85 mass%.
By using the component [D] having the above configuration, a molded product particularly excellent in impact resistance and / or appearance can be obtained.

The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the component [D] is preferably 0.1 to 1.5 dl / g, more preferably 0.1 to 0.1% from the viewpoint of moldability and impact resistance. 1.3 dl / g, more preferably 0.1 to 1.0 dl / g.
Here, the intrinsic viscosity [η] can be obtained in the following manner.
The above component [D] is dissolved in methyl ethyl ketone, 5 different concentrations are prepared, and the reduced viscosity of each concentration solution is measured at 30 ° C. using an Ubbelohde viscosity tube. Desired.

  The method for producing the component [D] is not particularly limited, and for example, emulsion polymerization, solution polymerization, bulk polymerization and the like can be applied.

  In the composition of the present invention, the component [D] may be included singly or in combination of two or more.

In the composition of the present invention, the content ratio of the components [A], [B], [C] and [D] is 100 masses of the total amount of the components [A], [B], [C] and [D]. %, 25 to 42 % by mass, 22 to 48% by mass, 8 to 14 % by mass, and 14 to 38 % by mass, and preferably 25 to 42 % by mass, 24 to 48% by mass, and 8 to 8 %, respectively. 14 wt% and 14-38 wt%, more preferably 25-42 wt%, 26-46 wt%, 8-14 wt% and 14-38 wt%, particularly preferably 27 to 42 wt%, 28 to 44 weight %, 8-14% by mass and 15-35% by mass. By making the content ratios of the components [A], [B], [C] and [D] in this way, formation of pearly luster and the like on the surface is suppressed, and the appearance is good, impact resistance, A molded product having an excellent balance of heat resistance, molding processability, molded appearance and flame retardancy can be obtained.
When there is too little content of the said component [B], it will be inferior to impact resistance and a flame retardance. On the other hand, when there is too much content of component [B], it will be inferior to shaping | molding workability and shaping | molding external appearance property.
When there is too little content of the said component [C], it will be inferior to impact resistance. On the other hand, when there is too much content of the said component [C], it is inferior to a flame retardance.
Moreover, when there is too little content of the said component [D], it will be inferior to shaping | molding external appearance property. On the other hand, when there is too much content of the said component [D], it is inferior to a flame retardance.

  In the composition of the present invention, the content of the rubbery polymer derived from the component [C] is selected from the components [A], [B], [C] and [C] from the viewpoint of impact resistance of the obtained molded product. D] is 100 to 10% by mass, preferably 3 to 10% by mass, preferably 4 to 10% by mass, and particularly preferably 4 to 8% by mass. In addition, when there is too little content of a rubbery polymer, it will be inferior to impact resistance, and when there is too much content of a rubbery polymer, it will be inferior to a flame retardance.

  In the composition of the present invention, the content of the structural unit (d1) derived from the component [D] is selected from the components [A], [B], [C] and [C] from the viewpoints of molding appearance and flame retardancy. D] is 10 to 22% by mass, where the total amount of D] is 100% by mass. In addition, when there is too little content of a structural unit (d1), it will be inferior to shaping | molding external appearance property, on the other hand, when there is too much content of a structural unit (d1), it will be inferior to flame retardance.

In the present invention, the content of the component [A] or [B] when the total amount of the components [A], [B], [C] and [D] is 100% by mass and the component [D] are constituted. When the ratio to the structural unit (d1) is within a specific range, a molded product having an excellent balance of heat resistance, molded appearance and flame retardancy can be obtained.
The calculated value obtained by dividing the content (total amount) of the component [A] by the content (total amount) of the structural unit (d1) constituting the component [D], that is, (the component [A] Content) / (Content of structural unit (d1)) is 1.5 to 3.0.
Further, the calculated value obtained by dividing the content (total amount) of the component [B] by the content (total amount) of the structural unit (d1) constituting the component [D], that is, (component [B ] / (Content of structural unit (d1)) is 1.5 to 4.0.

  Next, the component [E] is a phosphorus flame retardant, and conventionally known phosphorus-containing compounds can be used alone or in combination of two or more. Although the property of this flame retardant is not particularly limited, it is usually liquid or solid at room temperature.

  Phosphorus flame retardants include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate , Crecresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, etc., their modified compounds, condensed phosphoric acid represented by the following general formula (1) Examples thereof include ester compounds, phosphazene derivatives containing a phosphorus element and a nitrogen element.

（式中、Ｘは、芳香環を含む芳香族基であり、Ｒ^ａ、Ｒ^ｂ、Ｒ^ｃ及びＲ^ｄは、それぞれ、独立したアリール基であって、含まれる炭素原子に結合する水素原子の１つ以上が、他の原子又は官能基に置換された基であってもよい。ｎは１以上の整数、ｊ、ｋ、ｌ及びｍは、それぞれ、独立して０又は１である。）

(In the formula, X is an aromatic group containing an aromatic ring, and R ^a , R ^b , R ^c and R ^d are each an independent aryl group, which is a hydrogen atom bonded to the contained carbon atom. One or more may be a group substituted with another atom or functional group, n is an integer of 1 or more, and j, k, l, and m are each independently 0 or 1.)

X in the general formula (1) is exemplified below.

  Among these, a condensed phosphate compound is particularly preferable because a resin molded product having excellent flame retardancy and low environmental load can be obtained.

  In addition, as flame retardants, inorganic flame retardants such as aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium compounds, molybdenum compounds, zinc stannate; brominated epoxy compounds, brominated alkyl triazines Compound, Brominated bisphenol epoxy resin, Brominated bisphenol phenoxy resin, Brominated bisphenol polycarbonate resin, Brominated polystyrene resin, Brominated crosslinked polystyrene resin, Brominated bisphenol cyanurate resin, Brominated polyphenylene ether, Decabromodiphenyl oxide , Tetrabromobisphenol A and oligomers thereof, halogen-based flame retardants such as polytetrafluoroethylene; guanidine salts; silicone compounds, etc. are known, but can be used together if necessary.

  In the composition of the present invention, the content of the component [E] is such that good flame retardancy can be obtained without reducing impact resistance, heat resistance, molding processability and molding appearance. When the total amount of A], [B], [C] and [D] is 100 parts by mass, it is 10 to 25 parts by mass, preferably 11 to 20 parts by mass, more preferably 12 to 16 parts by mass. It is. When there is too much content of the said component [E], heat resistance and impact resistance will be inferior.

The composition of the present invention may contain other polymers (other resins).
Examples of other polymers include polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyester resins, polyamide resins, and fluororesins.
When the composition of the present invention contains another polymer (other resin), the upper limit of the content is the above-mentioned components [A], [B], [C], [D] and [E]. The total amount is preferably 30 parts by mass, more preferably 20 parts by mass with respect to 100 parts by mass.

  The composition of the present invention may further comprise a filler, a plasticizer, an antioxidant, an ultraviolet absorber, an anti-aging agent, a lubricant, a weathering stabilizer, a light stabilizer, a heat stabilizer, a charge, depending on the purpose and application. It may contain an inhibitor, a water repellent, an oil repellent, an antifoaming agent, an antibacterial agent, an antiseptic, a colorant (pigment, dye, etc.), a fluorescent whitening agent, a conductivity imparting agent and the like.

  Examples of the filler include heavy calcium carbonate, colloidal calcium carbonate, light calcium carbonate, magnesium carbonate, zinc carbonate, aluminum hydroxide, magnesium hydroxide, carbon black, clay, talc, fumed silica, calcined silica, precipitated silica, Ground silica, fused silica, kaolin, diatomaceous earth, zeolite, titanium oxide, quicklime, iron oxide, zinc oxide, barium oxide, aluminum oxide, magnesium oxide, aluminum sulfate, glass fiber, carbon fiber, glass balloon, shirasu balloon, saran Examples include balloons and phenol balloons. These can be used alone or in combination of two or more.

  Examples of the plasticizer include phthalic acid esters, trimellitic acid esters, pyromellitic acid esters, aliphatic monobasic acid esters, aliphatic dibasic acid esters, polyhydric alcohol esters, epoxy plasticizers, and polymeric plasticizers. And chlorinated paraffin. These can be used alone or in combination of two or more.

  Examples of the antioxidant include hindered amine compounds, hydroquinone compounds, hindered phenol compounds, sulfur-containing compounds, and phosphorus-containing compounds. These can be used alone or in combination of two or more.

  Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, and triazine compounds. These can be used alone or in combination of two or more.

  Examples of the anti-aging agent include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds, thiols. Examples thereof include bisphenol compounds, hindered phenol compounds, phosphite compounds, imidazole compounds, nickel dithiocarbamate salts, phosphoric compounds, and the like. These can be used alone or in combination of two or more.

  Examples of the lubricant include wax, silicone, and lipid. These can be used alone or in combination of two or more.

The thermoplastic resin composition of the present invention gives a molded product in which the formation of pearl luster or the like on the surface is suppressed, and is excellent in the balance of impact resistance, heat resistance, molding processability, molded appearance and flame retardancy.
The Charpy impact strength measured under the conditions described below is preferably 7 to 28 J / m ² , more preferably 8 to 25 J / m ² , and particularly preferably 10 to 25 J / m ² .
The deflection temperature under load measured under the conditions described later is preferably 53 ° C to 70 ° C, more preferably 55 ° C to 66 ° C, and particularly preferably 57 ° C to 66 ° C.
The melt flow rate measured under the conditions described below is preferably 45 to 95 g / 10 minutes, more preferably 48 to 95 g / 10 minutes, and particularly preferably 48 to 80 g / 10 minutes.
Flame retardancy (UL94 standard) measured under the conditions described later is the V-2 class.

  The composition of this invention can be manufactured by knead | mixing the raw material containing component [A], [B], [C], [D], and [E]. In kneading, conventionally known kneading apparatuses such as a twin screw extruder, a single screw extruder, a heatable twin or single screw feeder, a feeder ruder, a Banbury mixer, a roll mill, and the like can be used. A preferred production method is a method using a twin screw extruder. In addition, when kneading | mixing a raw material component, you may knead | mix kneading after collectively to a kneading apparatus, and you may knead | mix while adding multistage.

  The kneading temperature of the raw material is appropriately selected depending on the types of the components [A], [B], [C], [D] and [E], but is usually in the range of 220 ° C. to 260 ° C. is there.

  Since the composition of the present invention contains the components [A], [B], [C], [D] and [E], in the obtained molded product, formation of pearl luster or the like on the surface is suppressed, Greater impact resistance, heat resistance and flame resistance can be obtained than before. Moreover, when it is set as the composition containing a coloring agent, the molded article excellent in colored appearance can be obtained. That is, it is suitable not only for a non-colored molded product but also for forming a molded product or the like in which a defective phenomenon of colored appearance has been noticeable. And since a plant-derived material can be used as a component [A], the resin molded product with a low environmental impact can be obtained. Such a molded article is suitable as a member for vehicles, ships, electronic devices, home appliances, building materials, daily miscellaneous goods, sports equipment, stationery, etc., which requires the above-mentioned excellent properties, and has high flame resistance. It is particularly suitable as a member for electronic devices, home appliances, and the like that require high performance.

  The molded product of the present invention comprises the above thermoplastic resin composition of the present invention, or the raw material components that will form its constituent components, an injection molding device, a sheet extrusion molding device, a profile extrusion molding device, a hollow molding device, It can be manufactured by processing with a known molding apparatus such as a compression molding apparatus, a vacuum molding apparatus, a foam molding apparatus, a blow molding apparatus, an injection compression molding apparatus, a gas assist molding apparatus, or a water assist molding apparatus.

When manufacturing a molded article using the above molding apparatus, the molding temperature and mold temperature are the types of the above components [A], [B], [C], [D] and [E], or are used. It is appropriately selected depending on the types of raw material components (including other polymers).
When the composition of the present invention is subjected to injection molding, although depending on the shape of the molded product, the cylinder temperature at the time of molding is usually 200 ° C to 260 ° C. The mold temperature is usually 20 ° C to 90 ° C.
When the molded product is large, the cylinder temperature is generally set higher than the above temperature.

  The molded product of the present invention may be provided with a through hole, a groove, a concave portion, a convex portion, and the like at an arbitrary position according to the purpose and application.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. In the following, “part” and “%” are based on mass unless otherwise specified.

1. Production Raw Materials The raw materials (resin component and polymer component) used for the production of the thermoplastic resin composition are as follows. The measurement of the graft ratio, intrinsic viscosity [η], etc. was performed according to the method described above.

1-1. Raw material [P]
Polylactic acid “Ingeo Biopolymer 2003D” (trade name) manufactured by Nature Works was used. The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene by GPC are 194,000 and 99,000, respectively. The MFR according to ASTM D1238 is 6 g / 10 min at a temperature of 210 ° C. and a load of 2.16 kg, and 53 g / 10 min at a temperature of 220 ° C. and a load of 10 kg.

1-2. Raw material [Q]
Sumika Stylon Polycarbonate resin “Caliver 200-10” (trade name) manufactured by Polycarbonate Company was used. The viscosity average molecular weight (Mv) is 22,000.

1-3. Raw material [R]
This raw material [R] is a rubber-reinforced resin or copolymer obtained by polymerizing a vinyl monomer in the presence or absence of a rubbery polymer, as shown in Synthesis Examples 1 to 3 below. In addition, it is a commercially available vinyl copolymer. The rubber reinforced resin is a mixture comprising the rubbery polymer reinforced graft resin [C] according to the present invention and the (co) polymer [D].

Synthesis Example 1 (Synthesis of rubber reinforced resin R-1)
In a glass flask equipped with a stirrer, in a nitrogen stream, 35 parts of ion exchange water, 0.25 part of potassium rosinate, 0.15 part of tert-dodecyl mercaptan, a polybutadiene rubber having a weight average particle size of 300 nm (gel content 80 %) 120 parts of latex containing 48 parts, 30 parts of latex containing 12 parts of styrene / butadiene copolymer rubber (styrene unit amount 30%) having a weight average particle diameter of 600 nm, 9 parts of styrene and 3 parts of acrylonitrile were stirred and stirred. While raising the temperature. When the internal temperature reached 40 ° C., a solution in which 0.15 part of sodium pyrophosphate, 0.007 part of ferrous sulfate heptahydrate and 0.22 part of glucose was dissolved in 5 parts of ion-exchanged water was added. . Thereafter, 0.05 part of cumene hydroperoxide was added to initiate polymerization.
After polymerizing for 30 minutes, 30 parts of ion-exchanged water, 0.5 parts of potassium rosinate, 20 parts of styrene, 8 parts of acrylonitrile, 0.1 part of tert-dodecyl mercaptan and 0.07 part of cumene hydroperoxide were added for 3 hours. Over time. Thereafter, the polymerization was further continued for 1 hour, and 0.15 part of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) was added to complete the polymerization.
Next, an aqueous sulfuric acid solution was added to the latex containing the reaction product to coagulate the resin component and wash it with water. Then, it wash | cleaned and neutralized using potassium hydroxide aqueous solution, Furthermore, after washing with water, it dried and obtained rubber | gum reinforcement | strengthening resin R-1 (polymerization conversion rate is 98.5%). The graft ratio in the graft resin contained in this resin R-1 was 48%. The content of acetone-soluble matter was 11.2%, and its intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) was 0.35 dl / g.

Synthesis Example 2 (Synthesis of rubber reinforced resin R-2)
A glass flask equipped with a stirrer is charged with 45 parts of polybutadiene rubber having a volume average particle diameter of 300 nm, 0.3 part of sodium dodecylbenzenesulfonate and 100 parts of ion-exchanged water, and then 3 parts of styrene, 2 parts of acrylonitrile and methacrylic acid. 9 parts of methyl were charged. These mixtures were heated with stirring, and when the internal temperature reached 43 ° C., 0.02 part of sodium ethylenediaminetetraacetate, 0.001 part of ferrous sulfate heptahydrate and sodium formaldehyde sulfoxylate dihydrate A solution prepared by dissolving 0.08 part of the product in 6 parts of ion-exchanged water and 0.04 part of cumene hydroperoxide was added to initiate polymerization.
After polymerization for 1 hour, a monomer mixture comprising 9 parts of styrene, 5 parts of acrylonitrile, 27 parts of methyl methacrylate, 1.2 parts of tert-dodecyl mercaptan and 0.1 part of cumene hydroperoxide, and sodium ethylenediaminetetraacetate 0.01 part, 0.001 part of ferrous sulfate heptahydrate, 0.05 part of sodium formaldehyde sulfoxylate dihydrate and 0.3 part of sodium dodecylbenzenesulfonate are dissolved in 30 parts of ion-exchanged water. The solution was added continuously over 4 hours and polymerization was continued. Thereafter, 0.003 part of sodium ethylenediaminetetraacetate, 0.0002 part of ferrous sulfate heptahydrate, 0.01 part of sodium formaldehyde sulfoxylate dihydrate and 0.02 part of cumene hydroperoxide were ion-exchanged. A solution dissolved in 1 part of water was added and stirred for 1 hour, and then cooled to complete the polymerization.
Next, 0.67 part of a substance (“SANDWIN-45” manufactured by Toho Chemical Co., Ltd.) obtained by reacting p-cresol, dicyclopentadiene and isobutylene with the latex containing the reaction product and 0. 5 parts were added and magnesium sulfate was added to solidify the resin component. Thereafter, this resin component was sufficiently washed with water, dehydrated, and dried at a temperature of 80 ° C. for 24 hours to obtain a white powdered rubber-reinforced resin R-2 (polymerization conversion rate: 97.0%). The graft ratio in the graft resin contained in this resin R-2 was 52%, and the amount of methyl methacrylate units was 38%. Further, the acetone-soluble component is composed of methyl methacrylate unit, styrene unit and acrylonitrile unit (mass ratio 69: 24: 7), and the content of acetone-soluble component contained in the resin R-2 is 32%, Its intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) was 0.24 dl / g.

Synthesis Example 3 (Synthesis of styrene / acrylonitrile copolymer R-3)
A polymerization apparatus in which two jacketed polymerization reactors equipped with ribbon blades were connected was used. After purging each reactor with nitrogen gas, the first reactor was charged with a monomer mixture consisting of 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene, and tert-dodecyl mercaptan 0.15 as a molecular weight regulator. A first solution in which 5 parts of toluene was dissolved in 5 parts of toluene and a second solution in which 0.1 part of dicumyl peroxide as a polymerization initiator was dissolved in 5 parts of toluene were continuously fed and stirred while the temperature was increased. Polymerization was carried out at 110 ° C. The average residence time of the monomer mixture and the like for the polymerization was 2 hours, and the polymerization conversion after 2 hours was 56%.
Next, the polymer solution in the first reactor was continuously taken out by a pump provided outside the reactor and transferred to the second reactor. The amount to be continuously taken out is the same as the amount of the raw material such as the monomer mixture supplied to the first reactor. That is, the accommodation component of the first reactor and the accommodation component of the second reactor were each maintained to have the same volume. The polymer solution supplied from the first reactor was further polymerized at a temperature of 130 ° C. in the second reactor with an average residence time of 2 hours. The polymerization conversion after 2 hours was 74%.
Thereafter, the polymer solution in the second reactor was discharged and introduced into an extruder with a biaxial three-stage vent. Then, the unreacted monomer and toluene (polymerization solvent) were directly devolatilized to obtain a styrene / acrylonitrile copolymer R-3.
The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the styrene / acrylonitrile copolymer R-3 was 0.60 dl / g.

Moreover, the following copolymers were used as vinyl-type (co) polymers R-4 and R-5.
(1) R-4
Acrylic resin “Acrypet VH5” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. was used. This product is a copolymer composed of methyl methacrylate units and methyl acrylate units (mass ratio 98: 2), and the weight average molecular weight (Mw) in terms of polystyrene by GPC is 69,000.
(2) R-5
It is a copolymer consisting of methyl methacrylate units, styrene units and acrylonitrile units (mass ratio 66:21:13), and has a weight average molecular weight (Mw) in terms of polystyrene by GPC of 101,000. The intrinsic viscosity [η] (methyl ethyl ketone, 30 ° C.) is 0.42 dl / g.

1-4. Raw material [S]
The following compounds were used as flame retardants.
(1) 1,3-phenylenebis (dixylenyl) phosphate An aromatic condensed phosphate ester “PX-200” (trade name) manufactured by Daihachi Chemical Industry Co., Ltd. was used.
(2) α-Diphenoxyphosphoryl-ω-phenoxypoly (n = 1 to 3) [oxy-1,4-phenyleneisopropylidene-1,4-phenyleneoxy (phenoxyphosphoryl)]
Aromatic condensed phosphate ester “CR-741” (trade name) manufactured by Daihachi Chemical Industry Co., Ltd. was used.
(3) Melamine cyanurate “MC-4000” (trade name) manufactured by Nissan Chemical Industries, Ltd. was used.

2. Production and Evaluation of Thermoplastic Resin Composition Examples 1 to 11 and Comparative Examples 1 to 16
A thermoplastic resin composition using raw materials [P], [Q], [R] and [S] in the proportions shown in Table 1, Table 2, Table 3, Table 4, Table 5, Table 6, and Table 7. Got.
Of the raw materials [R], the rubber-reinforced resin is a mixture comprising the component [C] according to the present invention and a copolymer corresponding to the component [D]. Therefore, the content of the polymer corresponding to the component [D] of the present invention contained in the rubber reinforced resin is calculated using the graft ratio in the component [C], the composition of the acetone soluble component in the rubber reinforced resin, and the like. The total amount of the calculated value and the polymer component (resin component) other than the component [C] in the raw material [R] was defined as the component [D] contained in the thermoplastic resin composition. And the content of component [D] was shown in the "structure" column of each table | surface with content of component [A], [B], and [C]. In the “Configuration” column, the content of the component [E], the content of the structural unit (d1) constituting the component [D], the components [A], [B], [C] and [D] Content of structural unit (d1) and rubbery polymer relative to the total amount, and component [A] when the total amount of components [A], [B], [C] and [D] is 100% by mass Or the ratio of content of [B] and the structural unit (d1) which comprises component [D] was shown.

In evaluating the composition, a thermoplastic resin composition for evaluating physical properties containing an additive (antioxidant) prepared in the following manner was used.
<Method for preparing thermoplastic resin composition for physical property evaluation>
After mixing the raw materials [P], [Q], [R] and [S] with a Henschel mixer, the tris (2,4-di-tert-butylphenyl) as an antioxidant is added to 100 parts of this total amount. ) Phosphite (trade name “Adeka Stub 2112”, manufactured by ADEKA) 0.2 part of pentaerystyl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name “ 0.2 part of ADK STAB AO-60 "(manufactured by ADEKA) was added and mixed at 25 ° C. Then, this mixture was supplied to a twin-screw extruder “BT40” (model name) manufactured by Plastic Engineering Laboratory Co., Ltd. with a cylinder set temperature of 240 ° C., melted and kneaded, and pellets (a thermoplastic resin composition for evaluating physical properties). Got.

(1) Charpy impact strength Measured under conditions of notching and temperature of 23 ° C. according to ISO 179. The unit is “kJ / m ² ”.
The test piece was prepared using an injection molding machine “J110AD-180H” (model name) manufactured by Nippon Steel Works with a cylinder set temperature of 220 ° C. and a mold temperature of 50 ° C. after sufficiently drying the pellets. did.
(2) Deflection temperature under load According to ISO 75, measurement was performed under a load of 1.8 MPa. The unit is “° C.”.
The test piece was prepared using an injection molding machine “J110AD-180H” (model name) manufactured by Nippon Steel Works with a cylinder set temperature of 220 ° C. and a mold temperature of 50 ° C. after sufficiently drying the pellets. did.
(3) Mass melt flow rate According to ISO 1133, the measurement was performed under the conditions of a temperature of 220 ° C. and a load of 98N. The unit is “g / 10 minutes”.
(4) Flame retardancy According to UL94 test method, it evaluated using the test piece of thickness 1.2mm.
The test piece was prepared using an injection molding machine “EC40” (model name) manufactured by Toshiba Machine Co., Ltd. after the pellets were sufficiently dried and the set temperature of the cylinder was 200 ° C. and the mold temperature was 30 ° C.
(5) Appearance After the above pellets have been sufficiently dried, the pellets are supplied to an electric injection molding machine “ELJECT NEX30” (trade name) manufactured by Nissei Plastic Industry Co., Ltd. with a set temperature of the cylinder of 220 ° C. and a mold temperature of 50 ° C. Thus, a flat plate of 80 mm × 55 mm × 2.4 mm (with a side gate of 4 mm × 1 mm at the center of one side of 55 mm) was obtained. The surface of this flat molded product was visually observed, and the appearance was determined according to the following criteria.
4: No pearl luster was observed.
3: The pearl luster was partially observed.
2: The pearl luster was sparsely observed on the entire surface.
1: A large amount of pearl luster was observed on the entire surface.

From Tables 1 to 7, the following is clear.
Comparative Example 1 is an example outside the scope of the present invention in which the content of component [A] is too large, and is inferior in molding processability, impact resistance and flame retardancy. Comparative Example 2 is an example outside the scope of the present invention in which the contents of the components [A] and [B] are both too small, and is inferior in flame retardancy. Comparative Example 3 is an example outside the scope of the present invention in which the content of the component [B] is too small, and is inferior in flame retardancy. Comparative Example 4 is an example outside the scope of the present invention in which the content of component [B] is too large, and is inferior in molding appearance. Comparative Example 5 is an example outside the scope of the present invention in which the content of the structural unit (d1) derived from the component [D] is too small, and is inferior in molding appearance. Comparative Example 6 is an example outside the scope of the present invention in which the content of the structural unit (d1) derived from the component [D] is too large, and is inferior in flame retardancy. Comparative Example 7 is an example outside the scope of the present invention in which the content of the component [B] is too small and the content of the component [D] is too large, and the flame retardancy is poor. Comparative Example 8 is an example outside the scope of the present invention in which the content of component [D] is too small, and is inferior in molding appearance. The comparative example 9 is an example which does not contain a component [C], and is inferior to impact resistance. Comparative Example 10 is an example outside the scope of the present invention in which the content of the rubbery polymer is too large, and is inferior in flame retardancy. Comparative Example 11 is an example outside the scope of the present invention in which the content of component [E] is too small, and is inferior in flame retardancy. Comparative Example 12 is an example outside the scope of the present invention in which the content of component [E] is too large, and is inferior in molding processability, impact resistance and heat resistance. Comparative Example 13 is an example using melamine cyanurate instead of the phosphorus flame retardant, and is inferior in impact resistance and heat resistance.
On the other hand, according to Examples 1 11 impact resistance, heat resistance, moldability, it is apparent that an excellent balance between molding appearance and flame retardancy.

By using the thermoplastic resin composition of the present invention, formation of pearly luster and the like on the surface is suppressed and it has a good appearance, impact resistance, heat resistance, molding processability, molding appearance and flame retardancy A molded product having an excellent balance can be obtained. And this thermoplastic resin composition is used for members such as vehicles, ships, electronic devices, home appliances, building materials, daily goods, sports goods, stationery, etc., impact resistance, heat resistance, molded appearance, flame retardancy, etc. It is suitable for forming molded products that require properties.
Moreover, since plant-derived resin can be used as a raw material for component [A], the obtained molded article is preferably used as a resin molded article having a low environmental load. And since the resin composition which made content of component [A] 25 mass% or more is allowed to identify and display "biomass plastic" by the Japan Bioplastics Association, this prevents global warming, It is possible to spread the recognition that fossil fuel resources will be saved and to contribute to the conservation of the natural environment, and to promote its spread.

Claims (4)

[A] an aliphatic polyester resin;
[B] polycarbonate resin;
[C] a rubbery polymer reinforced graft resin obtained by polymerizing a polymerizable unsaturated monomer in the presence of a rubbery polymer;
[D] A polymer obtained by polymerizing a polymerizable unsaturated monomer (excluding the rubber polymer reinforced graft resin [C]), which is derived from a (meth) acrylate compound A polymer comprising a (co) polymer having the structural unit (d1);
[E] a phosphorus-based flame retardant,
A thermoplastic resin composition comprising:
When the total amount of the components [A], [B], [C] and [D] is 100% by mass, the content of the component [A] is 25 to 42 % by mass, and the component [B ] Is 22 to 48 mass%, the content of the above component [C] is 8 to 14 mass%, the content of the above component [D] is 14 to 38 mass%, The content of the rubbery polymer derived from C] is 3 to 10% by mass, the content of the structural unit (d1) derived from the component [D] is 10 to 22 % by mass,
Value obtained by dividing the content of the component [A] by the content of the structural unit (d1) constituting the component [D] (content of the component [A]) / (content of the structural unit (d1)) Is 1.5 to 3.0,
Value obtained by dividing content of component [B] by content of structural unit (d1) constituting component [D] (content of component [B]) / (content of structural unit (d1)) Is 1.5 to 4.0,
When the total amount of the components [A], [B], [C] and [D] is 100 parts by mass, the content of the component [E] is 10 to 25 parts by mass. Thermoplastic resin composition.   The thermoplastic resin composition according to claim 1, wherein the rubber polymer is a diene rubber.   The thermoplastic resin composition according to claim 1 or 2, wherein the component [E] is a phosphate ester.   A molded article obtained by using the thermoplastic resin composition according to any one of claims 1 to 3.