JP5860260B2 - Thermoplastic resin composition and molded article - Google Patents

Description

  The present invention relates to a thermoplastic resin composition and a molded article excellent in impact resistance and molded appearance.

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 thermoplastic resin composition and a molded article that are excellent in impact resistance and give a molded article in which formation of pearl luster and the like on the surface thereof is suppressed.

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 having a structural unit (dx) derived from and a polymer having a structural unit (dy) derived from another polymerizable unsaturated monomer, wherein the other polymerizable unsaturated monomer The polymer contains an aromatic vinyl compound, and the polymer [D] is a polymer containing a structural unit (dx) derived from a (meth) acrylic acid ester compound in an amount of 0% by mass to ₁ % by mass. D-1) and, the structural units (dx), the _{r 1} wt% ultra Te polymer comprising at _{r 2} mass% or less and (D-2), the structural units (dx), becomes from a polymer containing 100% by mass or less beyond _{r 2} wt% (D-3), and , R ₁ = 35 (mass%) and r ₂ = 65 (mass%) , and the content ratio of the polymers (D-1), (D-2) and (D-3) is the sum of these. The thermoplastic resin composition characterized by being 5 to 80% by mass, 3 to 70% by mass, and 5 to 80% by mass, respectively, when the content is 100% by mass.
2. When the content ratio of the above components [A], [B], [C] and [D] is 100% by mass of the total amount of the components [A], [B], [C] and [D] The thermoplastic resin composition according to 1 above, which is 15 to 75% by mass, 10 to 70% by mass, 5 to 65% by mass, and 10 to 70% by mass, respectively .
3. The polymer [D] is a mass ratio of the (meth) acrylic acid ester compound and other vinyl monomers from 100 to 70: 0 to 0 to 30:70 to 100, or 0. The thermoplastic resin composition according to the above 1 or 2, comprising a polymer obtained by polymerization while changing the charge amount from -30: 70 to 100 to 100 to 70: 0 to 30.
4). The content ratio of the structural unit (dx) contained in the polymer [D] is 5 to 95% by mass when the total of the structural units constituting the polymer [D] is 100% by mass. The thermoplastic resin composition according to any one of 1 to 3.
5. 5. The thermoplastic resin composition according to any one of 1 to 4 above, wherein the aliphatic polyester resin [ A ] is a polylactic acid resin.
6). The rubbery polymer used to form the rubbery polymer reinforced graft resin [ C ] is a diene rubber, and the polymerizable unsaturated monomer used to form the rubbery polymer reinforced graft resin [ C ]. 6. The thermoplastic resin composition according to any one of 1 to 5, wherein the monomer comprises an aromatic vinyl compound and a vinyl cyanide compound.
7). The thermoplastic resin composition according to any one of 1 to 6, wherein the other polymerizable unsaturated monomer forming the structural unit (dy) includes an aromatic vinyl compound and a vinyl cyanide compound.
8). The content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from the vinyl cyanide compound contained in the polymer [D] is, when these totals are 100% by mass, 8. The thermoplastic resin composition as described in 7 above, which is 40 to 95% by mass and 5 to 60% by mass.
9. When the content ratios of the polymers (D-1), (D-2), and (D-3) are 100% by mass, the content is 10 to 70% by mass and 5 to 60% by mass, respectively. The thermoplastic resin composition according to any one of 1 to 8 above, which is 5 to 70% by mass.
10. Further, [E] the flame retardant, wherein the total amount of the above-mentioned components [A], [B], [C] and [D] is 100 parts by mass, 10 to 25 parts by mass is contained. The thermoplastic resin composition according to any one of the above.
11. A molded article obtained by using the thermoplastic resin composition according to any one of 1 to 10 above.

According to the thermoplastic resin composition of the present invention, it is possible to obtain a molded article having excellent appearance and excellent impact resistance by suppressing formation of pearl luster and the like on the surface. 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.

It is a graph which shows the ratio (%) of a structural unit (dx) about the polymer for component [D] obtained by the power feed method, and the relationship of the production amount of the polymer for component [D].

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 having a structural unit (dx) derived from an acid ester compound and a structural unit (dy) derived from another polymerizable unsaturated monomer , and the other polymerizable unsaturated monomer, Polymer (D-1) containing an aromatic vinyl compound, wherein the component [D] contains a structural unit (dx) derived from a (meth) acrylic acid ester compound in an amount of 0% by mass to ₁ % by mass. , containing the structural units (dx), beyond _{r 1} wt% at _{r 2} wt% or less And Polymer (D-2), becomes the structural unit (dx), since polymers comprising at _{r 2} wt% of 100 wt% greater than or less and (D-3), and, _r 1 = 35 (wt% ) And r ₂ = 65 (mass%) , and the content ratios of the polymers (D-1), (D-2), and (D-3) are as follows: They are 5-80 mass%, 3-70 mass%, and 5-80 mass%, respectively.

  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] polymerizes a polymerizable unsaturated monomer (hereinafter referred to as “polymerizable unsaturated monomer (c1)”) in the presence of a rubbery polymer (hereinafter referred to as “graft polymerization”). Is a rubbery polymer reinforced graft resin (hereinafter referred to as “graft resin”) contained in a resin composition (hereinafter referred to as “rubber reinforced resin”). This graft resin is a resin in which a (co) polymer containing a structural unit derived from the polymerizable unsaturated monomer (c1) is grafted to a rubbery polymer. And a (co) polymer portion containing a structural unit derived from the unsaturated unsaturated monomer (c1).
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 (c1) used. The ungrafted polymer is usually contained in the component [D], and when the polymerizable unsaturated monomer (c1) contains a (meth) acrylic acid ester compound, the polymer (D-1) , Included in any of polymer (D-2) and polymer (D-3).

  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 (c1) 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.
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, the polymerizable unsaturated monomer (c1) contains a (meth) acrylic acid ester compound. The ungrafted polymer contains a structural unit derived from a (meth) acrylic acid ester compound (the same structural unit as the structural unit (dx) contained in the component [D]). D-1), the polymer (D-2) and the polymer (D-3).

  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 (c1) 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 (c1) 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 (c1) 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, Preferably it is 95 mass%. The upper limit is usually 100% by mass. The ratio of the aromatic vinyl compound and the vinyl cyanide compound is, when the total of both is 100% by mass, molding processability, chemical resistance, hydrolysis resistance, impact resistance, rigidity of the obtained molded product. From the viewpoints of dimensional stability, appearance, 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, respectively. % And 15 to 40% by mass.

As the component [C], preferred graft resins are as follows. Among these, aspects (1) and (3) are particularly preferable from the viewpoints of moldability and the balance of impact resistance, heat resistance, appearance, and flame retardancy of the obtained molded product.
(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, from the viewpoint of the balance of molding processability and the impact resistance, heat resistance, appearance, and flame retardancy of the molded product obtained, aromatic vinyl compounds, vinyl cyanide compounds and ( A graft resin obtained by polymerizing a polymerizable unsaturated monomer containing a (meth) acrylate compound, which is a structural unit derived from a (meth) acrylate compound ((meth) acrylic structural unit) A rubber-reinforced graft resin having an upper limit of 80% by mass is preferable. 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 monomer (c1) all together in the reaction system in the presence of the total amount of the rubbery polymer. Alternatively, the polymerization may be performed while being divided or continuously fed. In addition, in the presence or absence of a part of the rubbery polymer, the polymerizable unsaturated monomer (c1) may be supplied all at once to initiate polymerization, or may be supplied separately or continuously. May be. 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 (c1).
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 (c1).
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 (c1).

  Emulsion polymerization can be performed on well-known conditions according to kinds, such as a polymerizable unsaturated monomer (c1) and a polymerization initiator. 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 more preferably 15 to 150% from the viewpoints of moldability, impact resistance, appearance, and the like of the obtained molded product. Preferably it is 20 to 100%. If this graft ratio is too low, the impact resistance and 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 of polymerizable unsaturated monomer (c1). Time, 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) acrylate compound (dx ) In an amount of 0% by mass or more and r ₁ % by mass or less, and a polymer (D-1) containing a structural unit derived from another vinyl monomer described later (hereinafter referred to as “structural unit (dy)”). And a polymer (D-2) containing the structural unit (dx) in an amount exceeding r ₁ % by mass and r ₂ % by mass or less, and containing the structural unit (dy), and the structural unit (dx), r ₂ % by mass and 100% by mass or less, and optionally a polymer (D-3) containing a structural unit (dy). r ₁ is 35% by mass and r ₂ is 65% by mass.
Moreover, the content rate of the said polymer (D-1), a polymer (D-2), and a polymer (D-3) is 5-80 mass%, respectively, when these sum is 100 mass%. 3 to 70% by mass and 5 to 80% by mass .

  About the (meth) acrylic acid ester compound which forms the said structural unit (dx), 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 (dx) contained in the component [D] 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 C1-C4 hydrocarbon group is. 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 may be used. 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%.

  The content of the structural unit (dx) contained in the component [D] is preferably 5 to 95% by mass, more preferably 10 to 10% when the total of the structural units constituting the component [D] is 100% by mass. It is 90 mass%, More preferably, it is 15-85 mass%. When the content of the structural unit (dx) is 5 to 80% by mass, the appearance and impact resistance of the obtained molded product are excellent.

Other polymerizable unsaturated monomers that form the structural unit (dy) include aromatic vinyl compounds, and other vinyl cyanide compounds, maleimide compounds, unsaturated acid anhydrides, and carboxyl group-containing unsaturated monomers. Examples include compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, α-olefins, chlorine-containing unsaturated compounds (such as vinyl chloride and vinylidene chloride), and fluorine-containing unsaturated compounds. About these compounds, the exemplary compound of each compound which can be used as a polymerizable unsaturated monomer used for formation of the said component [C] is applied. The structural unit (dy) contained in the component [D] may be only one type or two or more types.
As the other vinyl monomers, aromatic vinyl compounds, vinyl cyanide compounds, maleimide compounds, and the like are preferable, and aromatic vinyl compounds and vinyl cyanide compounds are particularly preferable. As the aromatic vinyl compound, styrene and α-methylstyrene are preferable, as the vinyl cyanide compound, acrylonitrile is preferable, and as the maleimide compound, N-phenylmaleimide is preferable.

  When the structural unit (dy) includes a structural unit derived from an aromatic vinyl compound and a structural unit derived from a vinyl cyanide compound, the content ratio of these structural units is determined by the polymer (D-1) and the polymer. In all of (D-2) and the polymer (D-3), when the total of both is 100% by mass, preferably 40 to 95% by mass and 5 to 60% by mass, more preferably 50 to 50%, respectively. They are 90 mass% and 10-50 mass%, More preferably, they are 60-85 mass% and 15-40 mass%. Thereby, sufficient toughness and moldability are obtained.

  Said component [D] consists of a polymer (D-1), a polymer (D-2), and a polymer (D-3), but a polymer (D-1) in the case of containing a structural unit (dx) In the polymer (D-2) and the polymer (D-3), the type of the structural unit (dx) may be the same or different. The type of the structural unit (dy) may also be the same or different.

The polymer (D-1), the polymer (D-2) and the polymer (D-3) are polymers having different contents of the structural unit (dx) from each other. It is a polymer in which the content of is increased.
The component [D] is composed of the polymer (D-1), the polymer (D-2), and the polymer (D-3) having the above-described configuration, so that the component [D] is between the component [A] and the component [B]. Therefore, it is possible to obtain a molded article having a high effect of improving the compatibility and excellent in impact resistance and surface appearance. In particular, when the component [B] is used which is composed of a copolymer aggregate in which the content of the structural unit (dx) is in the range of 5 to 80% by mass as described above with respect to the component [D]. The above effects are remarkable.

The polymer (D-1) is a structural unit (dx), a polymer comprising at 0 wt% or more _r 1 (35) wt% or less, is exemplified below.
(1) (Co) polymer (D-1-1) comprising structural unit (dy)
(2) Copolymer (D-1-2) comprising structural units (dx) and (dy)
When each polymer in these embodiments is contained in the composition, any of them may be used alone or in combination of two or more. For example, when the polymer (D-1-2) is composed of two types of polymers and 0 <r ₁₁ <r ₁₂ ≦ 35 , the weight including the structural unit (dx) of r ₁₁ % by mass is included. A coalescence and a polymer containing ₁₂ % by mass of structural unit (dx) may be used in combination. Moreover, you may comprise a polymer (D-1) with the combination of a polymer (D-1-1) and (D-1-2).
The polymer (D-1) may be composed of a polymer containing no structural unit (dx), that is, a (co) polymer (D-1-1). When it contains (D-1-1), it is preferable that a polymer (D-1-2) is also included. At this time, the content ratio of the polymer (D-1-2) containing the structural units (dx) and (dy) is preferably 10% by mass or more, more preferably, with respect to the polymer (D-1). 30-100 mass%, More preferably, it is 50-100 mass%.

The content of the structural unit (dx) constituting the polymer (D-1) is preferably 35 wt% more than 0 mass% or less, more preferably 2-35 wt%.
r ₁ is 35 % by mass. When two or more types of polymers corresponding to the polymer (D-1) are included, the value shown as “content of structural unit (dx) contained in polymer (D-1)” is included in each polymer. It is an average value calculated from the content of the structural unit (dx).

The polymer (D-2) comprises a structural unit (dx) and a structural unit (dx) comprising structural units (dx) and (dy) containing r ₁ (35) mass% and r ₂ (65) mass% or less. It is a polymer. As described above, the polymer (D-2) can be composed of at least one polymer including a predetermined amount of the structural unit (dx). For example, when it is composed of two types of copolymers and 35 <r ₂₁ <r ₂₂ ≦ 65 , a polymer containing ₂₁ mass% of structural units (dx) and a structural unit (dx) of r _The polymer (D-2) which consists of a polymer containing ₂₂ mass% can be used.

_{R 2} is the upper limit of the content of the structural unit (dx) constituting the polymer (D-2) is 65 mass%. When two or more types of polymers corresponding to the polymer (D-2) are contained, the value shown as “content of structural unit (dx) contained in polymer (D-2)” is included in each polymer. It is an average value calculated from the content of the structural unit (dx).
In the present invention, since r ₂ is 65 mass%, in the compositions of the present invention, in particular, to improve the component (B), the compatibility with the polymer (D-3), further components (A) And the polymers (D-1) and (D-2) (particularly, the structural unit (dy) constituting the polymers (D-1) and (D-2) is an aromatic vinyl compound and cyanide). In the case where the structural unit derived from both of the vinyl halide compound is included), resulting in excellent compatibility between the components [A] and [B]. Excellent heat resistance and appearance.

The polymer (D-3) is a polymer containing the structural unit (dx) in an amount exceeding 100 mass% and exceeding r ₂ (65) mass%, and is exemplified below.
(1) (Co) polymer (D-3-1) comprising structural unit (dx)
(2) Copolymer (D-3-2) comprising structural units (dx) and (dy)
When each polymer in these embodiments is contained in the composition, any of them may be used alone or in combination of two or more. For example, when the polymer (D-3-2) is composed of two types of polymers, and 65 <r ₃₁ <r ₃₂ <100, the weight including the structural unit (dx) of ₃₁ % by mass of r A coalescence and a polymer containing ₃₂ % by mass of structural unit (dx) may be used in combination. Moreover, you may comprise a polymer (D-1) with the combination of a polymer (D-3-1) and (D-3-2).
The polymer (D-3) may be composed of a polymer containing no structural unit (dy), that is, a (co) polymer (D-3-1). When it contains (D-3-1), it is preferable that a polymer (D-3-2) is also included. At this time, the content ratio of the polymer (D-3-2) including the structural units (dx) and (dy) is preferably 10% by mass or more, more preferably, with respect to the polymer (D-3). 30-100 mass%, More preferably, it is 50-100 mass%.

The content of the structural unit (dx) constituting the polymer (D-3) is preferably less than 100% by weight exceeds 65 wt%, 95 wt% or less and more preferably more than 65 wt%. When two or more types of polymers corresponding to the polymer (D-3) are contained, the value indicated as “content of structural unit (dx) contained in polymer (D-3)” is included in each polymer. It is an average value calculated from the content of the structural unit (dx).

  The content ratio of the polymer (D-1), the polymer (D-2) and the polymer (D-3) constituting the component [D] is from the viewpoint of impact resistance and appearance of the obtained molded product. When the total of these is 100% by mass, it is 5 to 80% by mass, 3 to 70% by mass and 5 to 80% by mass, respectively, preferably 10 to 70% by mass, 5 to 65% by mass and 10%. It is -70 mass%, More preferably, it is 15-65 mass%, 10-65 mass%, and 15-65 mass%.

  As described above, in the polymer (D-1), the polymer (D-2) and the polymer (D-3), at least one kind is a structure derived from an aromatic vinyl compound as the structural unit (dy). It is preferable to include a unit and a structural unit derived from a vinyl cyanide compound. At this time, the structural unit derived from the aromatic vinyl compound and the structure derived from the vinyl cyanide compound included in the polymer [D]. The content ratio of the units is preferably 40 to 95% by mass and 5 to 60% by mass, more preferably 50 to 90% by mass when the total of these is 100% by mass from the viewpoint of toughness and molding processability. % And 10 to 50% by mass, more preferably 60 to 85% by mass and 15 to 40% by mass.

The polymer (D-1) is preferably another vinyl monomer containing at least an aromatic vinyl compound among the structural unit (dx) and an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound. Derived from other vinyl-based monomers including a structural unit (dy) derived from the body, and more preferably a structural unit (dx) and at least an aromatic vinyl compound and a vinyl cyanide compound And a structural unit (dy).
The polymer (D-2) is preferably another vinyl monomer containing at least an aromatic vinyl compound among the structural unit (dx) and an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound. Derived from other vinyl-based monomers including a structural unit (dy) derived from the body, and more preferably a structural unit (dx) and at least an aromatic vinyl compound and a vinyl cyanide compound And a structural unit (dy).
The polymer (D-3) is preferably another vinyl monomer containing at least an aromatic vinyl compound among the structural unit (dx) and an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound. A structural unit (dy) derived from the body, and a (co) polymer comprising only the structural unit (dx), more preferably the structural unit (dx) and at least an aromatic vinyl These are a copolymer comprising a compound and a structural unit (dy) derived from another vinyl monomer, and a (co) polymer comprising only a structural unit (dx).

In the composition of the present invention, the component [D] can be selected in a preferred mode depending on the configuration of the component [C].
(1) The rubbery polymer used for the formation of the component [C] is a diene rubber, the polymerizable unsaturated monomer is an aromatic vinyl compound and a vinyl cyanide compound, and is included in the component [D]. In the case where the structural unit (dy) includes a structural unit derived from an aromatic vinyl compound and a structural unit derived from a vinyl cyanide compound,
The content of the structural unit (dx) contained in the component [D] is preferably 5 to 95% by mass, more preferably 100% by mass when the total of the structural units constituting the component [D] is 100% by mass. The content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from the vinyl cyanide compound is 10% by mass to 10% by mass, more preferably 15% to 85% by mass. Sometimes, preferably 40 to 95% by weight and 5 to 60% by weight, more preferably 50 to 90% by weight and 10 to 50% by weight, still more preferably 60 to 85% by weight and 15 to 40% by weight, respectively. .
In this case, _{r 1} is 35 mass%, _{r 2} is 65 mass%. The relationship between r ₁ and r ₂ is (r ₂ −r ₁ ) ≧ 15 (mass%), preferably (r ₂ −r ₁ ) ≧ 20 (mass%), more preferably (r ₂ −r ₁ ) ≧ 25 (mass%). However, usually, (r ₂ −r ₁ ) ≦ 60 (mass%).
Moreover, when the content rate of the said polymer (D-1), (D-2), and (D-3) makes these totals 100 mass%, Preferably it is 10-70 mass%, respectively 5 -60 mass% and 5-70 mass%, more preferably 15-60 mass%, 10-55 mass% and 10-60 mass%, still more preferably 20-55 mass%, 15-50 mass% and 15-55. % By mass.

(2) The rubbery polymer used to form the component [C] is a diene rubber, and the polymerizable unsaturated monomer is an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester compound. In the case where the structural unit (dy) contained in the component [D] includes a structural unit derived from an aromatic vinyl compound and a structural unit derived from a vinyl cyanide compound,
The content of the structural unit (dx) contained in the component [D] is preferably 5 to 95% by mass, more preferably 100% by mass when the total of the structural units constituting the component [D] is 100% by mass. The content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from the vinyl cyanide compound is 10% by mass to 10% by mass, and more preferably 10% by mass to 100% by mass. Sometimes, preferably 40 to 95% by weight and 5 to 60% by weight, more preferably 50 to 90% by weight and 10 to 50% by weight, still more preferably 60 to 85% by weight and 15 to 40% by weight, respectively. .
In this case, _{r 1} is 35 wt%, _{r 2} is 65 mass%. The relationship between r ₁ and r ₂ is (r ₂ −r ₁ ) ≧ 15 (mass%), preferably (r ₂ −r ₁ ) ≧ 20 (mass%), more preferably (r ₂ −r ₁ ) ≧ 25 (mass%). However, usually, (r ₂ −r ₁ ) ≦ 60 (mass%).
Moreover, when the content rate of the said polymer (D-1), (D-2), and (D-3) makes these sum 100 mass%, respectively, Preferably it is 7-60 mass%, 5 It is -70 mass% and 5-75 mass%, More preferably, it is 18-55 mass%, 10-60 mass%, and 10-70 mass%.

When the ratios r ₁ and r ₂ are determined as described above, the content ratio of the polymers (D-1), (D-2), and (D-3) is determined based on the component [D] by liquid chromatography. Can be obtained by subjecting to For example, when the component [D] contains a methyl methacrylate / styrene / acrylonitrile copolymer, gradient analysis using chloroform, tetrahydrofuran, ethanol or the like can be applied.

  The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the component [D] is preferably 0.2 to 0.9 dl / g, more preferably 0, from the viewpoint of moldability and impact resistance of the molded product. .25 to 0.85 dl / g, more preferably 0.3 to 0.8 dl / g. In addition, when measuring the said intrinsic viscosity [(eta)], the measuring method with respect to the acetone soluble part (or acetonitrile soluble part) in the rubber reinforced resin containing the said component [C] is applicable.

  The method for producing the polymers (D-1), (D-2), and (D-3) constituting the component [D] is not particularly limited, and examples thereof include emulsion polymerization, solution polymerization, and bulk polymerization. Can be applied. For example, after producing the said polymers (D-1), (D-2), and (D-3) separately, component [D] can be formed by mixing. Moreover, in one reaction system, after producing any 2 types of polymers, it can mix with another 1 type and can form component [D]. Furthermore, you may manufacture three types of polymers in one reaction system.

In one reaction system, when producing two or three kinds of the polymers (D-1), (D-2) and (D-3), the (meta) for the reaction system For example, a method of proceeding polymerization while changing the charged amount (feed amount, feed rate) of the acrylate compound and other vinyl monomers is applied. For example, a power feed method disclosed in JP-A-50-63085 can be applied. According to this power feed method, the polymerization of a plurality of monomers proceeds sequentially at different rates. Therefore, while changing the charged amount of all the monomers (feed amount, feed rate), for example, the above-mentioned By continuously supplying the (meth) acrylic acid ester compound to the reaction system continuously or intermittently, the content ratio of the structural unit (dx) is in a wide range of 0% by mass to 100% by mass (both). It can consist of an aggregate | assembly of a polymer. In the present invention, the (co) polymer aggregate obtained by the power feed method is such that the polymers (D-1), (D-2), and (D-3) are each in a predetermined ratio. Since it can be contained, it is suitable as a method for producing the polymer for component [D].
In the present invention, the charge amount of the (meth) acrylic acid ester compound and the other vinyl monomer is changed from 100 to 70: 0 to 30 to 30 to 70 to 100 by mass ratio. The charged amount of the polymer obtained by polymerization and / or the (meth) acrylic acid ester compound and the other vinyl monomer is 0-30: 70-100 to 100-70: The polymer obtained by polymerization while changing to 0 to 30 is preferably part or all of the component [D]. By using a composition containing a polymer obtained by this method, a molded product having an excellent balance of impact resistance, heat resistance and appearance can be obtained.
FIG. 1 shows polymerization while changing the charged amount of the (meth) acrylic acid ester compound and the other vinyl monomer from 100 to 70: 0 to 30 to 70 to 100 by mass ratio. It is a graph which shows an example of distribution of the (co) polymer obtained by doing. In FIG. 1, there is almost no difference in the amount of production between polymers having different structural unit (dx) contents. However, for example, the amount of the polymer (D-1) can be increased or the polymer (D-3) can be increased by changing the amount of monomer charged (feed amount, feed rate) during the reaction. Can be produced, or a polymer for component [D] having a multi-modal distribution can be produced.

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]. % Is 15 to 75% by mass, 10 to 70% by mass, 5 to 65% by mass, and 10 to 70% by mass, preferably 20 to 70% by mass, 15 to 65% by mass, It is 55 mass% and 10-60 mass%, More preferably, it is 25-65 mass%, 20-60 mass%, 5-45 mass%, and 10-50 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, and impact resistance is improved. An excellent molded product can be obtained. In addition, a molded product having an excellent balance of impact resistance, heat resistance, molding processability and appearance can be obtained.
When there is too little content of the said component [B], the impact resistance of the molded article obtained may not be enough. On the other hand, when there is too much content of component [B], an external appearance property may be inferior.
If the content of the component [C] is too small, the impact resistance may not be sufficient. On the other hand, when there is too much content of the said component [C], heat resistance may not be enough.
Moreover, when there is too little content of the said component [D], the external appearance of the molded article obtained may not be enough. On the other hand, when there is too much content of the said component [D], impact resistance and heat resistance may not be enough.
In addition, when the above-mentioned component [A] is contained in an amount of 25% by mass or more with respect to the entire composition of the present invention (including all other polymers and additives described later), according to the Japan Bioplastics Association, Since the identification of “biomass plastic” is permitted, the lower limit of the content ratio of the component [A] is the sum of the components [A], [B], [C] and [D]. When the amount is 100% by mass, it is preferably 25% by mass, more preferably 27% by mass, and still more preferably 29% by mass.

  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 30% by mass, preferably 3 to 30% by mass, preferably 3 to 20% by mass, and particularly preferably 3 to 15% by mass. If the content of the rubbery polymer is too small, the impact resistance may not be sufficient. On the other hand, if the content of the rubbery polymer is too large, the heat resistance may not be sufficient.

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 sum of the above components [A], [B], [C] and [D] being 100. When it is made into a mass part, Preferably it is 30 mass parts, More preferably, it is 20 mass parts.

The composition of the present invention may further comprise flame retardants, fillers, plasticizers, antioxidants, ultraviolet absorbers, anti-aging agents, lubricants, weathering stabilizers, light stabilizers, heat stabilizers, depending on the purpose and application. Agent, antistatic agent, water repellent agent, oil repellent agent, antifoaming agent, antibacterial agent, preservative, colorant (pigment, dye, etc.), fluorescent brightener, conductivity enhancer, etc. it can.
When the composition of the present invention contains a flame retardant (hereinafter referred to as “component [E]” or “flame retardant [E]”), a molded article having excellent flame retardancy can be obtained.

  Examples of the component [E] include organic flame retardants, inorganic flame retardants, and reactive flame retardants. These can be used alone or in combination of two or more.

  Examples of organic flame retardants include phosphorus flame retardants, halogen flame retardants, guanidine salts, and phosphazene compounds. These may be used alone or in combination. In the present invention, a phosphorus-based flame retardant is preferably used, and conventionally known phosphorus-containing compounds can be used alone or in combination of two or more. The properties of the flame retardant are not particularly limited, but are usually liquid or solid at room temperature.

  Examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, Phosphate esters such as dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, modified compounds thereof, and condensed phosphate esters represented by the following general formula (1) Examples thereof include phosphazene derivatives containing a compound, phosphorus element and 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.

  As the phosphorus-containing compound, a condensed phosphate compound is particularly preferable because a resin molded product having excellent flame retardancy and low environmental load can be obtained.

  Examples of the halogen flame retardant include brominated epoxy compounds, brominated alkyl triazine compounds, brominated bisphenol epoxy resins, brominated bisphenol phenoxy resins, brominated bisphenol polycarbonate resins, brominated polystyrene resins, brominated crosslinked polystyrene. Examples thereof include resins, brominated bisphenol cyanurate resins, brominated polyphenylene ethers, decabromodiphenyl oxide, tetrabromobisphenol A and oligomers thereof.

  Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium compound, molybdenum compound, and zinc stannate.

  In the composition containing the component [E], the content of the component [E] provides good flame retardancy without deteriorating impact resistance, heat resistance, molding processability and appearance. Therefore, when the total amount of the components [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 Is 12 to 16 parts by mass. When there is too much content of the said component [E], heat resistance and impact resistance will be inferior.

  Other additives are as follows.

  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 composition of this invention can be manufactured by knead | mixing the raw material containing component [A], [B], [C] and [D], and component [E] used as needed. 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 components [A], [B], [C] and [D], and the type and amount of the component [E] used as desired. The temperature is in the range of 220 ° C to 260 ° C.

By using the thermoplastic resin composition of the present invention, it is possible to obtain a molded article that is excellent in impact resistance and that is excellent in surface appearance by suppressing formation of pearl luster and the like on the surface. And it is excellent in the balance of the impact resistance of the molded product obtained, heat resistance, and an external appearance property.
The Charpy impact strength measured under the conditions described below is preferably 8 to 80 J / m ² , more preferably 12 to 70 J / m ² , and particularly preferably 15 to 65 J / m ² .
The deflection temperature under load measured under the conditions described below is preferably 50 ° C to 95 ° C, more preferably 58 ° C to 95 ° C, and particularly preferably 70 ° C to 90 ° C.
Moreover, in the composition containing component [E], the flame retardance (UL94 standard) measured on the conditions mentioned later is a V-2 class on 1.2 mm conditions.

  The composition of the present invention is suitable not only for the formation of uncolored molded products but also for the formation of molded products and the like in which the phenomenon of poor 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 a molded product is produced using the molding apparatus, the molding temperature and the mold temperature are the above components [A], [B], [C] and [D], and the component [E] used as desired. Or the kind of raw material components (including other polymers) to be used.
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 obtained by polymerizing a vinyl monomer in the presence of a rubbery polymer, as shown in Synthesis Example 1 below. The rubber reinforced resin is a mixture comprising the rubbery polymer reinforced graft resin [C] according to the present invention and the polymer [D].

Synthesis Example 1 (Synthesis of rubber reinforced resin R1)
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. Thereafter, it was washed and neutralized with an aqueous potassium hydroxide solution, further washed with water and then dried to obtain a rubber reinforced resin R1 (polymerization conversion rate: 98.5%). The graft ratio in the graft resin contained in this resin R1 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.

1-4. Raw material [S]
The copolymer obtained by the following synthesis examples 2-8 was used.

Synthesis Example 2 (Synthesis of copolymer S1)
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., 0.2 part of diisopropylbenzene hydroperoxide, 0.28 part of tert-dodecyl mercaptan and 100 parts of methyl methacrylate were added to the reaction system over 3 hours. It dripped continuously and superposed | polymerized. Polymerization was completed at the same time as the dropping was completed, and latex (L1-1) containing polymethyl methacrylate was obtained.
On the other hand, in a glass flask equipped with a stirrer, 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate and 0.5 part of sodium hydrogen carbonate were placed in a nitrogen stream, and the temperature was raised while stirring. did. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., 0.2 parts of diisopropylbenzene hydroperoxide, 0.28 parts of tert-dodecyl mercaptan, 50 parts of methyl methacrylate, 37 parts of styrene and A mixture of 13 parts of acrylonitrile was added dropwise over 3 hours to carry out polymerization. Polymerization was completed at the same time as the dropping was completed, and latex (L1-2) containing methyl methacrylate / styrene / acrylonitrile copolymer was obtained.
Further, in another glass flask equipped with a stirrer, 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate and 0.5 part of sodium hydrogen carbonate were placed in a nitrogen stream, and the mixture was raised while stirring. Warm up. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C, a mixture of 0.2 parts of diisopropylbenzene hydroperoxide, 0.28 parts of tert-dodecyl mercaptan, 75 parts of styrene and 25 parts of acrylonitrile was added to the reaction system. It dripped over 3 hours and superposed | polymerized. Polymerization was completed at the same time as the dropping was completed, and a latex (L1-3) containing a styrene / acrylonitrile copolymer was obtained.
Next, the latexes (L1-1), (L1-2), and (L1-3) obtained above were mixed so that the polymer content ratio (mass ratio) was 35:30:35. And the polymer was solidified and washed with water using the magnesium sulfate solution. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material S1.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the raw material S1 was 0.42 dl / g.

Synthesis Example 3 (Synthesis of copolymer S2)
In this synthesis example, a first monomer comprising a mixture of 0.1 part diisopropylbenzene hydroperoxide, 0.14 part tert-dodecyl mercaptan, 47.5 parts methyl methacrylate and 2.5 parts styrene (at the start of synthesis) And a second monomer comprising a mixture of 0.1 part diisopropylbenzene hydroperoxide, 0.14 part tert-dodecyl mercaptan, 36.5 parts styrene and 13.5 parts acrylonitrile. At the start of synthesis, polymerization was carried out in the following manner using a second supply source) to obtain a raw material S2.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. Simultaneously with the supply of the first monomer, the second monomer was continuously supplied from the second supply source to the first supply source at a rate of 16.7 parts per hour. As a result, the composition of the monomer in the first supply source changed with time, and the composition of the monomer supplied from the first supply source to the reaction system was also changed sequentially. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of methyl methacrylate / styrene / acrylonitrile copolymers having different compositions.
Thereafter, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material S2.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the raw material S2 was 0.49 dl / g.

Synthesis Example 4 (Synthesis of copolymer S3)
In this synthesis example, a first monomer comprising a mixture of 0.1 part of diisopropylbenzene hydroperoxide, 0.14 part of tert-dodecyl mercaptan, 49.5 parts of methyl methacrylate and 0.5 part of n-butyl acrylate. (Contained in the first source at the start of synthesis) and a second mixture of 0.1 part diisopropylbenzene hydroperoxide, 0.14 part tert-dodecyl mercaptan, 37.5 parts styrene and 12.5 parts acrylonitrile. Polymerization was performed in the following manner using a monomer (stored in the second supply source at the start of synthesis) to obtain a raw material S3.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. Simultaneously with the supply of the first monomer, the second monomer was continuously supplied from the second supply source to the first supply source at a rate of 16.7 parts per hour. As a result, the composition of the monomer in the first supply source changed with time, and the composition of the monomer supplied from the first supply source to the reaction system was also changed sequentially. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of methyl methacrylate / n-butyl acrylate / styrene / acrylonitrile copolymers having different compositions.
Thereafter, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material S3.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the raw material S3 was 0.48 dl / g.

Synthesis Example 5 (Synthesis of copolymer S4)
In this synthesis example, a first monomer composed of a mixture of 0.1 part of diisopropylbenzene hydroperoxide, 0.14 part of tert-dodecyl mercaptan, 71.3 parts of methyl methacrylate and 3.7 parts of styrene (at the start of synthesis) A second monomer comprising a mixture of 0.1 part diisopropylbenzene hydroperoxide, 0.14 part tert-dodecyl mercaptan, 18.2 parts styrene and 6.8 parts acrylonitrile. At the start of synthesis, the polymerization was carried out in the following manner using the second supply source) to obtain a raw material S4.
A glass flask equipped with a stirrer was charged with 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate, and 0.5 part of sodium hydrogen carbonate in a nitrogen stream and heated with stirring. When the internal temperature reached 45 ° C., 0.06 part of ethylenediaminetetraacetic acid / tetrasodium / dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.12 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., continuous supply of the first monomer was performed from the first supply source to the reaction system at a rate of 33.3 parts per hour. Initiated and polymerized. Simultaneously with the supply of the first monomer, the second monomer was continuously supplied from the second supply source to the first supply source at a rate of 8.3 parts per hour. As a result, the composition of the monomer in the first supply source changed with time, and the composition of the monomer supplied from the first supply source to the reaction system was also changed sequentially. The time required to supply all the monomers is about 3 hours.
Simultaneously with the completion of the monomer supply, the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of methyl methacrylate / n-butyl acrylate / styrene / acrylonitrile copolymers having different compositions.
Thereafter, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material S4.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the raw material S4 was 0.39 dl / g.

Synthesis Example 6 (Synthesis of copolymer S5)
In this synthesis example, a first monomer comprising a mixture of 47.5 parts of methyl methacrylate, 0.1 part of diisopropylbenzene hydroperoxide and 0.14 part of tert-dodecyl mercaptan (at the start of synthesis, the first source Containment), 40 parts of styrene, 0.08 part of diisopropylbenzene hydroperoxide, 0.11 part of tert-dodecyl mercaptan (accommodated in the second source at the start of synthesis), acrylonitrile A third monomer consisting of a mixture of 12.5 parts, diisopropylbenzene hydroperoxide 0.02 parts and tert-dodecyl mercaptan 0.03 parts (accommodated in a third source at the start of synthesis), Polymerization was performed in the following manner to obtain a raw material S5.
To a glass flask equipped with a stirrer, 184 parts of ion-exchanged water, 2.0 parts of sodium dodecylbenzenesulfonate and 0.5 part of sodium bicarbonate were added in a nitrogen stream, and the temperature was raised while stirring. When the internal temperature reached 45 ° C., 0.062 part of ethylenediaminetetraacetic acid / tetrasodium dihydrate, 0.002 part of ferrous sulfate heptahydrate and 0.124 part of sodium formaldehyde sulfoxylate were ionized. A solution dissolved in 16 parts of exchange water was added. Thereafter, the temperature was further raised, and when the internal temperature reached 50 ° C., monomers were continuously supplied from the first, second and third supply sources to the reaction system, and polymerization was carried out over 3 hours. . The total amount of monomers to be supplied is successively constant (100 parts), and the amount of monomers supplied from each supply source is set to the first supply source: the second supply source at the start of supply. The third supply source was set to 95: 5: 0, and at the end of supply (after 3 hours), the first supply source: the second supply source: the third supply source = 0: 73: 27.
Simultaneously with the completion of the monomer supply (after the completion of the 3-hour supply), the polymerization was completed to obtain a latex containing a polymer mixture mainly composed of a plurality of methyl methacrylate / styrene / acrylonitrile copolymers having different compositions. .
Thereafter, a magnesium sulfate solution was added to the latex to coagulate the polymer and washed with water. Then, it dried and collect | recovered the polymer mixture. This polymer mixture was used as raw material S5.
The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the acetone-soluble component of the raw material S5 was 0.50 dl / g.

Synthesis Example 7 (Synthesis of copolymer S6)
A synthesis apparatus in which two jacketed polymerization reactors equipped with ribbon blades were connected was used. After purging nitrogen gas into each reactor, the first reactor was charged with a mixture of 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene, and 0.15 part of tert-dodecyl mercaptan as a molecular weight regulator. And a solution in which 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile), which is a polymerization initiator, is dissolved in 5 parts of toluene, are continuously supplied. Polymerization was carried out at 0 ° C. The average residence time of the supplied monomers and the like was 2 hours, and the polymerization conversion after 2 hours was 56%.
Next, the obtained polymer solution was continuously taken out by a pump provided outside the first reactor and supplied to the second reactor. The amount continuously taken out is the same as the amount supplied to the first reactor. In the second reactor, polymerization was performed at 130 ° C. for 2 hours, and the polymerization conversion after 2 hours was 74%.
Thereafter, the polymer solution was recovered from the second reactor, and this was introduced into an extruder with a biaxial three-stage vent. Then, the unreacted monomer and toluene (polymerization solvent) were directly devolatilized to recover the styrene / acrylonitrile copolymer. This styrene / acrylonitrile copolymer was used as raw material S6.
The intrinsic viscosity [η] of this raw material S6 (in methyl ethyl ketone, 30 ° C.) was 0.60 dl / g.

Synthesis Example 8 (Synthesis of copolymer S7)
In the same manner as in Synthesis Example 10, except that 75 parts of styrene and 25 parts of acrylonitrile were used instead of 50 parts of methyl methacrylate, 31 parts of styrene, and 19 parts of acrylonitrile, both monomers of methyl methacrylate, styrene, and acrylonitrile were used. A polymer was obtained. The polymerization conversion after 2 hours in the first reactor was 61%, and the polymerization conversion after 2 hours in the second reactor was 76%.
This methyl methacrylate / styrene / acrylonitrile copolymer was used as raw material S7.
The intrinsic viscosity [η] of this raw material S7 (in methyl ethyl ketone, 30 ° C.) was 0.33 dl / g.

1-5. Raw material [U]
As a flame retardant, 1,3-phenylenebis (dixylenyl) phosphate “PX-200” (trade name) manufactured by Daihachi Chemical Industry Co., Ltd. was used.

2. Production and Evaluation of Thermoplastic Resin Composition Examples 1 to 13 and Comparative Examples 1 to 5
The raw materials [P], [Q], [R], [S] and [U] were used in the ratios shown in Tables 1, 2, 3, and 4 to obtain thermoplastic resin compositions.
Of the raw materials [R], the rubber-reinforced resin obtained by Synthesis Example 1 is a mixture composed of 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 (dx) constituting the component [D], the components [A], [B], [C] and [D] The structural unit (dx) and the content ratio of the rubbery polymer relative to the total amount are 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 (impact resistance)
In accordance with ISO 179, measurement was performed under the conditions of a notch and a temperature of 23 ° C. 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 (heat resistance)
According to ISO 75, the 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) Bending strength Measured at 23 ° C. according to ISO 179. The unit is “MPa”.
(4) Flexural modulus Measured at 23 ° C. according to ISO 179. The unit is “MPa”.
(5) Molding appearance After the pellets are sufficiently dried, the electric injection molding machine “Erject NEX30” (trade name) manufactured by Nissei Plastic Industrial Co., Ltd. with a cylinder set temperature of 220 ° C. and a mold temperature of 50 ° C. Then, a flat plate of 80 mm × 55 mm × 2.4 mm (4 mm × 1 mm side gate provided 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.
3: No pearl luster was observed.
2: The pearl luster was partially observed.
1: A large amount of pearl luster was observed on the entire surface.
(6) 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.

From Tables 1 to 4, the following is clear.
Since Comparative Example 1 does not contain the component [D] according to the present invention, it is inferior in impact resistance and molded appearance. Since Comparative Example 2 does not contain the component [D] according to the present invention, it is inferior in impact resistance and molded appearance. Since Comparative Example 3 does not include the component [D] according to the present invention, that is, does not include the polymer (D-2), it is inferior in impact resistance and molding appearance. Since Comparative Example 4 does not contain the component [B] according to the present invention, it is inferior in impact resistance. Moreover, since the comparative example 5 does not contain the component [C] which concerns on this invention, it is inferior to impact resistance and shaping | molding external appearance property.
On the other hand, according to Examples 1-13, it is clear that it is excellent in impact resistance and shaping | molding external appearance property. Also, Example 1 using the raw material for component [D] (S1) prepared by latex blending, and the raw material for component [D] (S2) obtained by polymerization while changing the charged amount of the monomer When compared with Example 2 using the above, it can be seen that the latter is superior in impact resistance.

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 (11)

[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 structural unit (dx) obtained by polymerizing a polymerizable unsaturated monomer and derived from a (meth) acrylic acid ester compound and a structural unit (dy) derived from another polymerizable unsaturated monomer A thermoplastic resin composition comprising a polymer having the following (excluding the rubbery polymer reinforced graft resin [C]),
The other polymerizable unsaturated monomer includes an aromatic vinyl compound,
The polymer [D] includes a polymer (D-1) containing a structural unit (dx) derived from a (meth) acrylic acid ester compound in an amount of 0% by mass to ₁ % by mass and the structural unit (dx). ) In an amount of more than ₁ % by mass of r and ₂ % by mass or less of r, and a polymer (D-2) having a structural unit (dx) of more than ₂ % by mass of 100% by mass or less. D-3), and r ₁ = 35 (mass%) and r ₂ = 65 (mass%) ,
The content ratios of the polymers (D-1), (D-2), and (D-3) are 5 to 80% by mass and 3 to 70% by mass, respectively, when the total content is 100% by mass. And 5 to 80% by mass of a thermoplastic resin composition. When the content ratio of the above components [A], [B], [C] and [D] is 100% by mass of the total amount of the components [A], [B], [C] and [D] These are 15-75 mass%, 10-70 mass%, 5-65 mass%, and 10-70 mass%, respectively, The thermoplastic resin composition of Claim 1.   The polymer [D] is a mass ratio of the (meth) acrylic acid ester compound and other vinyl monomers from 100 to 70: 0 to 0 to 30:70 to 100, or 0. The thermoplastic resin composition according to claim 1 or 2, comprising a polymer obtained by polymerization while changing the charge amount from -30: 70-100 to 100-70: 0-30.   The content ratio of the structural unit (dx) contained in the polymer [D] is 5 to 95% by mass when the total of the structural units constituting the polymer [D] is 100% by mass. Item 4. The thermoplastic resin composition according to any one of Items 1 to 3. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the aliphatic polyester resin [ A ] is a polylactic acid resin. The rubbery polymer used to form the rubbery polymer reinforced graft resin [ C ] is a diene rubber, and the polymerizable unsaturated monomer used to form the rubbery polymer reinforced graft resin [ C ]. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the monomer comprises an aromatic vinyl compound and a vinyl cyanide compound.   The thermoplastic resin composition according to any one of claims 1 to 6, wherein the other polymerizable unsaturated monomer forming the structural unit (dy) includes an aromatic vinyl compound and a vinyl cyanide compound.   The content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from the vinyl cyanide compound contained in the polymer [D] is, when these totals are 100% by mass, It is 40-95 mass% and 5-60 mass%, The thermoplastic resin composition of Claim 7.   When the content ratios of the polymers (D-1), (D-2), and (D-3) are 100% by mass, the content is 10 to 70% by mass and 5 to 60% by mass, respectively. The thermoplastic resin composition according to any one of claims 1 to 8, wherein the thermoplastic resin composition is 5 to 70% by mass.   Further, [E] a flame retardant is contained in an amount of 10 to 25 parts by mass when the total amount of the components [A], [B], [C] and [D] is 100 parts by mass. The thermoplastic resin composition according to any one of the above.   A molded article obtained by using the thermoplastic resin composition according to any one of claims 1 to 10.

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