JP6284863B2 - Thermoplastic resin composition for supercritical foam molding and molded article - Google Patents

Description

  The present invention relates to a thermoplastic resin composition for supercritical foam molding and a molded article, and more particularly, to a polycarbonate resin reinforced with a rubbery graft copolymer having improved corrosiveness to a mold cavity surface during supercritical molding. The present invention relates to a thermoplastic resin composition and a molded product obtained by supercritical foam molding using the same.

  Polycarbonate resin is a resin excellent in heat resistance, mechanical properties, and electrical characteristics, and is widely used in, for example, automotive materials, electrical / electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. . In particular, a thermoplastic resin composition reinforced with a flame-retarded polycarbonate resin with a rubber-based graft copolymer has a good balance between flame retardancy and impact resistance, so computers, notebook computers, and various portable terminals It is preferably used as a part of electric / electronic devices such as printers and copying machines, OA / information devices, and the like.

  In recent years, these devices have been rapidly reduced in size and weight, and a foam molding method is being adopted in order to reduce the amount of resin used and reduce the weight. As foam molding, there is a method of manufacturing using a chemical foaming agent or a physical foaming agent, but the chemical foaming method is expensive because of the use of the foaming agent, and also due to the decomposition residue of the foaming agent remaining in the foam. There are problems such as discoloration of foam, generation of odor, and contamination of molding machine by chemical foaming agent.

  On the other hand, the gas foaming method using a physical foaming agent is a method of foam molding by melting a resin with a molding machine, supplying a low-boiling organic compound such as butane and kneading, and then releasing it into a low-pressure region. Since the low-boiling organic compound obtained has an affinity for the resin, it has excellent solubility and a high-magnification foam can be obtained. However, these foaming agents are expensive, and low-boiling organic compounds have dangers such as flammability.

  In order to solve such problems, a method has been proposed in which an inert gas such as nitrogen gas or carbon dioxide gas that is clean and inexpensive is used as a blowing agent. However, these inert gases have low solubility because they have a low affinity with the resin, and the resulting foam has a large and uneven cell diameter and low cell density. There's a problem.

Patent Document 1 describes a technique for obtaining a foam having a very fine cell diameter and a large cell density by using a supercritical fluid as a foaming agent and impregnating the supercritical fluid with a resin. In this supercritical foam molding, the supercritical liquid has excellent solubility close to liquid and excellent diffusibility close to gas, so the solubility in the resin is high, and the diffusion rate in the resin is also large. It becomes possible to impregnate the foaming agent in the resin in a short time.
However, in such a method in which a supercritical fluid is added to a molten resin and foamed, a problem of mold corrosion tends to occur. This problem occurs even with a polycarbonate resin composition that is used for normal injection molding and has no problem of mold corrosion, particularly rusting on the mold cavity surface. A serious problem arises.

  In the invention described in Patent Document 2, it has been proposed to mix a mold release agent having a thermal decomposition temperature of 280 ° C. or higher due to the problem of mold corrosion, but the purpose is to reduce corrosive gas, The effect of reducing the corrosion is manifested in the mold gas vent, and there was no effect on reducing the corrosion in an environment where the corrosion on the mold cavity surface occurred.

US Pat. No. 5,158,986 JP 2013-53271 A

  The present invention was devised in view of the above-mentioned problems of the prior art, and has a problem of corrosion on the mold cavity surface during supercritical foam molding for a polycarbonate resin reinforced with a rubbery graft copolymer. An object of the present invention is to provide a thermoplastic resin composition for supercritical foam molding which is solved.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have determined that MBS in which the content of a specific carboxylic acid component and an organic sulfonic acid compound is in a specific range in an alloy of polycarbonate resin and MBS resin type. The present inventors have found that a resin composition containing a resin solves the problem of corrosion on the mold cavity surface during supercritical foam molding, and has completed the present invention.
The present invention provides the following supercritical foam molding thermoplastic resin composition and molded article.

[1] 99.5-80 parts by mass of polycarbonate resin (A), graft polymer obtained by graft polymerization of (meth) acrylic acid ester monomer to rubber polymer, and / or rubber polymer ( 0.5-20 parts by mass of a graft copolymer (B) obtained by graft polymerization of a meth) acrylate monomer and an aromatic vinyl monomer component (however, the components (A) and (B) The total content is 100 parts by mass), and the content of one or more carboxylic acids of oleic acid, stearic acid, palmitic acid and abietic acid or salts thereof in the graft copolymer (B) And the content of the organic sulfonic acid compound is 0.5% by mass or less.
[2] The phosphorous flame retardant (C) is further contained in an amount of 3 to 30 parts by mass with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the graft copolymer (B). A thermoplastic resin composition for supercritical foam molding.
[3] The thermoplastic resin composition for supercritical foam molding as described in [2] above, wherein the phosphorus flame retardant (C) is a condensed phosphate ester and / or a phosphazene compound.
[4] Furthermore, the ABS resin (D) is contained in an amount of 1 to 50 parts by mass with respect to a total of 100 parts by weight of the polycarbonate resin (A) and the graft copolymer (B). The thermoplastic resin composition for supercritical foam molding according to any one of the above.
[5] Furthermore, the AS resin (E) is contained in an amount of 1 to 50 parts by mass with respect to a total of 100 parts by weight of the polycarbonate resin (A) and the graft copolymer (B). The thermoplastic resin composition for supercritical foam molding according to any one of the above.
[6] The thermoplastic resin composition for supercritical foam molding according to any one of [1] to [5], wherein the gas used for supercritical foaming is nitrogen.
[7] A molded product formed by supercritical foam molding using the thermoplastic resin composition for supercritical foam molding according to any one of [1] to [6].

  The thermoplastic resin composition for supercritical foam molding of the present invention can solve the problem of corrosion on the mold cavity surface during supercritical foam molding.

It is a figure which shows the structure of the metal mold | die used for evaluation of metal mold | die corrosivity in an Example.

Hereinafter, although an embodiment, an example thing, etc. are shown and explained in detail about the present invention, the present invention is limited to an embodiment, an example, etc. shown below and is not interpreted.
In the present specification, unless otherwise specified, “to” is used in a sense that includes numerical values described before and after it as a lower limit value and an upper limit value.

  The thermoplastic resin composition for supercritical foam molding of the present invention comprises 99.5 to 80 parts by mass of a polycarbonate resin (A) and a graft weight obtained by graft polymerization of a (meth) acrylate monomer to a rubbery polymer. 0.5-20 parts by mass of a graft copolymer (B) obtained by graft polymerization of a (meth) acrylate monomer and an aromatic vinyl monomer component to a polymer and / or rubber polymer The total of component (A) and component (B) is 100 parts by mass), and any one of oleic acid, stearic acid, palmitic acid and abietic acid in the graft copolymer (B) The total content of one or more carboxylic acids or salts thereof is 0.05 to 20% by mass, and the content of the organic sulfonic acid compound is 0.5% by mass or less.

[Polycarbonate resin (A)]
Examples of the polycarbonate resin (A) include an aromatic polycarbonate resin, an aliphatic polycarbonate resin, and an aromatic-aliphatic polycarbonate resin, preferably an aromatic polycarbonate resin, specifically, an aromatic dihydroxy compound. A thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting with phosgene or a diester of carbonic acid is used.

  Aromatic dihydroxy compounds include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), tetramethylbisphenol A, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol 4,4′-dihydroxydiphenyl and the like. Further, in order to improve flame retardancy, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the aromatic dihydroxy compound described above, a polymer having both ends phenolic OH groups having a siloxane structure, or an oligomer thereof is used. Also good.

  As a preferable example of the polycarbonate resin (A), 2,2-bis (4-hydroxyphenyl) propane or 2,2-bis (4-hydroxyphenyl) propane and another aromatic dihydroxy compound are used in combination as a dihydroxy compound. A polycarbonate resin is mentioned.

  The polycarbonate resin may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer.

  The molecular weight of the polycarbonate resin (A) is not limited, but it is a viscosity average molecular weight (Mv) converted from the solution viscosity measured at a temperature of 20 ° C. using methylene chloride as a solvent, preferably 10,000 to 40,000. More preferably, it is 14,000-32,000. When the viscosity average molecular weight is within this range, the resulting resin composition has good moldability in supercritical foam molding, and a molded product having high mechanical strength is easily obtained. The most preferable molecular weight range of the polycarbonate resin (A) is 16,000 to 30,000.

In the present invention, the viscosity average molecular weight (Mv) of the polycarbonate resin (A) is determined by measuring the viscosity of the methylene chloride solution of the polycarbonate resin at 20 ° C. using an Ubbelohde viscometer. Is a value calculated from the following Schnell viscosity equation.
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83

  The production method of the polycarbonate resin (A) is not particularly limited, and a polycarbonate resin produced by any of the phosgene method (interfacial polymerization method) and the melting method (transesterification method) can be used. Moreover, the polycarbonate resin which performed the post-process which adjusts the amount of terminal OH groups to the polycarbonate resin manufactured by the melting method is also preferable.

  Moreover, the polycarbonate resin (A) may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

  The polycarbonate resin (A) is not limited to the virgin raw material, but may be an aromatic polycarbonate resin regenerated from a used product, that is, a so-called material recycled aromatic polycarbonate resin. Used products include optical recording media such as optical disks, light guide plates, automobile window glass and automobile headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, glasses lenses, soundproof walls and glass windows, waves A building member such as a plate is preferred. In addition, as the recycled polycarbonate resin, non-conforming product, pulverized product obtained from sprue or runner, or pellets obtained by melting them can be used.

[Graft Copolymer (B)]
The thermoplastic resin composition for supercritical foam molding of the present invention includes a graft polymer obtained by graft polymerization of a (meth) acrylate monomer (b2) to a rubbery polymer (b1), and / or rubber. Graft copolymer (B) obtained by graft polymerizing (meth) acrylic acid ester monomer (b2) and aromatic vinyl monomer (b3) to polymeric polymer (b1), comprising oleic acid, stearin The total content of one or more carboxylic acids of acid, palmitic acid and abietic acid or their salts is 0.05 to 20% by mass, and the content of the organic sulfonic acid compound is 0.5% by mass % Of the graft copolymer (B) is contained. Such a graft copolymer (B) is contained.

  Specific examples of the rubbery polymer (b1) constituting the graft copolymer (B) include polybutadiene rubber, polyisoprene rubber, butadiene-acrylic composite rubber, styrene-butadiene rubber, and siloxane. These may be used alone or in admixture of two or more. Among these, diene rubbers, particularly polybutadiene rubber and styrene-butadiene rubber are preferable from the viewpoint of mechanical properties and surface appearance.

  The rubber polymer (b1) is graft-polymerized with a (meth) acrylic acid ester monomer (b2), or a (meth) acrylic acid ester monomer (b2) and an aromatic vinyl monomer (b3). To do.

Examples of the (meth) acrylic acid ester monomer (b2) to be graft-polymerized include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, methyl acrylate, ethyl acrylate, Preferable examples include butyl acrylate, cyclohexyl acrylate, octyl acrylate, and phenyl acrylate.
(Meth) acrylic acid ester monomer (b2) may be used individually by 1 type, or may mix and use 2 or more types.

The aromatic vinyl monomer (b3) to be graft-polymerized is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring, but has a substituent such as a functional group. None is preferred. Examples of the aromatic vinyl monomer (b3) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinyl Examples include xylene and vinyl naphthalene. Of these, styrene and α-methylstyrene are preferred, and styrene is particularly preferred.
The aromatic vinyl monomer (b3) can be used alone or in combination of two or more.

  Furthermore, other graft copolymerizable monomers other than the (meth) acrylic acid ester monomer (b2) and the aromatic vinyl monomer (b3) can be used in combination. Specific examples include acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate and benzyl acrylate. , Epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) acrylate; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; maleimide, N-methylmaleimi , N- maleimide compound of phenylmaleimide and the like; maleic acid, phthalic acid, alpha, such as itaconic acid, beta-unsaturated carboxylic acid compounds and their anhydrides (e.g., maleic acid, etc.). These monomers may be used individually by 1 type, or may use 2 or more types together.

The graft copolymer (B) is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. In particular, a core / shell graft copolymer consisting of a diene rubber core layer and a shell layer formed by graft copolymerization of a methacrylic acid ester monomer and further an aromatic vinyl monomer around it. Coalescence is particularly preferred.
In such a core / shell type graft copolymer, the rubber component is preferably contained in an amount of 40% by mass or more, more preferably 60% by mass or more. Moreover, what contains 10 mass% or more of an aromatic vinyl monomer component and a methacrylic acid ester monomer component is preferable.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Examples thereof include a combination (MB), a methyl methacrylate-acrylic / butadiene rubber copolymer, and a methyl methacrylate-acrylic / butadiene rubber-styrene copolymer. Such rubbery polymers may be used alone or in combination of two or more.

  The graft copolymer (B) used in the present invention has a total content of one or more carboxylic acids of oleic acid, stearic acid, palmitic acid and abietic acid or salts thereof of 0.05 to 20 mass. %, And the content of the organic sulfonic acid compound is 0.5% by mass or less. Among carboxylic acids, the content of oleic acid, stearic acid, palmitic acid and abietic acid or their salts is in such a range, and the content of the organic sulfonic acid compound is 0.5% by mass or less. It has been found that the graft copolymer (B) reduces the corrosiveness to the mold cavity surface during supercritical foam molding.

  As salts of oleic acid, stearic acid, palmitic acid and abietic acid, alkali metal salts are preferable, and sodium salts, potassium salts, ammonium salts and the like are particularly preferable.

  The content of oleic acid, stearic acid, palmitic acid and abietic acid or a salt thereof of the graft copolymer (B) is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more, especially 1% by mass or more, particularly 1.5% by mass or more is preferable, 2% by mass or more is particularly preferable, preferably 15% by mass or less, more preferably 12% by mass or less, and still more preferably. It is preferably 10% by mass or less, more preferably 9% by mass or less, and particularly preferably 8% by mass or less, particularly 7% by mass or less, and most preferably 6% by mass or less.

The organic sulfonic acid compound contained in the graft copolymer (B) typically includes alkyl benzene sulfonates, such as sodium salts such as dodecyl benzene sulfonic acid, stearyl benzene sulfonic acid, hexadecyl benzene sulfonic acid, A potassium salt can be illustrated. Such an organic sulfonic acid compound is considered to be derived from a surfactant used for emulsion polymerization of the graft copolymer (B).
The content of the organic sulfonic acid compound is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and still more preferably 0.01% by mass or less.

  The graft copolymer (B) is usually produced by a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method or the like, and any method can be used in the present invention.

When the graft copolymer (B) is produced by emulsion polymerization, the (meth) acrylic acid ester monomer (b2) or the methacrylic acid ester monomer in the latex of the rubbery polymer component (b1) A redox polymerization initiator in which a body (b2), an aromatic vinyl monomer (b3), and other monomers are added and a peroxide initiator, an azo initiator, or an oxidizing agent / reducing agent is combined. Using an emulsifier such as an anionic emulsifier and a nonionic emulsifier, a chain transfer agent, and the like, by emulsion graft polymerization.
In order to keep the contents of oleic acid, stearic acid, palmitic acid and abietic acid or their salts and organic sulfonic acid compounds within a predetermined range, it is possible to adjust the amount of them in the polymerization. In this case, these carboxylic acids or their salts or organic sulfonic acid compounds can be used as the above-mentioned emulsifiers, and the amount thereof can be adjusted. The contents of these carboxylic acids or their salts and organic sulfonic acid compounds can also be adjusted by washing the manufactured latex with water.

  The graft copolymer (B) in which the content of oleic acid, stearic acid, palmitic acid and abietic acid or their salts and the organic sulfonic acid compound is within a predetermined range is a commercially available graft copolymer. It is also possible to appropriately select and use one having a predetermined content from the inside.

  In the present invention, the graft copolymer (B) is not limited to an embodiment containing only one type of graft copolymer (B), for example, a combination of a plurality of types of graft copolymers having different monomer compositions and molecular weights. The aspect containing may be sufficient. When a plurality of types of graft copolymers are included in combination, the graft copolymer (B) in which the content of abietic acid, oleic acid, stearic acid and palmitic acid or their salts and organic sulfonic acid compound is within a predetermined range In addition, a graft copolymer having a content outside the predetermined range may be blended so that the content of the above compound as a whole is within a predetermined range as the graft copolymer.

  The content of the graft copolymer (B) is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the graft copolymer (B). When the content is less than 0.5 parts by mass, the impact resistance improving effect tends to be insufficient, and when the content exceeds 20 parts by mass, the appearance defect, heat resistance, difficulty of the molded product obtained by supercritical foam molding of the resin composition are difficult. Flammability is likely to decrease. The content of the graft copolymer (B) is more preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more, with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the ABS resin (B). Yes, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.

[Phosphorus flame retardant (C)]
The thermoplastic resin composition for supercritical foam molding of the present invention preferably contains a phosphorus-based flame retardant (C). By containing a phosphorus flame retardant (C), the flame retardancy of a molded product obtained by supercritical foam molding can be improved.
The phosphorus-based flame retardant (C) is a compound containing phosphorus in the molecule, and may be a low molecule, an oligomer, or a polymer. The condensed phosphate compound represented by the formula (1) and the phosphazene compounds represented by the general formulas (2) and (3) are particularly preferable.

-Condensed phosphate ester compound The condensed phosphate ester compound represented by the above general formula (1) may be a mixture of compounds having different numbers of k, and in the case of a mixture of condensed phosphate esters having different k K is the average of their mixture. k is usually an integer of 0 to 5, and in the case of a mixture of compounds having different k numbers, the average k number is preferably 0.5 to 2, more preferably 0.6 to 1.5, and even more preferably. Is in the range of 0.8 to 1.2, particularly preferably 0.95 to 1.15.

X ¹ represents a divalent arylene group such as resorcinol, hydroquinone, bisphenol A, 2,2′-dihydroxybiphenyl, 2,3′-dihydroxybiphenyl, 2,4′-dihydroxybiphenyl, 3,3 ′. -Dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, Divalent derivatives derived from dihydroxy compounds such as 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene It is a group. Of these, divalent groups derived from resorcinol, bisphenol A, and 3,3′-dihydroxybiphenyl are particularly preferable.

  Further, p, q, r and s in the general formula (1) each represent 0 or 1, and 1 is particularly preferable.

R ¹ , R ² , R ³ and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. Examples of such aryl groups include phenyl group, cresyl group, xylyl group, isopropylphenyl group, butylphenyl group, tert-butylphenyl group, di-tert-butylphenyl group, and p-cumylphenyl group. Group, cresyl group and xylyl group are more preferred.

As a specific example of the condensed phosphate ester compound represented by the general formula (1),
Triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate, bis- ( aromatic phosphates such as tert-butylphenyl) phenyl phosphate, tris- (tert-butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate;
Condensed phosphate esters such as resorcinol bis-diphenyl phosphate (RDP), resorcinol bis-dixylenyl phosphate (RDX), bisphenol A bis-diphenyl phosphate (BDP), biphenyl bis-diphenyl phosphate;
Etc.

  The acid value of the condensed phosphate ester compound represented by the general formula (1) is preferably 0.2 mgKOH / g or less, more preferably 0.15 mgKOH / g or less, still more preferably 0.1 mgKOH or less, Especially preferably, it is 0.05 mgKOH / g or less. The lower limit of the acid value can be substantially zero. On the other hand, the content of the half ester is more preferably 1.1 parts by mass or less, and still more preferably 0.9 parts by mass or less. When the acid value exceeds 0.2 mgKOH / g or the half ester content exceeds 1.5 mg, the thermal stability and hydrolysis resistance of the polycarbonate resin composition of the present invention are reduced.

  As the phosphoric ester compound, in addition to the above, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,3-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,4-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, containing phosphate ester moiety Naturally, polyester resins, polycarbonate resins or epoxy resins are also included.

Phosphazene compound Examples of the phosphazene compound represented by the general formulas (2) and (3) include phenoxyphosphazene and (poly) tolyloxyphosphazene (for example, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p- Cyclic, such as tolyloxyphosphazene, o, m-tolyloxyphosphazene, o, p-tolyloxyphosphazene, m, p-tolyloxyphosphazene, o, m, p-tolyloxyphosphazene), (poly) xylyloxyphosphazene and / or or linear _{C 1-6} alkyl _{C 6-20} aryloxy phosphazene, (poly) phenoxy tolyloxy phosphazene (e.g., phenoxy o- tolyloxy phosphazene, a phenoxy m- tolyloxyethyl phosphazene, a phenoxy p- Toriruokishiho Phazen, phenoxy o, m-tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o, m, p-tolyloxyphosphazene, etc.), (poly) phenoxyxyloxyphosphazene And cyclic and / or chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxy phosphazene such as (poly) phenoxytolyloxyxyloxyphosphazene.
Of these, cyclic and / or chain phenoxyphosphazene, cyclic and / or chain C _1-3 alkyl C _6-20 aryloxyphosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20 Aryloxyphosphazenes (eg, cyclic and / or chain tolyloxyphosphazenes, cyclic and / or chain phenoxytolylphenoxyphosphazenes, etc.).

In the cyclic phosphazene compound represented by the general formula (2), R ⁵ and R ⁶ may be the same or different and each represents an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, and a benzyl group. Among them, cyclic phenoxyphosphazene in which R ⁵ and R ⁶ are phenyl groups is particularly preferable.
Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene, octachlorocyclohexane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group. .

  Moreover, in formula (2), t represents an integer of 3 to 25. Among them, a compound in which t is an integer of 3 to 8 is preferable, and a mixture of compounds having different t may be used. Among them, a mixture of compounds in which t = 3 is 50% by mass or more, t = 4 is 10 to 40% by mass, and t = 5 or more is 30% by mass or less is preferable.

In formula (3), R ⁷ and R ⁸ may be the same or different and each represents an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, a benzyl group, and the like, and a chain phenoxyphosphazene in which R ⁷ and R ⁸ are phenyl groups is particularly preferable.
Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above-described method to reverse polymerization at a temperature of 220 to 250 ° C., and the obtained linear dichloromethane having a polymerization degree of 3 to 10,000. Examples thereof include compounds obtained by substituting phosphazene with a phenoxy group.

Also, R ⁹ is represented by -N = P (OR ⁷ ) ₃ groups, -N = P (OR ⁸ ) ₃ groups, -N = P (O) OR ⁷ groups, and -N = P (O) OR ⁸ groups. At least one selected is shown, and R ¹⁰ is -P (OR ⁷ ) ₄ group, -P (OR ⁸ ) ₄ group, -P (O) (OR ⁷ ) ₂ group, -P (O) (OR ⁸ ) At least one selected from _two groups.

  Moreover, in Formula (3), u shows the integer of 3-10,000, Preferably it is 3-1,000, More preferably, it is 3-100, More preferably, it is 3-25.

Further, the phosphazene compound may be a crosslinked phosphazene compound partially crosslinked. By having such a crosslinked structure, the heat resistance tends to be improved.
Examples of such crosslinked phosphazene compounds include compounds having a crosslinking structure represented by the following general formula (4), for example, 4,4′-sulfonyldiphenylene (bisphenol S residue), 2,2- (4 , 4′-diphenylene) isopropylidene group-crosslinked structure, 4,4′-oxydiphenylene group-crosslinked structure, 4,4′-thiodiphenylene group-crosslinked structure, etc. Examples thereof include compounds having a crosslinked structure of 4,4′-diphenylene group.

［式（４）中、Ｘ^２は−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−Ｓ−、又は−Ｏ−であり、ｖは０又は１である。］

[In Formula (4), X ² is —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—, and v is 0 or 1. ]

In addition, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound in which R ⁵ and R ⁶ are phenyl groups in the general formula (2) with a crosslinking group represented by the general formula (4). Alternatively, a crosslinked phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound in which R ⁷ and R ⁸ are phenyl groups in the general formula (3) with a crosslinking group represented by the general formula (4) is flame retardant. From the above point, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound with a crosslinking group represented by the general formula (4) is more preferable.

  The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (2) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (3) and Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  In the present invention, the phosphazene compound is a crosslinked phenoxy obtained by crosslinking the cyclic phenoxyphosphazene compound represented by the general formula (2) and the cyclic phenoxyphosphazene compound represented by the general formula (3) with a crosslinking group. In view of flame retardancy and mechanical properties, at least one selected from the group consisting of phosphazene compounds is preferable.

  The content of the phosphorus-based flame retardant (C) is preferably 3 to 30 parts by mass, preferably 5 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the graft copolymer (B). More preferably, it is 8 parts by mass or more, preferably 25 parts by mass or less, more preferably 20 parts by mass or less. When the blending amount of the phosphorus-based flame retardant (C) is less than 3 parts by mass, the flame retardancy tends to be insufficient, and when it exceeds 30 parts by mass, a significant decrease in heat resistance and mechanical properties are likely to occur.

[ABS resin (D)]
The thermoplastic resin composition of the present invention preferably contains an ABS resin (D).
The ABS resin is usually a copolymer resin composed of an aromatic vinyl monomer component, a diene rubbery polymer component and other monomer components, and preferably an aromatic vinyl monomer component (d1). 40-80% by mass, vinyl cyanide monomer component (d2) 10-30% by mass, diene rubbery polymer component (d3) 10-30% by mass, and other monomer components (d4) 0-30 It is ABS resin (D) which consists of mass%.

As the aromatic vinyl monomer component (d1) in the ABS resin (D), styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butyl Styrene, vinyl naphthalene, methoxy styrene, monobromo styrene, dibromo styrene, fluoro styrene, tribromo styrene and the like can be mentioned, and styrene is particularly preferable.
The proportion of the aromatic vinyl monomer component (d1) in the ABS resin (D) is preferably in the range of 40 to 80% by mass, more preferably 45% by mass in 100% by mass of the ABS resin (D). More preferably, it is 50% by mass or more, particularly preferably 55% by mass or more, more preferably 75% by mass or less, still more preferably 70% by mass or less, and particularly preferably 65% by mass or less.

Examples of the vinyl cyanide monomer component (d2) in the ABS resin (D) include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.
The proportion of the vinyl cyanide monomer component (d2) in the ABS resin (D) is in the range of 10 to 30% by mass in the ABS resin (D) 100% by mass, more preferably 12% by mass or more. Further, it is preferably 14% by mass or more, particularly preferably 15% by mass or more, more preferably 28% by mass or less, still more preferably 26% by mass or less, and particularly preferably 25% by mass or less.

  Examples of the diene rubbery polymer component (d3) of the ABS resin (D) include rubber components such as polybutadiene, polyisoprene, and styrene-butadiene copolymer, and the diene rubbery polymer component (d3). The ratio in the ABS resin (D) is preferably in the range of 10 to 30% by mass, more preferably 13% by mass or more, still more preferably 14% by mass or more, particularly in 100% by mass of the ABS resin (D). Preferably it is 15 mass% or more, More preferably, it is 28 mass% or less, More preferably, it is 26 mass% or less.

Further, it may be a copolymer of other monomer component (d4) copolymerizable with these. In this case, examples of other copolymerizable vinyl monomers include maleimide, N-methylmaleimide, N- Maleimide monomers such as cyclohexylmaleimide and N-phenylmaleimide, acrylamide monomers such as acrylamide and N-methylacrylamide, unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride, and unsaturated acids such as acrylic acid and methacrylic acid Glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methoxypolyethylene glycol methacrylate, and the like.
The proportion of the other monomer component (d4) in the ABS resin (D) is in the range of 100% by mass of the ABS resin (D), preferably 0 to 30% by mass, more preferably 20% by mass or less, More preferably, it is 10 mass% or less.

  Specific examples of the ABS resin (D) are preferably acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, acrylonitrile-butadiene-styrene-N-phenylmaleimide copolymer, and the like. Illustrated.

  The ABS resin is usually produced by a method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. In the present invention, any method can be used, but a bulk polymerization method is preferred.

  The content of the ABS resin (D) is preferably 1 to 50 parts by mass, more preferably 45 parts by mass or less, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the graft copolymer (B). More preferably, it is 40 parts by weight or less, particularly 35 parts by weight or less, especially 30 parts by weight or less, most preferably 25 parts by weight or less, more preferably 5 parts by weight or more, further preferably 10 parts by weight or more, particularly preferably. Is 13 parts by mass or more, most preferably 15 parts by mass or more, and most preferably 18 parts by mass or more. If the content of the ABS resin body (D) exceeds 50 parts by mass, the strength tends to be unsatisfactory, and if it is less than 1 part by mass, the effect of improving fluidity and foamability becomes insufficient.

[AS resin (E)]
It is also preferable that the thermoplastic resin composition of the present invention contains an AS resin (E).
The AS resin is an acrylonitrile-styrene copolymer and refers to a copolymer of acrylonitrile and one or more of styrene monomers.

  As the styrene monomer constituting the AS resin (E), styrene, α-methylstyrene, p-methylstyrene, bromostyrene and the like are preferable, styrene and α-methylstyrene are more preferable, and styrene is particularly preferable.

50-95 mass% is preferable and, as for the content rate of the styrene-type monomer in AS resin (E), 65-92 mass% is more preferable.
The melt flow rate (MFR) reflecting the molecular weight of the AS resin (E) is preferably in the range of 5 to 50 g / 10 minutes at 220 ° C. and a load of 10 kg, more preferably 10 to 30 g / 10 minutes. .

  A method for producing the AS resin (E) is not particularly limited, and a known method can be adopted. For example, a method such as bulk polymerization, solution polymerization, suspension polymerization, bulk suspension polymerization, emulsion polymerization, or the like is used. It can also be obtained by blending separately polymerized or copolymerized resins.

  As AS resin (E), what is marketed as acrylonitrile styrene copolymer (AS resin) or acrylonitrile styrene copolymer (SAN) can also be employ | adopted widely.

  The preferable content of the AS resin (E) is preferably 1 to 50 parts by mass, more preferably 45 parts by mass or less, with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the graft copolymer (B). More preferably, it is 40 parts by mass or less, especially 35 parts by mass or less, particularly 30 parts by mass or less, most preferably 25 parts by mass or less, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and particularly preferably. Is 13 parts by mass or more, particularly preferably 15 parts by mass or more, and most preferably 18 parts by mass or more.

[Release agent (F)]
Moreover, it is also preferable that the polycarbonate resin composition of this invention contains a mold release agent (F). Examples of the release agent (F) include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane silicone oils, and the like. .

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the term “aliphatic” is used as a term including alicyclic compounds.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine and comprise one ester may each be used 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized.

Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

  In addition, 1 type may contain the release agent mentioned above, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the release agent (F) is usually 0.001 part by mass or more, preferably 0.01 part by mass or more with respect to 100 parts by mass in total of the polycarbonate resin (A) and the graft copolymer (B). In addition, it is usually 2 parts by mass or less, preferably 1 part by mass or less. When the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the range, hydrolysis resistance And mold contamination during injection molding may occur.

[Fluoropolymer (G)]
The thermoplastic resin composition of the present invention preferably contains a fluoropolymer (G).
Examples of the fluoropolymer (G) include a fluoroolefin resin. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure. Specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. Examples of the fluoroethylene resin include a fluoroethylene resin having a fibril forming ability.

  Examples of the fluoroethylene resin having a fibril forming ability include “Teflon (registered trademark) 6J”, “Teflon (registered trademark) 640J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Polyflon F201L”, “Polyflon F103 manufactured by Daikin Industries, Ltd. ”,“ Polyflon FA500B ”,“ Polyflon FA500H ”and the like. Further, examples of commercially available aqueous dispersions of fluoroethylene resin include “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and “Fullon D-210C” manufactured by Daikin Industries, Ltd. Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such a fluoroethylene polymer include polystyrene-fluoroethylene composites, polystyrene-acrylonitrile-fluoroethylene. Examples include composites, polymethyl methacrylate-fluoroethylene composites, polybutyl methacrylate-fluoroethylene composites, etc. Specific examples include “Metablene A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex” manufactured by GE Specialty Chemical Co., Ltd. 449 "and the like. In addition, 1 type may contain the dripping inhibitor and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the fluoropolymer (G) is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the graft copolymer (B). Or more, more preferably 0.05 parts by mass or more, particularly preferably 0.1 parts by mass or more, and preferably 2 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.7 parts by mass. Or less. When the content of the fluoropolymer (G) is less than 0.01 parts by mass, the flame retardant effect due to the anti-dripping agent tends to be insufficient, and when the content exceeds 2 parts by mass, the thermoplastic resin composition Deterioration of the appearance and mechanical strength of the molded product obtained by molding is likely to occur.

[Silicate compound (H)]
It is also preferable to mix | blend a silicate compound (H) with the thermoplastic resin composition of this invention. The silicate compound (H) has a large effect of preventing dripping of the molten resin at the time of combustion, can further improve the flame retardancy of the resin composition, and can improve rigidity and dimensional stability.
Specific examples of the silicate compound (H) include talc, kaolin, clay, mica, montmorillonite, wollastonite, natural silica, synthetic silica, various glass fillers, zeolite and diatomaceous earth, or a mixture thereof. However, talc, mica and wollastonite are preferred, and talc is most preferred from the balance of flame retardancy and dimensional stability. Among the above, talc is particularly effective in preventing molten resin drip during combustion.

  Although talc is not particularly limited, it is preferably 1.0 to 20 μm, more preferably 1.5 to 18 μm in terms of a number average particle size measured by a sedimentation method (Asada method) using a light transmission particle size distribution analyzer. When the number average particle size is 1.0 μm or more, flame retardancy tends to be improved, and when it is 20 μm or less, the appearance of the molded product tends to be further improved.

The silicate compound (H) is a variety of coupling agents for the purpose of increasing the affinity or interfacial bonding force with the polycarbonate resin (A), the graft copolymer (B), and the graft copolymer (B). Can also be used.
As the coupling agent, silane-based, chromium-based and titanium-based coupling agents are usually used. Among them, those containing silane coupling agents such as epoxy silane compounds such as γ-glycidoxypropyltrimethoxysilane, vinyltrichlorosilane compounds and γ-aminopropyltriethoxysilane compounds are preferable. At this time, in order to improve mechanical strength and kneadability, treatment with various surfactants such as nonionic, cationic, and anionic types and dispersants such as fatty acids, metal soaps, and various resins may be performed. preferable.

  The preferable content of the silicate compound (H) is 0 to 5 parts by mass and 0.5 to 4 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin (A) and the graft copolymer (B). Is more preferable.

[Stabilizer (I)]
The thermoplastic resin composition of the present invention preferably contains a stabilizer, and the stabilizer is preferably a phosphorus stabilizer or a phenol stabilizer.

  Any known phosphorous stabilizer can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Particularly preferred.

Organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di- tert-butylphenyl) octyl phosphite and the like.
Specific examples of such organic phosphite compounds include, for example, “ADEKA STAB 1178”, “ADEKA STAB 2112”, “ADEKA STAB HP-10” manufactured by ADEKA, “JP-351” manufactured by Johoku Chemical Industry Co., Ltd., “ JP-360 ”,“ JP-3CP ”,“ Irgaphos 168 ”manufactured by BASF, and the like.
In addition, 1 type may contain phosphorus stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the phosphorus stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 100 parts by mass in total of the polycarbonate resin (A) and the graft copolymer (B). Is 0.03 parts by mass or more, and is usually 1 part by mass or less, preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass or less. If the content of the phosphorus stabilizer is less than the lower limit of the range, the thermal stability effect may be insufficient, and if the content of the phosphorus stabilizer exceeds the upper limit of the range, the effect May stop and become economical.

  As a phenol type stabilizer, a hindered phenol type antioxidant is mentioned, for example. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenyl) propionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] ] Methyl] phosphoate, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a -(Mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl- 4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-) tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6- Bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6 Di -tert- pentylphenyl acrylate.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such a phenolic antioxidant include “Irganox 1010”, “Irganox 1076” manufactured by BASF, “Adekastab AO-50”, “Adekastab AO-60” manufactured by ADEKA, and the like. Is mentioned.
In addition, 1 type may contain the phenol type stabilizer, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the phenol-based stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the graft copolymer (B). Moreover, it is 1 mass part or less normally, Preferably it is 0.5 mass part or less. When the content of the phenol-based stabilizer is less than the lower limit of the range, the effect as the phenol-based stabilizer may be insufficient, and the content of the phenol-based stabilizer exceeds the upper limit of the range. If this is the case, the effect may reach its peak and not economical.

[Other ingredients]
The thermoplastic resin composition for supercritical foam molding of the present invention may contain other components as necessary, in addition to those described above, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than those described above and various resin additives. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

Other resins Examples of the other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, polybutylene terephthalate resin; polyolefin resins such as polyethylene resin and polypropylene resin; polyamide resins; polyimide resins; Examples include imide resins; polyurethane resins; polyphenylene ether resins; polyphenylene sulfide resins;
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.

-Resin additive Examples of the resin additive include an ultraviolet absorber, a dye / pigment, an antistatic agent, an antifogging agent, an antiblocking agent, a fluidity improver, a plasticizer, a dispersant, and an antibacterial agent. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.

[Method for producing thermoplastic resin composition]
There is no restriction | limiting in the manufacturing method which manufactures the thermoplastic resin composition of this invention, The manufacturing method of a well-known thermoplastic resin composition can be employ | adopted widely.
For example, after the polycarbonate resin (A) and the graft copolymer (B) and other components to be blended as necessary are mixed in advance using various mixers such as a tumbler and a Henschel mixer. And a melt kneading method using a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader.

In addition, for example, the thermoplastic resin composition of the present invention is manufactured without mixing each component in advance or by mixing only a part of the components in advance and supplying the mixture to an extruder using a feeder and melt-kneading. You can also
Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, this master batch is again mixed with the remaining components and melt-kneaded. The thermoplastic resin composition of the present invention can also be produced.
In addition, for example, when mixing a component that is difficult to disperse, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance, and kneaded with the solution or the dispersion. It can also improve sex.

[Supercritical foam molding]
The thermoplastic resin composition of the present invention is made into a foam molded article by supercritical foam molding. As the molding machine, an injection molding machine, an extrusion molding machine, a blow molding machine or the like is used, and an injection molding machine or the like is preferably used.
Various known methods can be applied to the supercritical foam molding. One specific example will be explained. First, the obtained pellets of the thermoplastic resin composition are put into a molding machine from a hopper of an injection molding machine and heated and melted in a conveying zone and a compression zone of a molding machine screw. And then sent to the metering zone and compression zone of the molding machine screw. Then, nitrogen or carbon dioxide gas as a supercritical fluid is injected from the injection port provided in the measuring zone, and the supercritical fluid and the molten resin are pressurized and single-phased, from the nozzle of the injection molding machine. It is injected, flows while maintaining a single phase in the sprue and runner, sent to the mold cavity, and after passing through the gate, bubble nuclei are generated, filling the mold progresses while the bubbles expand Thus, supercritical foam molding is performed. Here, the generation of bubble nuclei is performed by reducing the pressure in the mold to a pressure equal to or lower than the critical pressure of nitrogen or carbon dioxide, so that nitrogen or carbon dioxide is supersaturated, and the molten resin composition becomes supersaturated. This is done by generating a large number of cell nuclei.

[Molded body]
The thermoplastic resin composition of the present invention is molded into an arbitrary shape by supercritical foam molding and used as a molded product. There are no restrictions on the shape, pattern, color, size, etc. of the molded product, and it may be set arbitrarily according to the application of the molded product.

  Examples of the molded article include parts such as electric / electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, and lighting equipment. Among these, it is particularly suitable for various parts of electric / electronic devices and OA devices.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.

  Each component used in the following Examples and Comparative Examples is as shown in Table 1 below.

[Measurement of content of carboxylic acid or salt in graft copolymer (B)]
In Table 1, the content of oleic acid, stearic acid, palmitic acid and abietic acid or their salts in the graft copolymer (B) was measured as follows.
The supernatant obtained when 2.4 g of the graft copolymer (B) was dissolved in dichloromethane and reprecipitated with hexane was filtered and then concentrated and dried. The obtained dried product was measured by the following GC method.
The measurement conditions are as follows. For determination, stearic acid (special grade), palmitic acid (special grade), oleic acid and abietic acid manufactured by Wako Pure Chemical Industries, Ltd. were used as references.
Measuring instrument: GC / MS-QP2010 (manufactured by Shimadzu Corporation)
Column: UA1 (MS / HT)
(Manufactured by Frontier Laboratories, 0.25 mm × 15 m, film thickness 0.25 μm)
Column temperature: 50 to 350 ° C. (12.5 ° C./min)
Gas flow rate: 3ml / min

[Measurement of content of organic sulfonic acid compound in graft copolymer (B)]
In addition, the measurement of the content of the organic sulfonic acid compound in the graft copolymer (B) was confirmed in advance as containing only dodecylbenzenesulfonic acid (salt) as the organic sulfonic acid compound. The content of dodecylbenzenesulfonic acid (salt) was measured as follows.

The solid matter obtained by extracting and drying the methanol-soluble component obtained by dispersing 5 g of the graft copolymer (B) in methanol was measured by the following liquid chromatograph (LC) method.
The measurement conditions are as follows. For quantification, dodecylbenzenesulfonic acid (soft type) manufactured by Tokyo Chemical Industry Co., Ltd. was used as a reference.
Column: SunShell C18
(Chronic Technology Co., Ltd., 4.6 × 50 mm, particle size 2.7 μm)
Column temperature: 40 ° C
Mobile phase: 0.1 mol / L
Water / acetonitrile containing sodium perchlorate = 45/55
Flow rate: 1.3 mL / min
Injection volume: 5 μL
Detector: UV (230 nm)

(Examples 1-10, Comparative Examples 1-2)
[Manufacture of resin pellets]
Of the components described in Table 1 above, components other than the C1 component were blended in the proportions (mass ratio) described in Table 2 below, mixed for 20 minutes with a tumbler, and then manufactured by Nippon Steel Works, Ltd. equipped with 1 vent. While supplying the twin screw extruder (TEX30α) from the upstream feeder and further supplying the C1 component from the middle of the barrel, the rotational speed is 250 rpm, the discharge amount is 45 kg / hour, the barrel temperature is Example 1, and the comparative example 1 is 280 ° C. Otherwise, the melted resin was kneaded at 260 ° C., and the molten resin extruded in a strand shape was quenched in a water bath and pelletized using a pelletizer to obtain pellets of the resin composition.

[Evaluation of mold corrosion]
The mold corrosivity was evaluated as follows.
For normal molding, the pellets of the obtained resin composition were preliminarily dried at 80 ° C. for 6 to 12 hours in advance, and the cylinder temperature was determined in Example 1 and Comparative Example 1 using a J85AD injection molding machine manufactured by Nippon Steel Works. The normal injection molding was carried out at a setting of 280 ° C., 260 ° C. for the others, and all mold temperatures of 50 ° C. and 1 cycle 30 seconds.
On the other hand, for supercritical foam molding, nitrogen that was made supercritical using a MuCell SCF device (model: SII-TRJ-10-A) manufactured by TREXEL was transferred to the cylinder of the Nippon Steel Works J85AD injection molding machine. Supercritical foam molding was performed in a series of cycles in which a fixed amount was injected, mixed with a molten resin composition, and injected into a mold. The preliminary drying and molding conditions of the resin composition pellets were the same as those for normal molding, and the supercritical nitrogen injection amount was set to 0.2% by mass of the normal molding quality.

The mold corrosivity was evaluated using a mold having the structure shown in FIG. 1A is a sectional plan view, and FIG. 1B is a sectional side view. 1 is a sprue, 2 is a runner, 3 is a cavity (20 mm × 60 mm × 3 mm to 1 mm thickness), 4 is a protruding pin, and 5 shown by a broken line is a slot portion.
After forming 200 shots, the insert of the mold was removed, and evaluation was performed by visually confirming the rust state of the insert after being left for 1 hour under conditions of a temperature of 65 ° C. and a humidity of 85%.
The criteria for visual evaluation of the cavity portion are as follows.
A: Rust corrosion cannot be visually confirmed B: Discoloration due to rust corrosion is less than 10% of the cavity surface area C: Discoloration due to rust corrosion is 10% to 30% of the cavity surface area D: Discoloration due to rust corrosion More than 30% to less than 60% of cavity surface area E: Discoloration due to rust corrosion is more than 60% of cavity surface area

The evaluation results are shown in Table 2 below.
In the following examples, other mechanical properties or the like were not particularly deteriorated.

  Since the thermoplastic resin composition for supercritical foam molding of the present invention has no problem of corrosion of the mold cavity surface during supercritical foam molding, it can produce good molded products with high productivity in various supercritical foam molding. , Its industrial applicability is high.

Claims (7)

  99.5-80 parts by weight of polycarbonate resin (A), graft polymer obtained by graft polymerization of (meth) acrylic acid ester monomer to rubber polymer, and / or (meth) acrylic to rubber polymer 0.5-20 parts by mass of graft copolymer (B) obtained by graft polymerization of acid ester monomer and aromatic vinyl monomer component (however, the total of component (A) and component (B) is 100) The total content of one or more carboxylic acids or their salts of oleic acid, stearic acid, palmitic acid and abietic acid in the graft copolymer (B). A thermoplastic resin composition for supercritical foam molding, which is 0.05 to 20% by mass and the content of the organic sulfonic acid compound is 0.5% by mass or less.   The supercritical foam molding according to claim 1, further comprising 3 to 30 parts by mass of the phosphorus-based flame retardant (C) with respect to 100 parts by mass in total of the polycarbonate resin (A) and the graft copolymer (B). Thermoplastic resin composition.   The thermoplastic resin composition for supercritical foam molding according to claim 2, wherein the phosphorus-based flame retardant (C) is a condensed phosphate ester and / or a phosphazene compound.   Furthermore, ABS resin (D) is contained in 1-50 mass parts with respect to a total of 100 weight part of polycarbonate resin (A) and a graft copolymer (B), The any one of Claims 1-3 contained. A thermoplastic resin composition for supercritical foam molding.   Furthermore, 1-50 mass parts of AS resin (E) is contained with respect to a total of 100 weight part of polycarbonate resin (A) and a graft copolymer (B), It is any one of Claims 1-4. A thermoplastic resin composition for supercritical foam molding.   The thermoplastic resin composition for supercritical foam molding according to any one of claims 1 to 5, wherein the gas used for supercritical foaming is nitrogen.   The molded article formed by supercritical foam molding using the thermoplastic resin composition for supercritical foam molding of any one of Claims 1-6.

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