JP2006182841A - Thermoplastic resin composition and molded product using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition that can give molded products occurring an extremely reduced amount of VOC (for example, styrene, toluene, benzene or the like) without large adverse effects to the excellent flame retardancy, mechanical properties and the like in the thermoplastic resin relating to the alloys of polycarbonate and styrene resin such as PC/ABS alloy. <P>SOLUTION: The thermoplastic resin composition comprises (A) 50 to 90 %wt. of a polycarbonate resin, (B) 10 to 50 %wt. of a styrene resin, and (C) 0.1 to 10 pts.wt. of hydrophobic zeolite, (D) polyorganohydrogensiloxane and/or (E) 0.0001 to 1 pt.wt. of a coupling agent, further if desired, 2 to 20 pts.wt. of phosphoric acid ester and (G) 0.05 to 2 pts.wt. of fiber-forming fluorine resin, each based on 100 pts.wt. of the resins (A) and (B). The thermoplastic resin composition is molded to give the molded products. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin composition comprising a styrenic resin such as a polycarbonate resin and an ABS resin, a hydrophobic zeolite, and, optionally, a phosphate ester flame retardant, and a molded article formed by molding the same. More specifically, a molded article formed by molding a thermoplastic resin such as an alloy of polycarbonate resin / ABS resin (hereinafter sometimes abbreviated as PC / ABS alloy) without impairing mechanical properties such as impact resistance. The present invention relates to a thermoplastic resin composition such as PC / ABS alloy having a very low volatile organic gas (hereinafter abbreviated as VOC (Volatile Organic Chemicals)) and further imparting flame retardancy if desired.

  PC / ABS alloys are extremely excellent in mechanical properties (especially impact resistance), electrical characteristics, heat resistance, thermal stability, etc., and as an engineering plastic, they are used in various fields such as office equipment and electrical / electronic equipment fields. Widely used in the field.

Particularly in the field of office equipment, the alloy is flame-retarded with phosphorus flame retardants and the like, and is actively used as a material for housings and interior / exterior parts of computers, printers, copiers, fax machines and the like.

  However, in recent years, with the rapid spread of these office equipments, it is said that VOCs emitted from plastic materials constituting these equipments may affect the human body, and countermeasures are urgently required.

On the other hand, zeolite is used as a deodorant from the viewpoint of removing odor components. (Patent Documents 1 and 2) However, there is no disclosure or suggestion about removal of VOCs (particularly compounds such as styrene, toluene, benzene) generated from molded articles in applications such as office equipment and electrical / electronic equipment. Absent.
Japanese Patent Application Laid-Open No. 07-227940 JP 07-316342 A

  The present invention relates to a VOC emitted from a molded product formed by molding a thermoplastic resin related to an alloy of a polycarbonate resin such as PC / ABS alloy and a styrene resin without significantly impairing the flame retardancy and mechanical properties. The present invention provides a thermoplastic resin composition characterized by extremely low (specific examples: compounds such as styrene, toluene and benzene).

  As a result of intensive studies to solve such problems, the present inventor has obtained a thermoplastic resin in which a specific amount of a specific zeolite and an additive are blended in an alloy of a polycarbonate resin such as PC / ABS alloy and a styrene resin. By using the composition, the VOC generated from the molded product obtained by molding the composition is suppressed to a surprisingly low level, and, if desired, a phosphate compound and a fiber-forming fluororesin may be added. Thus, the present inventors have found that flame retardancy is also improved and have reached the present invention.

  That is, in the first aspect of the present invention, the hydrophobic zeolite (C) 0.1 is added per 100 parts by weight of the total amount of the polycarbonate resin (A) 50 to 90% by weight and the styrene resin (B) 10 to 50% by weight. It provides a thermoplastic resin composition comprising 10 to 10 parts by weight and 0.001 to 1 part by weight of a coupling agent (E) having a polyorganohydrogensiloxane (D) and / or a reactive functional group. is there.

The second aspect of the present invention is that the hydrophobic zeolite (C) is 0.1 per 100 parts by weight of the total amount of the polycarbonate resin (A) 50 to 90% by weight and the styrene resin (B) 10 to 50% by weight. -10 parts by weight, polyorganohydrogensiloxane (D) and / or reactive functional group-containing coupling agent (E) 0.0001-1 part by weight, phosphate ester (F) 2-20 parts by weight, and fiber-forming type A thermoplastic resin composition comprising 0.05 to 2 parts by weight of a fluororesin (G) is provided.

Furthermore, a third aspect of the present invention relates to a molded article formed by molding the thermoplastic resin composition described in the first aspect or the second aspect.

  The thermoplastic resin composition of the present invention generates very little VOC, and is excellent in balance of flame retardancy, fluidity, physical properties, etc., especially products such as office equipment casings and exteriors, interior parts, etc. Can be suitably used as an industrial utility value.

  The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. A typical example of the polymer is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane 1,1-bis (4-hydroxy-3- Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4 Bis (hydroxyaryl) alkanes such as -hydroxy-3,5-dichlorophenyl) propane; (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3, Dihydroxy diaryl ethers such as 3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'- Dihydroxydiaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxydiaryls such as 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone Sulfonic acids, and the like.

  These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, and the like may be used in combination.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  Although there is no restriction | limiting in particular in the viscosity average molecular weight of polycarbonate resin (A), Usually, it is 10,000-100000, More preferably, it is 15000-30000, More preferably, it is 17000-23000 from the surface of moldability and intensity | strength. Moreover, when manufacturing this polycarbonate resin, a molecular weight modifier, a catalyst, etc. can be used as needed.

  The styrenic resin (B) used in the present invention is a resin obtained by polymerizing the aromatic vinyl monomer component (a), or another copolymerizable monomer using the resin as an essential component. It refers to a copolymer. Specifically, a copolymer containing a polystyrene resin and an aromatic vinyl monomer component (a), a vinyl cyanide monomer component (b) and a rubbery polymer (c) as constituent components of the copolymer Examples thereof include (B-1) and a copolymer (B-2) containing (a) as a constituent component of the copolymer.

  Examples of the preferred copolymer (B-1) include those containing a graft copolymer obtained by graft copolymerization of the components (a) and (b) in the presence of the rubbery polymer (c). An acrylonitrile-butadiene-styrene copolymer preferably made by bulk polymerization is used.

  Examples of the aromatic vinyl monomer component (a) include styrene, α-methylstyrene, o-, m-, p-methylstyrene, vinylxylene, ethylstyrene, vinylnaphthalene, and the like. More than seeds can be used. Styrene is preferably used.

  Examples of the vinyl cyanide monomer component (b) include acrylonitrile, methacrylonitrile and the like, and these can be used alone or in combination. Preferably, acrylonitrile is used.

  Examples of the rubber polymer (c) include polybutadiene, styrene-butadiene random copolymer or block copolymer, hydrogenated product of the block copolymer, acrylonitrile-butadiene copolymer, isoprene-butadiene copolymer, and the like. Diene rubber, ethylene-propylene random copolymer or block copolymer, polyisoprene, ethylene and α-olefin copolymer, ethylene-unsaturated carboxylic acid ester such as ethylene-methacrylate, ethylene-butyl acrylate Copolymer, acrylic ester-butadiene copolymer, acrylic elastic polymer such as butyl acrylate-butadiene copolymer, copolymer of ethylene and fatty acid vinyl such as ethylene-vinyl acetate, ethylene-propylene -Hexadiene copolymer Ethylene - propylene non-conjugated diene terpolymers, butylene - Isoburen copolymers, chlorinated polyethylene and the like, may be used them in one or two or more thereof. Preferred rubbery polymers are diene rubbers, ethylene-propylene non-conjugated diene terpolymers and acrylic elastic polymers, particularly preferably polybutadiene and styrene-butadiene copolymers.

  There is no restriction | limiting in particular in the composition ratio of each component of said (a), (b), and (c), It can adjust according to a use. In addition to the above components (a), (b), and (c), the copolymer (B-1) may be prepared by using a monomer copolymerizable with these components without impairing the object of the present invention. Can be used in a range.

  Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( Α, β-unsaturated carboxylic acid esters such as (meth) acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; And imide compounds of α, β-unsaturated dicarboxylic acids such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide, and the like. Can be used alone or in combination of two or more.

  The copolymer (B-2) is composed of a copolymer having the above-mentioned aromatic vinyl monomer component (a) as an essential component, preferably the aromatic vinyl monomer component (a) and cyanide. A styrene-acrylonitrile copolymer (SAN resin) composed of the vinyl monomer component (b) is used. A copolymer (B-2) contributes to the improvement of the moldability (fluidity) of the obtained thermoplastic resin composition.

  There is no restriction | limiting in particular in the composition ratio of each component of said (a), (b), Although it can adjust according to a use, Preferably, (a) component is 95 to 50 weight%, (b) component is 5 to 50% by weight, more preferably (a) is 90 to 65% by weight, and (b) is 10 to 35% by weight.

Moreover, in the copolymer (B-2), in addition to the component (a), a monomer copolymerizable therewith can be used as long as the object of the present invention is not impaired. Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( Α, β-unsaturated carboxylic acid esters such as (meth) acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; And imide compounds of α, β-unsaturated dicarboxylic acids such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide, and the like. Can be used alone or in combination of two or more.

  The blending amount of the styrene resin (B) is 10 to 50% by weight based on the polycarbonate resin (A). If the blending amount is less than 10% by weight, the fluidity is inferior. If it exceeds 50% by weight, the flame retardancy and heat resistance are inferior. It is preferably in the range of 15 to 40% by weight, more preferably in the range of 20 to 30% by weight.

As the hydrophobic zeolite (C) used in the present invention, a high silica zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 40 or more can be suitably used. A more preferred SiO ₂ / Al ₂ O ₃ molar ratio is in the range of 100 to 1000. This is different from the usual hydrophilic zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of around 1 to 10, and since it has a large amount of SiO ₂ component, the composition and structure of the crystal are slightly changed to be hydrophobic. . As a result, water molecules are less likely to be adsorbed, and conversely, the affinity with organic substances increases. Thus, the hydrophobic zeolite exhibits a selective adsorption power for the organic matter in the gas phase and the liquid phase in the mixed system of water and the organic matter. As the hydrophobic zeolite, “Absents” manufactured by UOP in the United States, “ZSM-5” manufactured by Eka Nobel Acteborag, Sweden, “HSZ series” manufactured by Tosoh Corporation, and the like are commercially available. The maximum pore size of the hydrophobic zeolite is preferably about 5 to 8 mm. If it is less than 5 mm, it is smaller than the target VOC molecular diameter, so that they are not effectively adsorbed, and if it exceeds 8 cm, these substances may be easily desorbed.

  The compounding quantity of hydrophobic zeolite (C) is 0.1-10 weight part with respect to 100 weight part of resin components which consist of polycarbonate resin (A) and styrene resin (B). When the blending amount is less than 0.1 parts by weight, the VOC adsorption / removal effect is poor, which is not preferable. Moreover, when a compounding quantity exceeds 10 weight part, not only the impact strength of a thermoplastic resin composition will fall, but it will become disadvantageous also in cost, and economical efficiency will be impaired significantly. More preferably, it is in the range of 0.5 to 7.0 parts by weight, and more preferably 1.0 to 3.0 parts by weight.

Examples of the polyorganohydrogensiloxane (D) used in the present invention include methylhydrogenpolysiloxane, methylhydrogenpolycyclosiloxane, and the like, particularly selected from the following general formulas (1) to (3). Compounds are preferred.
General formula (1)

Wherein R is a monovalent hydrocarbon group free from aliphatic unsaturation,
a is 1.00-2.10,
b is 0.1 to 1.0,
(A + b) is 2.00 to 2.67. )

General formula (2)

  General formula (3)

(A, B and n in the general formula (3) are the same as those shown in the general formula (2).)

  When a polyorganohydrogensiloxane other than the above general formulas (1) to (3) is used, a decrease in the molecular weight of the polycarbonate resin (A) is observed at the time of melt kneading at a high temperature, and a large amount of gas is generated during molding processing. Silver streaks may occur.

  The polyorganohydrogensiloxane (D) is directly blended into the mixture of the components (A), (B), (C) or (A), (B), (C), (F), (G) as it is. It is also possible to do. Further, before blending with these components, the hydrophobic zeolite (C) of the present invention is once surface-treated with the polyorganohydrogensiloxane (D), and then this is treated with (A), (B), or (A), (B ), (F), (G) may be added to the component.

  As the surface treatment method, either a wet method or a dry method may be used. Examples of the wet method include a method in which the hydrophobic zeolite (C) of the present invention is added to a mixed solution of the polyorganohydrogensiloxane (D) and the low boiling point solvent, and the solvent is removed after stirring. Then, you may heat-process further at the temperature of 120-200 degreeC. Examples of the dry method include a method in which the polyorganohydrogensiloxane (D) and the hydrophobic zeolite (C) are mixed and stirred by a mixing apparatus such as a super mixer, a Henschel mixer, or a V-type tumbler. At this time, heat treatment may be performed at a temperature of 120 to 200 ° C.

  Examples of the coupling agent (E) having a reactive functional group used in the present invention include isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds.

  Particularly preferred as the coupling agent (E) having a reactive functional group is an organic silane compound (silane coupling agent), and specific examples thereof include gamma-glycidoxypropyltrimethoxysilane, gamma-glycol. Mercapto groups such as sidoxypropyltriethoxysilane, epoxy group-containing alkoxysilane compounds such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane and gamma-mercaptopropyltriethoxysilane Ureido group-containing alkoxysilane compounds such as gamma-ureidopropyltriethoxysilane, gamma-ureidopropyltrimethoxysilane, gamma- (2-ureidoethyl) aminopropyltrimethoxysilane , Gamma-isocyanatopropyltriethoxysilane, gamma-isocyanatopropyltrimethoxysilane, gamma-isocyanatopropylmethyldimethoxysilane, gamma-isocyanatopropylmethyldiethoxysilane, gamma-isocyanatopropylethyldimethoxysilane, gamma-isocyanate Isocyanato group-containing alkoxysilane compounds such as natopropylethyldiethoxysilane, gamma-isocyanatopropyltrichlorosilane, gamma- (2-aminoethyl) aminopropylmethyldimethoxysilane, gamma- (2-aminoethyl) aminopropyltrimethoxysilane Amino group-containing alkoxysilane compounds such as gamma-aminopropyltrimethoxysilane, gamma-hydroxypropyltrimethoxysilane, gamma-hydride Hydroxyl-containing alkoxysilane compounds such as loxypropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -gamma -Carbon / carbon unsaturated group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane and hydrochloride. In particular, amino group-containing alkoxysilane compounds and phenyl group-containing alkoxysilane compounds are preferably used. These may be used alone or in combination of two or more.

The treatment of the hydrophobic zeolite (C) with these silane coupling agents is a method of adsorbing the silane coupling agent on the hydrophobic zeolite (C) in a polar solvent such as water, methanol, ethanol or the like or a mixed solvent thereof. Alternatively, a method of adding hydrophobic zeolite (C) to a high speed stirring mixer such as a Henschel mixer and dropping it in the form of an aqueous solution containing a silane coupling agent or an organic solvent while stirring, and further hydrophobicity Any method of adding a silane coupling agent directly to zeolite (C) and mixing and adsorbing it in a mortar or the like may be used. When the hydrophobic zeolite (C) is treated with a silane coupling agent, it is preferable to mix water, acidic water, alkaline water and the like at the same time in order to promote hydrolysis of the alkoxy group of the silane coupling agent. In this case, in order to increase the reaction efficiency of the silane coupling agent, water such as methanol or ethanol and an organic solvent that dissolves both the silane coupling agent may be mixed. The reaction can be further promoted by heat-treating the hydrophobic zeolite (C) treated with such a silane coupling agent. It should be noted that a so-called integral in which a hydrophobic zeolite (C) and a component other than the component are melted and kneaded without prior treatment with a hydrophobic zeolite (C) coupling agent is added. A blending method may be used.

  In the present invention, the compounding amount of the polyorganohydrogensiloxane (D) and / or the coupling agent (E) having a reactive functional group is 100 parts by weight of the resin component comprising the polycarbonate resin (A) and the styrene resin (B). On the other hand, it is 0.0001 to 1 part by weight. When the blending amount is less than 0.0001 parts by weight, the polycarbonate resin (A) is decomposed, which is not preferable. On the other hand, if the blending amount exceeds 1 part by weight, gas or silver streak is generated at the time of molding, which also causes trouble, which is not preferable. More preferably, it is 0.001-0.5 weight part, More preferably, it is the range of 0.01-0.1 weight part. In the present invention, both the polyorganohydrogensiloxane (D) and the coupling agent (E) having a reactive functional group may be used in combination.

  Examples of the phosphate ester (F) used in the present invention include compounds represented by the following general formula (4).

  General formula (4)

  In the general formula (4), Ar1 to Ar4 in the formula are the same or different monovalent aromatic groups, and examples thereof include a phenyl group, a cresyl group, a xylyl group, and a t-butylphenyl group. X is an aromatic group derived from divalent phenols, and includes catechol, resorcinol, hydroquinol, 4-t-butylcatechol, 2-tert-butylhydroquinone, bisphenol A, bisphenol S sulfide, bisphenol F, Bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxylphenyl) sulfone and the like can be mentioned. These divalent phenols are preferably resorcinol, hydroquinol, and bisphenol A, and more preferably resorcinol and bisphenol A. The polyphosphate can be obtained by reacting these divalent phenols and monovalent phenols represented by Ar.OH with phosphorus oxychloride.

  The above polyphosphates include phenyl resorcin polyphosphate, cresyl resorcin polyphosphate, phenyl cresyl resorcin polyphosphate, phenyl hydroquinone polyphosphate, cresyl hydroquinone polyphosphate, phenyl cresyl hydroquinone polyphosphate, phenyl 2, 2-bis (4-oxyphenyl) propane (: bisphenol A type) polyphosphate, cresyl 2,2-bis (4-oxyphenyl) propane (: bisphenol A type) polyphosphate, phenyl cresyl 2, 2-bis (4-oxyphenyl) propane (: bisphenol A type) polyphosphate, xylyl-resorcin polyphosphate, phenyl-pt-butylphenyl resorcin-polyphosphate DOO, phenyl isopropylphenyl resorcin polyphosphate, cresyl xylyl resorcinol polyphosphate, phenyl-isopropylphenyl-diisopropylphenyl resorcinol polyphosphate, and the like as examples. These are easily available as commercial products.

  The compounding quantity of phosphoric ester (F) is 2-20 weight part with respect to 100 weight part of resin components which consist of polycarbonate resin (A) and styrene resin (B). If the blending amount is less than 2 parts by weight, sufficient flame retardancy cannot be obtained. On the other hand, if it exceeds 20 parts by weight, the heat resistance is greatly impaired, which is not preferable. Preferably it is 6-16 weight part, More preferably, it is the range of 8-13 weight part.

  As the fiber-forming fluororesin (G) used in the present invention, one that forms a fiber structure (fibrillar structure) in the resin component of the polycarbonate resin (A) and the styrene resin (B) is good. Manufactured from polytetrafluoroethylene, tetrafluoroethylene copolymer (eg, tetrafluoroethylene / hexafluoropropylene copolymer, etc.), partially fluorinated polymer as shown in US Pat. No. 4,379,910, and fluorinated diphenol The polycarbonate etc. which are made are mentioned. These exhibit a dripping prevention effect when used in combination with the phosphoric ester (F) of the present invention.

  The blending amount of the fiber-forming fluororesin (F) is 0.05 to 2 parts by weight with respect to 100 parts by weight of the resin component composed of the polycarbonate resin (A) and the styrene resin (B). If the blending amount is less than 0.05 parts by weight, the effect of preventing dripping at the time of combustion may be inferior, and if it exceeds 2 parts by weight, granulation becomes difficult and stable production may be hindered. More preferably, it is 0.1-1 weight part, More preferably, it is the range of 0.3-0.6 weight part. In this range, the balance of flame retardancy, impact strength and granulation properties is further improved.

  Various blending components of the present invention, polycarbonate resin (A), styrene resin (B), hydrophobic zeolite (C), polyorganohydrogensiloxane (D), coupling agent (E) having a reactive functional group, phosphate ester (F) The method and order of mixing the fiber-forming fluororesin (G) is not particularly limited, and is mixed with an optional mixer such as a tumbler, ribbon blender, high-speed mixer, etc. It can be easily melt-kneaded with an extruder or the like.

In addition, a known additive such as a phenol-based or phosphorus-based heat stabilizer [2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4, 6-dimethylphenol, 4,4'-thiobis- (6-t-butyl-3-methylphenol), 2,2-methylenebis- (4-ethyl-6-t-methylphenol), n-octadecyl 3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate, tris (2,4-di-t-butylphenyl) phosphite, 4,4'biphenylenediphosphinic acid tetrakis (2,4-di-t- Butylphenyl), etc.], UV absorber [pt-butylphenyl salicylate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hex ) Oxy] -phenol, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t) -Octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl) -2H-benzotriazole, etc.], mold release agent [beeswax, glycerol monostearate, montanic acid Wax, polyethylene wax, pentaerythritol tetrastearate, etc.], colorant [titanium oxide and other dyes and pigments], spreading agent [epoxidized soybean oil, liquid paraffin, etc.], monophosphate ester, flame retardant [brominated polycarbonate oligomer, aroma Group sulfur-containing metal salt, perfluorobutanesulfonic acid metal salt, polytetrafluoro Ethylene, etc.] can be further used a variety of rubber-like elastic material below. Acrylic elastomers, isoprene elastomers (including hydrogenated products), various olefin elastomers, polyester elastomers, and core / shell structures (the core is composed of polybutadiene and the shell is composed of methyl (meth) acrylate and / or styrene) One or two or more vinyl monomers in a rubber-like elastic body or a composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are intertwined so that they cannot be separated from each other A composite rubber-based graft copolymer obtained by graft polymerization is preferably used.
In addition, as other thermoplastic resins, for example, polyethylene terephthalate, polybutylene terephthalate, amorphous polyester, polyphenylene ether, polymethyl methacrylate and the like can be blended as necessary.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “parts” and “%” are based on weight.

The detail of the various compounding components used is as follows.
(A) Polycarbonate resin (hereinafter abbreviated as PC)
Caliber 200-20 manufactured by Sumitomo Dow (molecular weight: 18700)
(B) Styrenic resin (hereinafter abbreviated as ABS)
Santac AT07 (bulk polymerized product) manufactured by Japan A & L
(C) Hydrophobic zeolite (hereinafter abbreviated as ZEO)
UOP Hydrophobic Zeolite / Absent 3000 (Adsorption pore size: 6 mm)
(D) Polyorganohydrogensiloxane (hereinafter abbreviated as SiH)
KF99 manufactured by Shin-Etsu Chemical Co., Ltd.
(E) Silane coupling agent (hereinafter abbreviated as SiC)
Toray Dow Corning Silicone Phenylmethoxysilane AZ6207
(F) Phosphate ester (hereinafter abbreviated as P flame retardant)
CR-841 manufactured by Daihachi Chemical Industry Co., Ltd.
(G) Fiber-forming fluororesin (hereinafter abbreviated as PTFE)
Asahi Glass Co. Fullon G340

  As a blending method, the above-mentioned various blending components are collectively put into a tumbler at blending ratios shown in Tables 1 to 4, and after dry mixing for 10 minutes, using a twin-screw extruder (Kobe Steel KTX37). And kneading at a melting temperature of 240 ° C. to obtain pellets of various resin compositions.

In the experimental example using SiC, the surface treatment of ZEO was previously performed with SiC as follows. (The obtained treated ZEO is hereinafter abbreviated as surface treated ZEO)
(A) 120 g of SiC is diluted 2 to 5 times with water or an aqueous alcohol solution (water / isopropyl alcohol = 1/9) and stirred until uniform.
(I) 6 Kg of ZEO is charged into a 20 L super mixer manufactured by Kawada Seisakusho and stirred.
(C) The entire amount of the SiC aqueous solution prepared in (a) is dropped into the stirred ZEO over several tens of minutes.
(D) Continue stirring for another 10 minutes.
(E) The obtained surface-treated ZEO is uniformly spread on a tray and dried at 150 ° C. for 1 hour.

  Further, two types of VOC reduction rates were obtained from the data on the amount of VOC released per unit time: a styrene gas reduction rate and a styrene equivalent total VOC reduction rate. The measuring method of the amount of VOC emission per unit time is as follows.

(VOC emission)
After 0.1 g of pellets of the resin composition were heated at 80 ° C. for 1 hour in an inert gas stream, the out gas generated from the pellet samples was collected and concentrated with an adsorbent, and then per hour by GC-MS. The amount of VOC released was determined.
The used heat introduction apparatus and GC-MS are as follows.
Heating introduction device:
TurboMatrix ATD made by Perkin Elmer
GC-MS:
Made by Agilent Technologies
HP5973N / GC6890
Adsorbent:
Tenax GR manufactured by Chromatography Research
Quantitation limit:
10ng / g · hr

The amount of VOC released per unit time was calculated by dividing into the following two types.
Styrene gas release (ng / g · hr):
From the obtained outgas data, paying attention only to styrene as VOC
The amount released.
Styrene conversion total VOC release (ng / g · hr):
From the obtained outgas data, the release amount of all components was converted to styrene.
More calculated amount of release.

(VOC reduction rate calculation method and evaluation criteria)
Styrene gas reduction rate:
In each of the resin compositions, when a hydrophobic zeolite is blended, and
Use the pellet sample when not blended to determine the amount of styrene gas released.
The styrene gas reduction rate was obtained from the following formula. The styrene gas reduction rate is
More than 30% was accepted.
Styrene gas reduction rate (%) = (STY2-STY1) × 100 / STY2
STY1: Amount of styrene gas released from a sample containing hydrophobic zeolite
STY2: Styrene gas release amount of sample not containing hydrophobic zeolite Reduction rate of total VOC in terms of styrene:
In each of the resin compositions, when a hydrophobic zeolite is blended, and
Styrene conversion total VOC release using pellet sample when not blended
The amount was determined, and the reduction rate of total VOC in terms of styrene was determined according to the following formula. Still
The total VOC reduction rate converted to 40% or more was regarded as acceptable.
Reduction rate of total VOC in styrene (%)
= (ALL2-ALL1) x100 / ALL2
ALL1:
Total VOC release from styrene in samples containing hydrophobic zeolite
ALL2:
Total amount of VOC emission in styrene conversion of samples not containing hydrophobic zeolite

(Izod impact strength with notch)
Using pellets of various resin compositions shown in Tables 1 to 4, using a J100E-C5 injection molding machine manufactured by Nippon Steel Works, a 3.2 mm thick Izod impact strength test piece was used under the condition of a melting temperature of 260 ° C. Created. The notched Izod impact strength was measured at a measurement temperature of 23 ° C. in accordance with ASTM D256. An impact value of 10 kg / cm / cm or more was regarded as acceptable. The results are shown in Tables 1 to 4.

(Combustion test)
Using pellets of various resin compositions shown in Tables 3 and 4, flame retardancy (self-extinguishing property) was measured with a 1.6 mm-thick test piece according to UL94. The test piece is allowed to stand for 48 hours in a temperature-controlled room with a temperature of 23 ° C and a humidity of 50%. Was evaluated. UL94V is a method for evaluating flame retardance from the afterflame time and drip properties after indirect flames of a burner for 10 seconds on a test piece of a predetermined size held vertically, and is divided into the following classes: .
V-0 V-1 V-2
10 seconds or less for each sample 30 seconds or less 30 seconds or less Afterflame time 5 samples for 50 seconds or less 250 seconds or less 250 seconds or less Total afterflame time No drip None Yes Attached cotton ignition This is the length of time that the test piece continues to burn in flame after moving away from the ignition source. The ignition of cotton by drip means that the marking cotton, which is about 300 mm below the lower end of the test piece, moves from the test piece. It is determined by whether or not it is ignited by a drip. As a standard for evaluation, V-0 was accepted in the 1.6 mm thickness test.

(Archimedes spiral flow fluidity)
Using the pellets of various resin compositions shown in Tables 1 to 4, the flow length at a flow channel thickness of 2 mm was measured using an Archimedes spiral flow mold under the condition of a melting temperature of 280 ° C. A flow length of 40 cm or more was accepted.

(Silver Streak)
Using the pellets of various resin compositions shown in Tables 1 to 4, silver streaks generated on the surface of a test piece of size: 60 (length) × 50 (width) × 3 mm (thickness) were visually determined.

Table 1 Mixing ratio of components and evaluation results

○： 合格 ×： 不合格

○: Pass ×: Fail

Table 2 Blending ratios and evaluation results of blending components

○： 合格 ×： 不合格

○: Pass ×: Fail

  As shown in Table 1, when the first aspect of the present invention was satisfied (Examples 1 to 4), the standards were satisfied over all evaluation items.

As shown in Table 2, in the case where the first aspect of the present invention was not satisfied, each case had some drawbacks.
Comparative Example 1 is a case where the blending amount of the hydrophobic zeolite (C) component of the present invention is less than the specified amount, and the styrene gas reduction rate and the styrene equivalent total VOC reduction rate did not satisfy the standard.
Comparative Example 2 is a case where the amount of the polyorganohydrogensiloxane (D) component of the present invention is less than the specified amount, and the deactivation of the zeolite is insufficient, so that the polycarbonate resin is decomposed. Therefore, a large amount of silver streaks occurred on the surface of the molded product.
Comparative Example 3 is a case where the amount of the polyorganohydrogensiloxane (D) component of the present invention is larger than the specified amount. Since a large amount of gas derived from the siloxane is generated, a large amount of silver streak is generated on the surface of the molded product.
In Comparative Example 4, the amount of the hydrophobic zeolite (C) component of the present invention was greater than the specified amount, and the impact strength did not satisfy the standard.

Table 3 Blending ratios and evaluation results of blending components

○： 合格 ×： 不合格

○: Pass ×: Fail

Table 4 Blending ratios and evaluation results of blending components

○： 合格 ×： 不合格 ＮＲ：ＵＬ９４のどのクラスにも属さないことを表す。

○: Pass ×: Fail NR: Represents not belonging to any class of UL94.

  As shown in Table 3, when the second aspect of the present invention was satisfied (Examples 5 to 10), the standard was satisfied over all evaluation items.

As shown in Table 4, in the case where the second aspect of the present invention was not satisfied, each case had some drawbacks.
In Comparative Example 5, since the polycarbonate resin (A)) component of the present invention was less than the specified amount, the flame retardancy was rejected.
In Comparative Example 6, since the hydrophobic zeolite (C) component of the present invention was further less than the specified amount, the VOC reduction rate did not satisfy the standard.
In Comparative Example 7, since the blending amount of the hydrophobic zeolite (C) component of the present invention was larger than the specified amount, the impact strength was rejected.
In Comparative Example 8, a large amount of silver streaks occurred because the polyorganohydrogensiloxane (D) of the present invention was not blended.

Claims (6)

  Hydrophobic zeolite (C) 0.1-10 parts by weight and polyorganohydrogensiloxane (D) per 100 parts by weight of the total amount of polycarbonate resin (A) 50-90% by weight and styrene-based resin (B) 10-50% by weight A thermoplastic resin composition comprising 0.0001 to 1 part by weight of a coupling agent (E) having a reactive functional group.   Hydrophobic zeolite (C) 0.1 to 10 parts by weight, polyorganohydrogensiloxane (D) per 100 parts by weight of the total amount of polycarbonate resin (A) 50 to 90% by weight and styrene resin (B) 10 to 50% by weight And / or coupling agent (E) having a reactive functional group (0.0001 to 1 part by weight), phosphate ester (F) (2 to 20 parts by weight) and fiber-forming fluororesin (G) 0.05 to 2 parts by weight A thermoplastic resin composition characterized by comprising parts.   Styrenic resin (B) is acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), polystyrene (PS), and methyl methacrylate-butadiene-styrene copolymer (MBS resin). The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is one or more selected from the group consisting of:   The thermoplastic resin composition according to claim 1 or 2, wherein the styrenic resin (B) is an acrylonitrile-butadiene-styrene copolymer (ABS resin) produced by a bulk polymerization method.   The coupling agent (E) having a reactive functional group is one or more selected from an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. The thermoplastic resin composition according to claim 1 or 2. A molded article obtained by molding the thermoplastic resin composition according to claim 1.