JP2004002897A - Thermoplastic resin composition for tray - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition for trays, forming moldings having excellent flame retardance, rigidity, moldability and plating adhesiveness. <P>SOLUTION: This thermoplastic resin composition for trays comprises 1-97 wt.% thermoplastic resin (A), 1-97 wt.% polycarbonate (B), 1-30 wt.% flame retardant (C) and 1-30 wt.% inorganic filler (D), wherein the thermoplastic resin (A) is obtained by polymerizing, in the presence of 0-90 wt.% rubber-like polymer (a), 100-10 wt.% at least one monomer (b) selected from a group consisting of aromatic vinyl, vinyl cyanide, (meth)acrylic ester, acid anhydride and maleimide and the inorganic filler (D) is at least one selected from (D1) inorganic filler having 0.5-20 μm mean particle diameter, (D2) fibrous inorganic filler and (D3) inorganic filler surface-treated with a silane coupling agent. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a thermoplastic resin composition for trays, and more particularly, to a thermoplastic resin composition for trays that provides molded articles having excellent flame retardancy, rigidity, and plating adhesion.

An alloy material of ABS resin and polycarbonate is known as a material having excellent heat resistance, impact resistance, and moldability. Recently, DVDs, CD-ROMs, CDs, and the like used in OA equipment, home electric appliances, and the like. Is used as a material for trays for storing, transporting, and assembling various electronic components including semiconductors such as ICs and liquid crystals. Due to the demand for lighter and smaller trays, a resin material that can form a thin and highly rigid tray has been demanded. However, the rigidity of an alloy of ABS resin and polycarbonate alone is insufficient. Inorganic fillers are further compounded.

ト レ ー In the case of trays for storing electronic components, etc., plating may be applied to the entire surface or a part of the tray to provide electromagnetic wave shielding. However, when plating for imparting electromagnetic wave shielding properties is performed on a tray made of an alloy of ABS resin and polycarbonate with increased rigidity by blending an inorganic filler, the plating layer is easily peeled off by tape peeling. The problem arises.

In addition, since the plating characteristics generally depend on the processing time and the processing temperature with the etching solution in the pre-plating process, etching conditions for obtaining a molded product having good plating characteristics are limited. Therefore, from the viewpoint of reducing the defective rate of the plated product and improving the productivity, it is possible to provide a molded product which has excellent plating characteristics without depending on the etching processing time and processing temperature and which can be suitably used as a tray. It is desired to provide a plastic resin composition.

A thermoplastic resin composition comprising an alloy of an ABS resin and a polycarbonate excellent in weld strength, weld appearance, thermal stability, chemical resistance, plating properties, etc., mixed with a flame retardant and capable of adding various fillers is known. (For example, see Patent Document 1). However, in this thermoplastic resin composition, the problem that the plating characteristics depend on the processing time and the processing temperature with the etching solution in the pre-plating process has not been solved.

Also, in order to enhance the plating characteristics (peeling resistance) of a molded article made of a resin composition obtained by blending an inorganic filler with an alloy of an ABS resin and a polycarbonate, an alloy of an ABS resin and a polycarbonate is used. A method is known in which a halogen compound, antimony oxide phosphate, and a flaky filler having an aspect ratio of 2 or more and an average particle diameter of 1 to 100 μm are contained (for example, see Patent Document 2). With this method, the plating properties of the molded article are improved, but the problem that the plating properties depend on the processing time or the processing temperature with the etching solution in the pre-plating processing step is solved similarly to the thermoplastic resin composition described above. Not.
JP-A-7-173362 JP-A-8-193157

The present invention has been made in view of the above circumstances, and has as its object to solve the above-mentioned problems, and to provide excellent flame retardancy, rigidity, moldability and plating adhesion, and the plating adhesion is improved by plating pretreatment. It is an object of the present invention to provide a thermoplastic resin composition for trays that gives a molded product that does not depend on etching conditions in a process.

That is, the first gist of the present invention is that the thermoplastic resin (A) 1 to 97% by weight, the polycarbonate (B) 1 to 97% by weight, the flame retardant (C) 1 to 30% by weight, and the inorganic filler (D) 1 to 30% by weight (however, (A) + (B) + (C) + (D) = 100% by weight), and the thermoplastic resin (A) is a rubber-like polymer (a) 0 to In the presence of 90% by weight, 100 to 10% by weight of at least one monomer (b) selected from the group consisting of aromatic vinyl, vinyl cyanide, (meth) acrylate, acid anhydride and maleimide ( However, (a) + (b) = 100% by weight) is obtained by polymerization, and the inorganic filler (D) is at least one selected from the following inorganic fillers (D1) to (D3). One type of thermoplastic resin composition for trays.

(D1): inorganic filler having an average particle size of 0.5 to 20 μm (D2): fibrous inorganic filler (D3): inorganic filler surface-treated with a silane coupling agent

The second gist of the present invention is that the thermoplastic resin (A) is 1 to 97% by weight, the polycarbonate (B) is 1 to 97% by weight, the flame retardant (C) is 1 to 30% by weight, the inorganic filler (D '). ) 100 parts by weight of a resin composition consisting of 1 to 30% by weight (provided that (A) + (B) + (C) + (D ') = 100% by weight), The thermoplastic resin (A) contains aromatic vinyl, vinyl cyanide, (meth) acrylate, acid anhydride in the presence of 0 to 90% by weight of the rubbery polymer (a). And at least one monomer (b) selected from the group consisting of a product and a maleimide, obtained by polymerizing 100 to 10% by weight (provided that (a) + (b) = 100% by weight), The polymer (E) is at least one selected from the following polymers (E1) to (E3). DOO lies in the tray for the thermoplastic resin composition characterized.

(E1): at least one monomer (b) selected from the group consisting of aromatic vinyl, vinyl cyanide, (meth) acrylate, acid anhydride and maleimide in the presence of the modified polyorganosiloxane (e) (E2): Polytetrafluoroethylene (E3) having an average particle diameter of 0.1 to 80 μm: Nonpolar α-olefin (co) polymer and vinyl (co) polymer And a polymer containing

Hereinafter, the present invention will be described in detail. The present invention according to the first aspect (hereinafter, referred to as a first invention) comprises a thermoplastic resin (A), a polycarbonate (B), a flame retardant (C), and an inorganic filler (D). The invention according to the gist (hereinafter referred to as the second invention) comprises a thermoplastic resin (A), a polycarbonate (B), a flame retardant (C), an inorganic filler (D '), and a polymer (E). Therefore, since the composition for trays of each invention of the present application overlaps or is similar in most of the components used, the components used in each invention will be described first for convenience of explanation.

The thermoplastic resin (A) in the first invention and the second invention contains aromatic vinyl, vinyl cyanide, (meth) acrylate, acid in the presence of 0 to 90% by weight of the rubbery polymer (a). It is obtained by polymerizing 100 to 10% by weight (where (a) + (b) = 100% by weight) of at least one monomer (b) selected from the group consisting of anhydride and maleimide.

Examples of the rubbery polymer (a) include polybutadiene, styrene-butadiene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene- (non-conjugated diene) copolymer, and ethylene-butene-1- (non-conjugated). Diene) copolymer, isobutylene-isoprene copolymer, acrylic rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butene-styrene copolymer (SEBS), etc. Hydrogenated diene (block, random and homo) weight products, polyurethane rubber, etc., among these, polybutadiene, styrene-butadiene copolymer, ethylene-propylene- (non-conjugated diene) copolymer, Hydrogenated diene polymers are preferred.

In this case, the rubbery polymer (a) may be composed of two or more rubbery polymers having different compositions and / or two or more rubbery polymers having different particle diameters. By mixing and using rubbery polymers having different particle diameters as the rubbery polymer (a), it is possible to obtain the thermoplastic resin composition of the present invention which is more excellent in impact resistance and physical property balance. . As the above rubbery polymer, a combination of a rubbery polymer of 800 to 1800 ° and a rubbery polymer of 1800 to 4800 ° is preferable.

Examples of the aromatic vinyl include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, methyl-α-methylstyrene, and brominated styrene. , Styrene, α-methylstyrene and p-methylstyrene are preferred.

ビ ニ ル The above-mentioned vinyl cyanide includes, for example, acrylonitrile, methacrylonitrile and the like, and among these, acrylonitrile is preferable.

Examples of the (meth) acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Among these, methyl methacrylate, Butyl acrylate is preferred.

マ As the acid anhydride, maleic anhydride is preferable.

Examples of the maleimide include maleimide, N-methylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexylmaleimide. Among them, N-phenylmaleimide is preferred. Maleimide particularly has an effect of improving the heat resistance of the thermoplastic resin composition of the present invention, and its use amount is usually preferably in the range of 20 to 80% by weight of the monomer (b).

When polymerizing at least one monomer (b) in the presence or absence of the rubbery polymer (a) to produce a thermoplastic resin (A), the sum of (a) and (b) When the amount is 100% by weight, the proportion of the rubbery polymer (a) used is usually 0 to 90% by weight, preferably 15 to 80% by weight, more preferably 20 to 70% by weight. When the amount of the rubber-like polymer (a) is more than 90% by weight, poor appearance and deterioration in molding processability occur.

The thermoplastic resin (A) can be produced by a known emulsion polymerization method, solution polymerization method, suspension polymerization method, or the like. The polymerization in the presence of the rubbery polymer (a) is usually a graft polymerization using the rubbery polymer (a) as a trunk polymer. In the case of the emulsion polymerization method, usually, a powder obtained by coagulation with a coagulant is purified by washing with water and drying.

As the radical initiator at the time of polymerization, known ones can be used. Specifically, for example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide, Lauroyl peroxide, t-butyl peroxylaurate, t-butyl peroxy monocarbonate and the like can be mentioned.

When the thermoplastic resin (A) is produced using a rubber-like polymer, the graft ratio to the rubber-like polymer varies depending on the type of the graft component, but is usually 10 to 150% by weight, preferably 30 to 130% by weight. % By weight, more preferably 40 to 120% by weight. When the graft ratio of the thermoplastic resin (A) is less than 10% by weight, poor appearance and lower impact strength occur. On the other hand, if it exceeds 150% by weight, the moldability is poor.

The graft ratio is determined by the following formula, where Xg is the rubber component in 1 g of the thermoplastic resin (A) and Yg is the methyl ethyl ketone insoluble content of the thermoplastic resin (A).

The intrinsic viscosity (η) of the matrix resin in the thermoplastic resin (A) (measured in methyl ethyl ketone at 30 ° C.) is usually 0.1 to 1.5 dl / g, preferably 0.3 to 1.0 dl / g. It is. When the intrinsic viscosity [η] is in the above range, a resin composition of the present invention having excellent impact resistance and moldability (fluidity) can be obtained.

Representative examples of the thermoplastic resin (A) include acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-EPDM-styrene copolymer (AES resin), and acrylonitrile-styrene copolymer (AS resin) Styrene-methyl methacrylate copolymer, styrene-N-phenylmaleimide copolymer, polystyrene (PS), polymethyl methacrylate (PMMA), and the like. Among these, ABS resin, AES resin, and AS resin are preferable.

When the thermoplastic resin (A) is an ABS resin or an AES resin, the content of the rubbery polymer is usually 5 to 65% by weight, preferably 15 to 55% by weight, and the graft ratio is usually 40 to 65%. It is 150% by weight, preferably 50 to 120% by weight, and the intrinsic viscosity [η] of the matrix resin (ABS resin or AES resin) is usually 0.1 to 1.5 dl / g.

When the thermoplastic resin (A) is an AS resin, the copolymerization ratio of acrylonitrile is usually 10 to 45% by weight, preferably 15 to 35% by weight, more preferably 20 to 32% by weight. Yes, the intrinsic viscosity (η) of the AS resin is usually 0.3 to 0.8 dl / g, preferably 0.4 to 0.7 dl / g.

In the production of the thermoplastic resin (A), in addition to the monomer (b), that is, aromatic vinyl, vinyl cyanide, (meth) acrylic acid ester, acid anhydride, and maleimide, a functional group-containing resin is contained. A vinyl monomer may be copolymerized. Examples of such a functional group include an epoxy group, a hydroxyl group, a carboxylic acid group, an amino group, an amide group, and an oxazoline group. Specific examples of the functional group-containing vinyl monomer include glycidyl methacrylate, glycidyl acrylate, Examples thereof include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, acrylic acid, methacrylic acid, and vinyl oxazoline.

界面 By copolymerizing the above functional group-containing vinyl monomer, the interfacial adhesion (compatibility) with the polycarbonate (B) or other thermoplastic resin in the thermoplastic resin composition of the present invention can be increased. The copolymerization amount of the functional group-containing vinyl monomer is usually 0.1 to 15% by weight, preferably 0.5 to 12% by weight.

The thermoplastic resin (A) may be a single resin or a blend of two or more resins. Particularly preferred thermoplastic resin (A) is as shown in Table 1 below.

The polycarbonate (B) in the first and second inventions can be obtained by various methods such as a reaction between dihydroxyaryl and phosgene (phosgene method) and a transesterification reaction between dihydroxyaryl and diphenyl carbonate (ester exchange method). A typical polycarbonate (B) is an aromatic polycarbonate obtained by reacting 2,2'-bis (4-hydroxyphenyl) propane with phosgene. The thermoplastic resin composition for trays of the present invention includes various trays, particularly trays for storing DVDs, CD-ROMs, CDs and the like used in OA equipment and home appliances, semiconductors such as ICs, and liquid crystals. It is used as a material for forming trays for storing, transporting and assembling various electronic components. Therefore, chlorine ions volatilized from the tray material may contaminate the electronic components and the like to be stored and may be defective.It is desirable that the polycarbonate does not contain chlorine as much as possible. It is preferred to use.

Examples of the above dihydroxyaryl include bis (4-hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, 2,2'-bis (4-hydroxyphenyl) propane, and 2,2'-bis (4-hydroxyphenyl) butane, 4,4'-dihydroxy-3,3'-dimethyldiphenylether, 4,4'-dihydroxyphenylsulfide, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3, 3'-dimethyldiphenyl sulfone, hydroquinone, resorcin and the like. Further, such a dihydroxyaryl may have an aromatic ring substituted with an organic substituent such as halogen (preferably bromine), a methyl group or an ethyl group.

(4) The viscosity average molecular weight of the polycarbonate (B) is usually 15,000 to 40,000, preferably 17,000 to 30,000, and more preferably 18,000 to 28,000. When the viscosity average molecular weight of the polycarbonate (B) is in the above range, the thermoplastic resin composition of the present invention having particularly excellent moldability can be obtained.

Examples of the flame retardant (C) in the first invention and the second invention include a halogen compound, an organic phosphorus compound, a nitrogen compound, a metal hydroxide, an antimony compound, and the like. You can do it. Among them, from the viewpoint of environmental problems due to halogen-containing compounds and heavy metals, organic phosphorus compounds, nitrogen compounds and metal hydroxides are preferable, and organic phosphorus compounds are particularly preferable.

Examples of the above-mentioned halogen-based compound include oligomers of tetrabromobisphenol-A and epichlorohydrin (both terminals or one terminal thereof may be sealed with an epoxy group, tribromophenol, or the like), and brominated styrene. Examples include polymers, brominated polystyrene, oligomers of brominated polycarbonate, tetrabromobisphenol-A, decabromodiphenyl ether, and aliphatic chlorine compounds.

オ リ ゴ マ ー Among the halogen compounds, oligomers of tetrabromobisphenol-A and epichlorohydrin are preferred. The molecular weight of the oligomer is usually 800 to 6,000, preferably about 1,200 to 3,500. The bromine content of the above brominated compound is usually 30 to 65% by weight, preferably 45 to 60% by weight. The softening point (melting point) of the halogen compound is usually 70 to 280 ° C, preferably 80 to 200 ° C.

Examples of the organophosphorus compound include triphenyl phosphate, triphenyl thiophosphate, trixylenyl phosphate, tricresyl phosphate, trixylenyl thiophosphate, hydroquinone bis (diphenyl phosphate), and resorcinol bis ( Diphenyl phosphate), resorcinol bis (dixylenyl phosphate), and oligomers of triphenyl phosphate.

Among the organic phosphorus compounds, triphenyl phosphate, trixylenyl phosphate, and resorcinol bis (dixylenyl phosphate) are preferable. The phosphorus content of the organic phosphorus compound is usually 4 to 30% by weight, preferably 6 to 25% by weight. The melting point of the organic phosphorus compound is usually 40 to 150 ° C, preferably 45 to 145 ° C.

窒 素 Examples of the above-mentioned nitrogen compound include melamine and cyclized products of isocyanate. A compound in which hydrogen of melamine is substituted by an alkyl group having 1 to 18 carbon atoms or an aromatic group can also be used.

と し て Examples of the metal hydroxide include magnesium hydroxide and aluminum hydroxide.

ア ン チ Examples of the antimony compound include antimony trioxide and antimony pentoxide.

The inorganic filler (D) in the first invention is selected from the group consisting of wollastonite, talc, mica, zinc oxide whiskers, calcium titanate whiskers, etc., which meet the following conditions of the inorganic fillers (D1) to (D3). The species must be alone or two or more. In the first invention, rigidity can be imparted without impairing plating adhesion by using a filler that meets the above selection conditions. As the inorganic filler (D), talc or mica is preferable, and talc is more preferable.

The inorganic filler (D1) is an inorganic filler having an average particle diameter in a specific range. That is, it is an inorganic filler having an average particle size of 0.5 to 20 μm, preferably 1 to 15 μm, more preferably 1.3 to 13 μm. When the average particle size is less than 0.5 μm, agglomeration occurs at the time of kneading, and the appearance and plating adhesion of the molded product are inferior. When it exceeds 20 μm, physical properties such as impact resistance and appearance are impaired.

The inorganic filler (D2) is a fibrous inorganic filler, and its length is usually 0.5 μm or more, preferably 1.0 μm or more. Examples of such a filler include fibrous talc obtained from serpentinite obtained from the Sanbagawa-denatured layer. This fibrous talc is a light green fibrous. When a fibrous inorganic filler is used, peeling of plating is prevented, and the adhesion can be improved. Since mica is in the form of scale, it does not correspond to the inorganic filler (D2) in the present invention.

The inorganic filler (D3) is an inorganic filler surface-treated with a silane coupling agent. The coating amount of the silane coupling agent with respect to the inorganic filler is usually in the range of 0.1 to 5% by weight, preferably 0.5 to 3% by weight. As the silane coupling agent, those having a functional group such as an epoxy group, an amino group, a vinyl group, and a hydroxyl group can be used. As the functional group, an epoxy group or an amino group is preferable.

無機 The inorganic filler (D ') in the second invention is not particularly limited because it is blended with the polymer (E) described below. In addition, rigidity can be imparted without impairing plating adhesion. Specific examples of the inorganic filler (D ′) include wollastonite, talc, mica, zinc oxide whiskers, calcium titanate whiskers, and glass flakes. However, it is preferred that the inorganic filler (D ') be selected from the aforementioned inorganic fillers (D).

重合 The polymer (E) in the second invention is a polymer selected from the following polymers (E1) to (E3), and two or more of them can be used in combination.

The polymer (E1) is a copolymer of at least one monomer selected from the group consisting of aromatic vinyl, vinyl cyanide, (meth) acrylate, acid anhydride and maleimide in the presence of the modified polyorganosiloxane (e). It is a polymer obtained by polymerizing the compound (b).

As the modified polyorganosiloxane (e), a modified organosiloxane (e) obtained by co-condensing an organosiloxane and a graft crosslinking agent is usually used. Examples of the organosiloxane include, for example, a general formula R ¹ _n SiO _{(4-n) / 2} (where R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, and n is an integer of 1 to 3) And a structural unit represented by the following formula: Such an organosiloxane may have a linear, branched or cyclic structure, but is preferably an organosiloxane having a cyclic structure.

Specific examples of the above-mentioned organosiloxane include cyclic compounds such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexanesiloxane, and trimethyltriphenylcyclotrisiloxane. Alternatively, a branched organosiloxane can be used.

Specific examples of the above grafting agent include p-vinylphenylmethyldimethoxysilane, 1- (p-vinylphenyl) methyldimethylisopropoxysilane, 2- (p-vinylphenyl) ethylenemethyldimethoxysilane, and 3- (p -Vinylphenoxy) propylmethyldiethoxysilane, 1- (o-vinylphenyl) -1,1,2-trimethyl-2,2-dimethoxydisilane, vinylmethyldimethoxysilane, tetravinyltetramethylcyclosiloxane, allylmethyldimethoxysilane , Γ-mercaptopropylmethylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, methyltrimethoxysilane and the like. Among these, p-vinylphenylmethyldimethoxysilane, 2- (p-vinylphenyl) G) Ethylmethyldimethoxysilane and 2- (p-vinylphenyl) ethylenemethyldimethoxysilane are preferred.

When the modified polyorganosiloxane (e) is produced, the proportion of the graft crosslinking agent used is usually 0.1 to 10% by weight, preferably 0.3 to 5% by weight, more preferably 0.4 to 3% by weight. is there. When the use amount of the graft crossing agent is less than 0.1% by weight, the graft ratio of the obtained polymer (E1) is low, so that the modified polyorganosiloxane (e) and the polymer portion grafted thereto are not Interfacial adhesive strength is reduced, and interfacial peeling is likely to occur.

The preferred weight average molecular weight in terms of polystyrene of the modified polyorganosiloxane (e) is usually from 30,000 to 1,000,000, preferably from 50,000 to 300,000. By using the polymer (E1) produced by graft-polymerizing the monomer (b) to the modified polyorganosiloxane (e), the thermoplastic resin of the present invention having an excellent balance between impact resistance and fluidity A composition can be obtained.

When the monomer (b) is graft-polymerized to the modified polyorganosiloxane (e), when the total amount of (e) and (b) is 100% by weight, the use ratio of the modified polyorganosiloxane (e) is as follows: Usually, it is 5 to 90% by weight, preferably 10 to 80% by weight, more preferably 10 to 70% by weight. If the modified polyorganosiloxane (e) is less than 5% by weight, sufficient impact strength cannot be obtained, and if the modified polyorganosiloxane (e) exceeds 90% by weight, poor appearance and reduced impact strength occur.

(4) The graft ratio of the polymer (E1) is usually 10% by weight or more, preferably 20% by weight or more, and more preferably 30% by weight or more. When the graft ratio of the polymer (E1) is less than 10% by weight, poor appearance and lower impact strength occur.

The intrinsic viscosity (η) of the matrix resin of the polymer (E1) (measured in methyl ethyl ketone at 30 ° C.) is usually 0.1 to 1.3 dl / g, preferably 0.3 to 0.9 dl / g. When the intrinsic viscosity (η) is in the above range, a resin composition of the present invention having particularly excellent impact resistance and moldability (fluidity) can be obtained.

The polymer (E2) is polytetrafluoroethylene having an average particle size of 0.1 to 80 μm, and can be produced by a suspension polymerization method, an emulsion polymerization method, or the like. When the average particle size of the polymer (E2) is less than 0.1 μm, the effect of improving plating adhesion is not sufficient, and when it exceeds 80 μm, poor appearance is liable to occur. The above average particle size is a value of a 50% by weight average particle size determined by a light transmission method.

嵩 The bulk density of the polymer (E2) is usually 0.2 to 0.8 g / ml, preferably 0.3 to 0.7 g / ml. The melting point of the polymer (E2) is usually from 280 to 380 ° C, preferably from 300 to 330 ° C. The specific gravity of the polymer (E2) is usually from 2.0 to 2.4, preferably from 2.1 to 2.3. Specific examples of the polymer (E2) include so-called sliding polytetrafluoroethylene.

The polymer (E3) contains a non-polar α-olefin (co) polymer and a vinyl (co) polymer. The non-polar α-olefin (co) polymer is not particularly restricted but includes, for example, polyethylene, polypropylene, poly (ethylene-propylene) copolymer and the like, and the vinyl (co) polymer is particularly restricted. Although not mentioned, for example, the above-described AS resin described as a typical example of the thermoplastic resin (A), in addition to polystyrene, may be used.

The number-average degree of polymerization of the vinyl (co) polymer is usually in the range of 5 to 10,000, preferably 10 to 5,000. The content of the olefin polymer in the polymer (E3) is usually 5 to 95% by weight, preferably 20 to 90% by weight. The non-polar α-olefin (co) polymer and the vinyl (co) polymer form a graft polymer. Specific examples of such a graft polymer include a polymer obtained by grafting an AS resin to polyethylene and a polypropylene. Examples include a polymer obtained by grafting an AS resin.

The polymer (E3) usually has a multiphase structure in which one (co) polymer is dispersed in the other (co) polymer. As such a polymer having a multiphase structure (E3), a polymer in which a (co) polymer of a different component is dispersed spherically in an olefin polymer or a vinyl-based (co) polymer matrix is exemplified. . The particle diameter of the spherical polymer is usually 0.001 to 10 μm, preferably 0.005 to 7 μm, and more preferably 0.01 to 5 μm. When the particle size is less than 0.001 μm or more than 10 μm, the mechanical strength decreases.

前 記 The polymer (E) in the second invention has an effect of improving plating adhesion even when any kind of inorganic filler is used. It is presumed that the improvement in plating adhesion is attributed to the improvement in chemical resistance due to the polymer (E). That is, appropriate etching is performed in the etching step, and the plating adhesion is improved.

に お い て In the thermoplastic resin composition of the first invention, the mixing ratio of each component is as follows. That is, the thermoplastic resin (A) is 1 to 97% by weight, preferably 10 to 80% by weight, more preferably 15 to 40% by weight, and the polycarbonate (B) is 1 to 97% by weight, preferably 10 to 70% by weight. % By weight, more preferably 20 to 60% by weight, the flame retardant (C) is 1 to 30% by weight, preferably 5 to 20% by weight, more preferably 8 to 15% by weight, and the inorganic filler (D) is It should be 1-30% by weight, preferably 5-20% by weight, more preferably 8-15% by weight. However, (A) + (B) + (C) + (D) = 100% by weight.

成形 When the blending ratio of the thermoplastic resin (A) is less than 1% by weight, the moldability is poor, and when it exceeds 97% by weight, the heat resistance is poor. When the blending ratio of the polycarbonate (B) is less than 1% by weight, heat resistance is poor, and when it exceeds 97% by weight, fluidity and moldability are poor. When the blending ratio of the flame retardant (C) is less than 1% by weight, the flame retardancy is insufficient, and when it exceeds 30% by weight, the mechanical strength is poor. If the amount of the inorganic filler (D) is less than 1% by weight, the rigidity is insufficient, and if it exceeds 30% by weight, the impact resistance and plating adhesion are poor.

In addition, the thermoplastic resin composition of the second invention comprises a preliminary composition comprising a thermoplastic resin (A), a polycarbonate (B), a flame retardant (C), and an inorganic filler (D ') (provided that (A') + (B) + (C) + (D ′) = 100% by weight) and the polymer (E), and the mixing ratio of the preliminary composition and the polymer (E) is as follows. It is. That is, in the preliminary composition, the thermoplastic resin (A) is 1 to 97% by weight, preferably 10 to 80% by weight, more preferably 15 to 40% by weight, and the polycarbonate (B) is 1 to 97% by weight. Preferably 10 to 70% by weight, more preferably 20 to 60% by weight, the flame retardant (C) is 1 to 30% by weight, preferably 5 to 20% by weight, more preferably 8 to 15% by weight, inorganic filler (D ') must be 1 to 30% by weight (preferably 5 to 20% by weight, more preferably 8 to 15% by weight. On the other hand, the polymer (E) is based on 100 parts by weight of the preliminary composition. , 0.5 to 20 parts by weight, preferably 0.7 to 10 parts by weight, more preferably 1 to 8 parts by weight.

The reasons for limiting the respective blending of the thermoplastic resin (A), the polycarbonate (B), the flame retardant (C), and the inorganic filler (D ′) are the same as those described for the thermoplastic resin composition of the first invention. It is. When the amount of the polymer (E) is less than 0.5 part by weight, the effect of improving plating adhesion is not sufficient, and when it exceeds 20 parts by weight, rigidity is poor.

The above-described thermoplastic resin compositions of the present invention (first and second inventions) (hereinafter abbreviated as basic compositions) further include a known polytetrafluoroethylene (PTFE); an inorganic phosphorus compound; Additives such as weathering agents, antioxidants, plasticizers, lubricants, coloring agents, antistatic agents, silicone oils; and other polymers.

配合 By the addition of the above-mentioned known polytetrafluoroethylene (PTFE), dripping (drip of the melt) during combustion can be prevented, and a higher flame retardant level can be achieved. As the PTFE, a dispersion type PTFE dispersed in a solvent such as water can be used.

The molecular weight of the above PTFE is usually 500,000 or more, preferably 1,000,000 or more, and the average particle size is usually 90 to 600 µm, preferably 100 to 500 µm, more preferably 120 to 400 µm, and the specific gravity is usually 1 to 100 µm. 0.5 to 2.5, preferably 2.1 to 2.3, and the bulk density is usually 0.5 to 1.0 g / ml, preferably 0.6 to 0.9 g / ml.

The amount of the PTFE is usually 0.01 to 2.0 parts by weight, preferably 0.1 to 1.0 part by weight, based on 100 parts by weight of the basic composition of the present invention. When the compounding amount of PTFE is less than 0.01 part by weight, the effect of preventing dripping is small, and when it exceeds 2.0 parts by weight, problems such as poor biting in a hopper during pelletization of the composition may occur. Occurs.

無機 The inorganic phosphorus compound can suppress the decomposition reaction of the polycarbonate compounded in the thermoplastic resin composition of the present invention, and can suppress the above-mentioned deterioration in physical properties. That is, since the residual emulsifier, coagulant, etc. in the ABS usually cause a decomposition reaction of the polycarbonate and reduce the molecular weight, a resin polymerized using the emulsion polymerization method as the thermoplastic resin (A) in the present invention is used. In such a case, the physical properties of the alloy material, which is a composition, are reduced. Such a decomposition reaction of polycarbonate remarkably proceeds particularly at a high temperature (such as during molding). In such a case, by incorporating an inorganic phosphorus compound into the basic composition, the decomposition reaction of the polycarbonate can be suppressed even at a high temperature, and a decrease in the physical properties of the composition can be suppressed.

The above inorganic phosphorus compounds include sodium dihydrogen phosphate, disodium monohydrogen phosphate and hydrates thereof. The compounding amount is usually 0.01 to 2 parts by weight, preferably 0.1 to 1 part by weight based on 100 parts by weight of the basic composition.

The above phosphorus compound may be added at the time of melt-kneading the thermoplastic resin composition of the present invention, or the thermoplastic resin (A) or the polycarbonate (B) used in the present invention. May be blended when synthesizing.

In addition, among the above-mentioned known weathering agents, antioxidants, plasticizers, lubricants, coloring agents, antistatic agents, and additives such as silicone oil, as weathering agents, phosphorus-based, sulfur-based organic compounds, hydroxyl groups, Organic compounds containing vinyl groups are preferred. Examples of the antistatic agent include a polyether and a sulfonate having an alkyl group. The preferable amount of these additives is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the basic composition of the present invention. Known antioxidants, plasticizers, lubricants, coloring agents, antistatic agents, silicone oils, and the like can be used.

The other polymer includes a thermoplastic resin and a thermosetting resin, and can be blended according to the characteristics required for the thermoplastic resin composition of the present invention. Examples of the other polymer include polypropylene, polyamide, polyester, polysulfone, polyethersulfone, polyphenylene sulfide, liquid crystal polymer, polyvinylidene fluoride, styrene-vinylidene acetate copolymer, polyamide elastomer, polyamideimide elastomer, polyester elastomer, An ether ester amide, a phenol resin, an epoxy resin, a novolak resin, a resol resin, and the like can be appropriately blended. The compounding amount of these other polymers is usually 1 to 150 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the basic composition.

永久 Permanent antistatic properties can be imparted by blending a polyamide elastomer, polyetheresteramide, or the like among the other polymers described above. The preferred amount is usually 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the basic composition.

The thermoplastic resin composition of the present invention is prepared by using various kneading apparatuses such as a kneading extruder, a Banbury mixer, a kneader, and a roll, with the components constituting the basic composition and additives to be blended as necessary. It can be manufactured by kneading. A particularly preferred production method is a method using a twin-screw kneading extruder. The order of kneading the components is not particularly limited, and all the components may be added at once and kneaded, or the components may be sequentially added and kneaded by a multi-stage addition method.

The thermoplastic resin composition of the present invention produced as described above can be formed into various molded products by a molding method such as injection molding, sheet extrusion, vacuum molding, profile extrusion, or foam molding. Various molded products obtained by the molding method described above utilize their excellent properties to store various trays, especially DVDs, CD-ROMs, CDs, and the like used in OA equipment and home electric appliances, and to store ICs and the like. It can be suitably used as a tray for storing, transporting and assembling various electronic components including semiconductors and liquid crystals. Further, the thermoplastic resin composition of the present invention can be printed and marked by using a laser marking method.

According to the present invention described above, it is possible to provide a thermoplastic resin composition having excellent flame retardancy, rigidity and plating adhesion at the same time, and by using these resin compositions, various trays, particularly, To manufacture trays for storing DVDs, CD-ROMs, CDs, etc. used in OA equipment and home appliances, and for storing, transporting, and assembling various electronic components including semiconductors such as ICs and liquid crystals. Can be done. Therefore, the industrial value of the present invention is great.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention. In addition, various measurement items in the examples were as follows.

(1) Average particle size:
The average particle diameter of the dispersed particles was calculated by integrating the particle diameter of the dispersed particles in the latex before addition 70 times by the cumulant method which is a light scattering method (using "LPA-3100" manufactured by Otsuka Electronics Co., Ltd.). Was measured. The particle diameter in the composition was confirmed by an electron microscope that the particle diameter of the latex added directly showed the particle diameter of the dispersed particles in the resin.

(2) Graft rate:
When the rubber component in 1 g of the thermoplastic resin (A) was Xg and the methyl ethyl ketone insoluble content of the thermoplastic resin (A) was Yg, it was determined by the following formula.

(3) Intrinsic viscosity (η):
The sample was dissolved in methyl ethyl ketone as a solvent, and measured with an Ubbelohde viscometer at a temperature of 30 ° C.

(4) Izod impact strength:
The measurement was performed according to ASTM D256. Measured with notch.

(5) Flowability (melt flow rate):
The measurement was performed according to ASTM D1238. The measurement temperature was 240 ° C. and the load was 10 kg.

(6) Heat deformation temperature:
The measurement was performed according to ASTM D648.

(7) Flexural modulus:
The measurement was performed according to ASTM D790.

(8) Combustion test:
Compliant with UL-94 V test. The thickness was 1.6 mm.

(9) Plating adhesion test:
First, electroless copper plating is performed on the resin surface, and then electroless nickel plating is performed thereon. Then, an adhesive cellophane tape (manufactured by NITTO) is attached to the formed plating layer surface, and then the tape is removed. The adhesion was evaluated according to the following criteria based on the state of peeling of the plating layer at the time of peeling. The etching conditions were variously changed in temperature and time as described in Tables 4 and 6.

調製 Preparation of thermoplastic resin (A):

(A-1): <Preparation of ABS resin>:
In a 7-liter glass flask equipped with a stirrer, 100 parts by weight of ion-exchanged water, 1.5 parts by weight of sodium dodecylbenzenesulfonate, 0.1 part by weight of t-dodecylmercaptan, 40 parts by weight of polybutadiene, 15 parts by weight of styrene And 5 parts by weight of acrylonitrile, and the mixture was heated while stirring.

When the temperature reaches 45 ° C., 0.1 parts by weight of sodium ethylenediaminetetraacetate, 0.003 parts by weight of ferrous sulfate, 0.2 parts by weight of formaldehyde sodium sulfoxylate dihydrate and 15 parts of ion-exchanged water One part by weight of an aqueous solution of an activator and 0.1 part by weight of diisopropylbenzene hydroperoxide were added, and the reaction was continued for 1 hour while stirring.

Thereafter, 50 parts by weight of ion-exchanged water, 1 part by weight of sodium dodecylbenzenesulfonate, 0.1 part by weight of t-dodecylmercaptan, 0.2 parts by weight of diisopropyl hydroperoxide, 30 parts by weight of styrene and 10 parts by weight of acrylonitrile were added for 3 hours. And the polymerization reaction was continued.

After completion of the addition, stirring was further continued for 1 hour, 0.2 parts by weight of 2,2-methylene-bis- (4-ethylene-6-t-butylphenol) was added, and the reaction product was taken out of the flask. After coagulation with 2 parts by weight of calcium chloride, the reaction product was thoroughly washed with water and dried at 75 ° C. for 24 hours to obtain a white powder. The polymerization conversion was 97.2%, the graft ratio was 750%, and the intrinsic viscosity was 0.44 dl / g.

(A-2): <AS resin>:
Composition: styrene / acrylonitrile = 73/27 (wt%), intrinsic viscosity: 0.50 dl / g. Production method: solution polymerization product.

(A-3): <N-phenylmaleimide-containing resin>:
Composition: styrene / N-phenylmaleimide / acrylonitrile = 35/45/20 (% by weight). Production method: Emulsion polymerization product.

Preparation of polycarbonate (B) component:
(B-1): polycarbonate (manufactured by Teijin Chemicals: Panlite L1125, manufactured by the phosgene method)

(B-2): polycarbonate (viscosity average molecular weight: 22000, produced by transesterification method, chlorine content: 300 ppm or less)

Preparation of flame retardant (C) component:
(C-1): An oligomer of tetrabromobisphenol-A.
The end is sealed with tribromophenol. The bromine concentration is 56% by weight. The molecular weight is about 2,000.

(C-2): Antimony trioxide.

(C-3): triphenyl phosphate (TPP).

(C-4): resorcinol bis (dixylenyl pheosphate).

調製 Preparation of inorganic filler (D) component (also applicable to D ′ component):

(D-1): Talc having an average particle size of about 3 μm (manufactured by Fuji Talc: LMR).

(D-2): Fibrous talc (manufactured by Fuji Talc: RF talc).

(D-3): talc having an average particle size of about 2 μm (Nippon Talc: Micro Ace P-3) surface treated with 0.1% by weight of epoxy silane (A-187) manufactured by NUC Silicone.

(D-4): Talc having an average particle size of 0.05 μm.

調製 Preparation of polymer (E) component:

Preparation of the modified polyorganosiloxane (e) used in (E-1):
1.5 parts by weight of p-vinylphenylmethyldimethoxysilane and 98.5 parts by weight of octamethylcyclotetrasiloxane were mixed, and the mixture was placed in 300 parts by weight of distilled water in which 2.0 parts by weight of dodecylbenzenesulfonic acid was dissolved. The mixture was stirred for 3 minutes with a homomixer to be emulsified and dispersed. This mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, heated at 90 ° C. for 6 hours while stirring and mixing, then cooled to 5 ° C. and left for 24 hours to complete the condensation reaction. Was.

縮合 The resulting modified polyorganosiloxane had a condensation rate of 92.8%. This modified polyorganosiloxane latex was neutralized to pH 7 with an aqueous sodium carbonate solution. The average particle size of the resulting modified polyorganosiloxane latex was 2,800 °.

(E-1) Synthesis of silicone rubber-modified resin:
In a 7 L glass flask equipped with a stirrer, 100 parts by weight of ion-exchanged water, 1.5 parts by weight of sodium dodecylbenzenesulfonate, 0.1 part by weight of t-dodecylmercaptan, 40 parts of modified polyorganosiloxane (e) Parts by weight, 15 parts by weight of styrene and 5 parts by weight of acrylonitrile were added, and the temperature was increased with stirring. When the temperature reached 45 ° C., 0.1 parts by weight of sodium ethylenediaminetetraacetate and 0.003 parts by weight of ferrous sulfate were added. , An activator aqueous solution consisting of 0.2 parts by weight of formaldehyde sodium sulfoxylate dihydrate and 15 parts by weight of ion-exchanged water and 0.1 part by weight of diisopropylbenzene hydroperoxide were added, and the reaction was carried out for 1 hour. Continued.

Thereafter, 50 parts by weight of ion-exchanged water, 1 part by weight of sodium dodecylbenzenesulfonate, 0.1 part by weight of t-dodecylmercaptan, 0.2 parts by weight of diisopropyl hydroperoxide, 30 parts by weight of styrene and 10 parts by weight of acrylonitrile were added for 3 hours. And the polymerization reaction was continued. After completion of the addition, stirring was further continued for 1 hour, and then 0.2 parts by weight of 2,2-methylene-bis- (4-ethylene-6-t-butylphenol) was added, and the reaction product was taken out of the flask.

カ ル シ ウ ム 2 parts by weight of calcium chloride was added to the latex as a reaction product to coagulate the latex, and the reaction product was thoroughly washed with water and dried at 75 ° C. for 24 hours to obtain a white powder of a silicone-modified resin. The polymerization conversion of this resin was 97.2%, the graft ratio was 90%, and the intrinsic viscosity was 0.47 dl / g.

(E-2): Asahi Fluoro L series (L150J).
Average particle size 9 μm, bulk density 0.38 g / dl, melting point 325 ° C.

(E-3): Modiper A1400 (LDPE-gr-AS) manufactured by NOF Corporation.

(Inorganic phosphorus compound): Sodium dihydrogen phosphate dihydrate was used.

(Other components: PTFE): TF1620 manufactured by Hoechst.
Average particle size 220 μm, bulk density 0.85 g / dl, specific gravity 2.15.

Preparation of thermoplastic resin composition:
As Test Examples 1 to 7 and Test Examples 8 to 11, thermoplastic resins (A) to polymer (E), other polymers and additives were blended at the ratios shown in Table 3 or Table 5, and 220 to 250 ° C. The mixture was melt-kneaded using an extruder under the following temperature conditions, and injection-molded to obtain a thermoplastic resin composition for evaluation in each test example and comparative example.

(4) The thermoplastic resin composition for evaluation in the above Test Example was measured and evaluated by the above-mentioned measuring methods, and the results are shown in Table 4 or Table 6. According to these results, all of the thermoplastic resin compositions of Test Examples 1 to 7 exhibited excellent rigidity and plating adhesion. In particular, good plating adhesion was obtained regardless of the plating conditions, from low to high temperatures and short to long times.

On the other hand, when inorganic fillers other than the present invention were blended as in Test Examples 8 to 11, the range of conditions under which plating with excellent adhesion was performed was narrow. Further, as shown in Test Example 9, when the compounding amount of the inorganic filler (D) exceeds the range of the present invention, rigidity was obtained, but impact resistance and molding workability were poor. Further, as shown in Test Example 10, when the compounding amount of the inorganic filler (D) was less than the range of the present invention, rigidity was not obtained. Further, as shown in Test Example 11, when the amount of the polymer (E) component exceeded the range of the present invention, good plating adhesion was obtained, but rigidity was poor. Therefore, the thermoplastic resin compositions of Test Examples 8 to 11 were unsuitable for tray use.

After drying the thermoplastic resin composition pellets prepared in Test Example 3 at 80 ° C. for 3 hours, the injection molding machine having a mold clamping force of 350 tons is used. A tray-shaped molded product for transporting box-shaped electronic device parts was injection molded. The molding was performed under the conditions of a cylinder setting temperature of 250 ° C. and a mold setting temperature of 50 ° C.

(4) A part of the obtained tray-shaped molded product was used as a cut-out test piece, and the test piece was measured and evaluated by the above-described measuring method. The results are shown in Table 7. According to these results, the tray-shaped molded product obtained in the example exhibited excellent rigidity and plating adhesion. In particular, good plating adhesion was obtained regardless of the processing temperature of the etching solution in the pre-plating process from a low temperature to a high temperature, and a short processing time to a long processing time.

Claims (5)

It contains 1 to 97% by weight of a thermoplastic resin (A), 1 to 97% by weight of a polycarbonate (B), 1 to 30% by weight of a flame retardant (C) and 1 to 30% by weight of an inorganic filler (D) (however, (A) + (B) + (C) + (D) = 100% by weight), and the thermoplastic resin (A) is an aromatic vinyl resin in the presence of 0 to 90% by weight of a rubbery polymer (a). , Vinyl cyanide, (meth) acrylic acid ester, acid anhydride and maleimide at least one kind of monomer (b) 100 to 10% by weight (provided that (a) + (b) = 100 % By weight), and the inorganic filler (D) is at least one selected from the following inorganic fillers (D1) to (D3). Thermoplastic resin composition.
(D1): inorganic filler having an average particle size of 0.5 to 20 μm (D2): fibrous inorganic filler (D3): inorganic filler surface-treated with a silane coupling agent Resin composition comprising 1 to 97% by weight of thermoplastic resin (A), 1 to 97% by weight of polycarbonate (B), 1 to 30% by weight of flame retardant (C), 1 to 30% by weight of inorganic filler (D ') 100 parts by weight (provided that (A) + (B) + (C) + (D ′) = 100% by weight) contains 0.5 to 20 parts by weight of the polymer (E), and the thermoplastic resin (A) is at least one selected from the group consisting of aromatic vinyl, vinyl cyanide, (meth) acrylate, acid anhydride and maleimide in the presence of 0 to 90% by weight of the rubbery polymer (a). The polymer (E) is obtained by polymerizing 100 to 10% by weight of a kind monomer (b) (provided that (a) + (b) = 100% by weight). A thermoplastic resin for a tray, which is at least one selected from (E1) to a polymer (E3). Fat composition.
(E1): at least one monomer (b) selected from the group consisting of aromatic vinyl, vinyl cyanide, (meth) acrylate, acid anhydride and maleimide in the presence of the modified polyorganosiloxane (e) (E2): Polytetrafluoroethylene (E3) having an average particle diameter of 0.1 to 80 μm: Nonpolar α-olefin (co) polymer and vinyl (co) polymer And a polymer containing The thermoplastic resin composition for a tray according to claim 1, wherein the inorganic filler (D1) and / or (D2) is talc. The thermoplastic resin composition for a tray according to any one of claims 1 to 3, wherein the polycarbonate (B) is obtained by a transesterification reaction between dihydroxyaryl and diphenyl carbonate. The thermoplastic resin composition for a tray according to any one of claims 1 to 4, wherein the flame retardant (C) is an organic phosphorus compound.