JPS6151052A - Electrically conductive thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent moldability, mehanical strength and resistance to impact and heat and causes little formation of warpage and sink marks, consisting of a thermoplastic polyester, an arom. polycarbonate, a thermoplastic non-rigid resin and a metal-coated particulate phenolic resin. CONSTITUTION:5-94pts.wt. thermoplastic polyester (A) obtd. by condensing an arom. dicarboxylic acid (ester forming derivative) with a 2-6C aliph. glycol (ester forming derivative), 5-94pts.wt. arom. polycarbonate (B) [e.g. poly-2,2-bis (4-hydroxyphenyl)propanecarbonate], 1-40pts.wt. thermoplastic non-rigid resin (C) having a glass transition temp. of 0 deg.C or below (e.g. polyurethane), and 5- 800pts.wt. metal-coated particulate phenolic resin (D) having an apparent specific gravity of 1.5-3.0 and electrical resistance of 1,000OMEGA or below (e.g. nickel-coated particulate phenolic resin) are blended in such a proportion that A+B+C=100 and D/40<=C<=D/40+80.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to conductive thermoplastic resin compositions. The conductive thermoplastic resin composition obtained by the present invention can be used for surface heating elements or static electricity removal applications such as IC packaging magazines and photosensitive film packaging, but it can also be used for various electromagnetic shielding applications. Used for electronic device housings, power cables, and shielded wires.

PRIOR ART A number of compositions of molding materials for plastic housings for Ta magnetic wave shields are already known, in which conductive fillers such as metal fibers are blended with thermoplastic resins. However, at present, little progress has been made in the practical application of these compositions.

One of the major reasons for this is that these conductive filler formulations are mostly made of ABS resin, polypropylene,
Housing resins such as polyphenyl ether and polycarbonate are used as matrix polymers, but combinations of these matrix polymers and various conductive fillers such as metal powder, metal flakes, and metal fibers each have the following disadvantages. There is. In the case of metal powder, it is necessary to add a large amount to obtain sufficient conductivity, which leads to poor moldability.

Physical properties decrease significantly and specific gravity increases. In the case of metal flakes, in addition to deteriorating moldability and physical properties, uniform dispersion is extremely difficult, resulting in poor surface smoothness of molded products. In the case of metal fibers, excellent conductivity can be obtained with a relatively small amount of mixing, but the mixing process is complicated, impact strength and weld line strength are reduced, and the surface smoothness of the molded product is deteriorated.

These drawbacks are fatal because the plastic housing, which is an alternative to metal, is characterized by its ability to be integrally molded into complex shapes, which is difficult to do with metal.

In addition, polyester resins such as polybutylene terephthalate have low hygroscopicity and excellent dimensional stability, so they are used for machine parts, etc., but they tend to warp and have poor Wt impact resistance, so they are used for housings. is restricted to. Furthermore, nylon resin has the disadvantage of being highly hygroscopic and lacking in dimensional stability.

Problems to be Solved by the Invention The present invention provides a conductive composite resin for magnetic wave shielding, which has excellent moldability such as Mf and mobility, and is suitable for surface characteristics oozing.

Means for Solving the Problems The present invention provides impact resistance when a metal-coated granular phenolic resin is blended into a matrix polymer of a specific composition, which includes a sweetfish polyester, an aromatic polycarbonate, and a thermoplastic soft resin as essential components.

There is no or little deterioration in various physical properties such as fluidity, moldability,
This is based on the discovery that a polymerization resin with excellent conductivity and electromagnetic shielding properties can be obtained.

That is, the present invention comprises 5 to 94 parts by weight of thermoplastic polyester (A), 5 to 94 parts by weight of aromatic polycarbonate (B),
(A), CB), (C) and (DJ The respective formulations ff1 (duty No. 1 parts) are as follows:

A + B + C = 100...
[I] D/40 S C≦D/40 + 30
... [II] The present invention will be explained in detail below.

The thermoplastic polyester used in the present invention is a linear polymer having ester bonds in its molecular chain, and is usually obtained by a condensation reaction between a dicarboxylic acid component and a diol component.

Examples of dicarboxylic acid components include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-
Aromatic dicarboxylic acids such as dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid,
Succinic acid, Chellaic acid.

adipic acid, sebacin r1fi aliphatic dicarboxylic acid,
and ester-forming derivatives thereof.

In addition, examples of diol components include ethylene glycol,
1,4-butadiol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol tyrene glycol, triethylene glycol, 1.

1-Cyclohexane dimetatool, 1.4-cyclohexane dimetatool, xylylene collection call.

2,2-bis-(4-hydroxyphenyl)propane,
Bis-(4-hydroxyphenyl)-sulfone, bis-
(Hydroxyethoxy)-benzene.

Examples include ethylene oxide adducts of 2,2-bis-(4-hydroxyphenyl)-furopane, propylene oxide adducts of 2,2-bis-(4-hydroxyphenyl)-propane, and ester-forming derivatives thereof.

Furthermore, polycaprolactone, polypivalolactone, polyβ
-Lactone polyesters such as propiolactone are also mentioned in the series of vapor-plastic polyesters (4) used in the present invention. Particularly preferred thermoplastic polyesters include polyethylene terephthalate and polybutylene terephthalate.

The aromatic polycarbonate (B) used in the present invention is a homo- or copolycarbonate or a mixture thereof, and is a combination of known bisphenols and phosgene or carbonic diester. Obtained by i24 reaction.

Examples of bisphenols include the following compounds. Hydroquinone, resorcinol.

Dihydroxydiphenyl, bis-(hydroxyphenyl)-alkane, bis-(hydroxyphenyl)-cycloalkane, bis-(hydroxyphenyl)-sulfide, bis-(hydroxyphenyl)-ether, bis-(
hydroxyphenyl)-ketone, bis-(hydroxyphenyl)-sulfoxide, bis-(hydroxyphenyl)-sulfone, and α-. l-bis-(hydroxyphenyl)-diisopropylbenzene. Particularly preferred aromatic polycarbonates are poly-2,2-bis-(4-hydroxyphenyl)-propane-carbonate, poly-
2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane-carbonate is mentioned.

Furthermore, bis-(hydroxyphenyl)-alkane-based polycarbonate (ester-carbonate) can be used as the aromatic poly-carbonate, which can be added to the above-mentioned bis-(hydroxyphenyl)-alkane-based poly-carbonate,
It is a copolymer of aromatic dicarboxylic acids such as terephthal a and isophthalic acid.

The thermoplastic soft FIJ resin (C) used in the present invention may be any thermoplastic resin that exhibits rubber elasticity at elevated temperatures, and preferably has a glass transition temperature of 0°C or lower, more preferably -20°C or lower. be. The soft εd fat (C) is, for example, a homopolymer of vinyl monomers or random.

J3 from B5 consisting of a block, graft copolymer, or polyurethane, polyester elastomer, or polyamide elastomer.

The vinyl monomers used in the present invention are olefin monomers, such as ethylene, propylene, 1- and 2-butene, imbutylene, 1- and 2-pentene.

l- and 2-hexene etc. Vinyl halide monomers, such as vinyl fluoride, vinyl fluoride, chlorotrifluoroethylene, tetrachloroethylene, vinyl chloride, vinylidene chloride, and vinyl bromide.

Vinylidene bromide, vinyl iodide, etc. Diene monomers, such as butadiene, isoprene, piperylene.

Chlorprene, 1,5-hexadiene, norbornadiene, ethylidene norbornene, etc. aromatic vinyl sm body,
For example, styrene, α-methylstyrene.

α-Chlorstyrene, P-chlorostyrene, 2,4-dichlorostyrene, P-methylstyrene, 3,4-dimethylstyrene, 0 and P-divinylbenzene, 1)-methyl-α-methylstyrene, P-chlor -α-methylstyrene, etc. Acrylic acid or methacrylic acid derivatives, such as acrylic acid, methacrylic acid, acrylonitrile, methacriconitrile. Methyl acrylate, ethyl acrylate, n- and fso-propyl acrylate, n- and is acrylate.

Butyl, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n- and 1so-propyl methacrylate, n- and 1so-butyl methacrylate, cyclohexyl methacrylate.

Acrylic I! 1! Allyl, allyl methacrylate, sodium, calcium acrylic acid or methacrylate.

Zinc, magnesium gold@salt, etc. Vinyl ester monomers, such as vinyl acetate, vinyl propionate.

Vinyl laurate, vinyl laurate, vinyl laurate, etc. Vinyl ether monomers, such as methyl vinyl ether, ethyl vinyl ether, etc. Unsaturated dibasic w derivatives, such as maleic acid, maleic anhydride, methyl maleate, etc. are mentioned,
Homopolymers, random, block, and graft copolymers of vinyl monomers can be obtained by known radical polymerization or ionic polymerization. ! Examples include ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer,
propylene copolymer, ethylene-propylene-butadiene copolymer, ethylene ethyl acrylate copolymer, styrene-butadiene block copolymer, selectively hydrogenated styrene-butadiene block copolymer, ethylene-propylene-styrene grant copolymer, enalene-propylene-styrene -acrylonitrile graft copolymer, ethylene-propylene-butadiene,
Styrene craft copolymer, ethylene-propylene-butadiene-styrene-acrylonitrile graft copolymer, acrylonitrile-butanene-styrene graft copolymer, butadiene-styrene-methyl meccrylate graft copolymer.

Butadiene-acryloni!・Licopolymer, butadiene-styrene-acrylonitrile-methyl methacrylate graft copolymer, butadiene, acrylonitrile-
Methacrylic wire copolymer, styrene-maleic anhydride skeleton copolymer, ethylene-malein 6°i graft copolymer, styrene-ethyl acrylate-acrylic fA n-
There are butyl-methacrylic atomized allyl branched allyl graft copolymers, zinc salts of ethylene-methacrylic copolymers, and magnesium salts of ethylene-methacrylic type copolymers. - The polyurethane used in the invention is at least one
A polyester containing two or more active hydrogen atoms in its molecule.

71 of polyadenobe or low molecular weight polyols with one or two F, X or more! It is a thermoplastic polyurethane that can be browned by reacting a polyfunctional incyanate with a polyfunctional incyanate.

Possible polyesters include 4'Yxa such as phthalic acid, adipine, and maleic acid, and glycols such as ethylene glycol, propylene glycol, butylene glycol, or if necessary, small amounts of trimethylolpropane and glycerin. or lactone polyesters such as polycaprolactone, polypivalolactone, and polyβ-propiolactone.

Suitable polyethers are, for example, polyoxyethylene glycol, polyoxypropylene glycol, poly(oxypropylene), poly(oxyethylene) glycol,
It is polyoxytetramethylene glycol.

Low molecular weight polyol is ethylene glycol.

Refers to glycols such as propylene glycol and butylene glycol, and triols such as trimethylolpropane and glycerin.

Suitable examples of polyfunctional incyanates include tolylene diisocyanate, tolylene diisocyanate dimer, diphenylmethane-4,4'-diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, and the like. .

The polyester elastomer used in the present invention is a copolymer consisting of an aromatic polyester block and a polyether block or an aromatic polyester block and an aliphatic polyester block. Examples of the dicarboxylic acid forming the aromatic polyester block include terephthalic acid, inphthalic acid, naphthalene dicarboxylic acid, adipine h, and sebacic acid, with terephthalic acid and isophthalic acid being particularly preferred. Examples of the diol include tetramethylene glycol, ethylene glycol, propylene glycol, hexamethylene glycol, and cyclohexane glycol, with tetramethylene glycol being particularly preferred. Examples of polyether include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, etc., with polyoxytetramethylene glycol being particularly preferred.6 Aliphatic polyesters include, for example, polyadipate, polysebacate, polyoxytetramethylene glycol, etc. Examples include caprolactone, and polycaprolactone is particularly preferred.

The polyamide elastomer used in the present invention is a copolymer consisting of a polyamide plotter such as polycaprolactam or polylaurolactam, and a polyester block or a polyether block such as polyoxyethylene, polyoxypropylene, or polyoxytetramethylene.

The blending amounts of the thermoplastic 5J F14 polyester, aromatic polyester (BJ, and thermoplastic resin (C) of the present invention are 5 to 94 jrfa parts, preferably tL).
, <C 15 to 80 parts by weight, (B) 5 to 94 parts by weight, preferably 15 to 80 parts by weight, (C) 1 to 40 parts by weight, preferably 5 to 30 parts by weight, (5), ( Is),
The total amount of (C) is 100 parts by weight. A more preferable range is (A) 20 to 70 parts by weight;
(B) 20 to 70 parts by weight; (C) 10 to 25 parts by weight.

If (4) is less than 5-fold J bar part or (B) is more than 94-fold part, moldability such as fluidity and solvent crack resistance will deteriorate, and mechanical properties such as impact resistance will deteriorate. descend. or(
a) exceeds 94 parts by weight or (B) exceeds 5 parts by weight
In the case of l'd, the moldability is also poor, warpage is likely to occur, and the impact resistance and weld line strength are insufficient. If (C) exceeds 40 parts by weight or D/40+30, x: deformation temperature, tensile strength 2 bending strength.

Bending: 1 sex ratio etc. decreases and (C) is less than 1 weight 1 part or D
If it is less than /40, the surface smoothness of the molded product, military resistance, and weld line strength are insufficient.

Metal-coated granular phenolic tree IJFi used in the present invention
(D) is a granulated phenol resin containing a reactive methylol group, which is manufactured by crushing and granulating a cured resol resin, and a granular phenol resin containing a reactive methylol group, which is sold under the trade name Bell Pearl. , nickel, iii, aluminum by known plating methods and thermal bonding methods.

Examples include those coated with gold, such as iron and alloys of iron and the like. Particularly preferably, IQ
This is a nickel-coated granular phenol made by nickel-plating Lupal. In normal cases, the thickness of the nickel coat is 0.01 to 30 It, and the diameter of the nickel is 0.
Use one with a diameter of 1 to 150μ. In addition, when a granular phenolic resin containing a reactive methylol group is coated with a metal or/and a granular phenolic resin containing a reactive methylol group is blended as an inorganic filler, the molded product is heated to By heat-treating at a temperature in the range of 100 to 250°C for 3 minutes or more, the heat deformation temperature of the molded product can be further improved.

The metal-coated positional phenolic resin commercially used in the present invention includes: (5) containing Fl-like carbon particles with a particle size of 0.1 to 150μ or a secondary coagulation product thereof; and (B) at least 50% by weight of the total (C) Granular or powdered phenol aldehyde resin or granular or powdered phenol aldehyde resin having a size that allows it to pass through a sieve of 100% Tyler Messier and (C) free phenol content of 50 ppm or less as measured by liquid chromatography. The surface of nitrogen-containing phenol/aldehyde resin (hereinafter abbreviated as granular phenol resin) is coated with metal and has an apparent specific gravity of 1.5 to 3.
．． 0 electrical resistance of 10,000 or less is suitable.

The preferred granular phenol 4ii1 fat used for gold-coating in the present invention is infusible, insoluble, and has excellent heat resistance;
Specific gravity is 1.2-1. :), most of them are (A) distributed between 0.1 and 150μ in particle size, and (D) at least 50% of the total particle size is 100 Tyler Messier's mouth; b
(C) As measured by liquid chromatography, the free phenol-containing group (50
It is less than pp+n.

Therefore, the top office lady! M-shaped rough phenol resin The conductive granular phenol ε・→ fat used in the present invention, which has been subjected to chemical plating or vacuum plating, has excellent heat resistance and has a specific gravity of 1°5 to 3.
．． Since it is as small as 0, it has good uniform dispersibility in plastics and rubbers, and can also reduce the weight of the target material.

Further, since the conductive particulate phenol resin used in the present invention has a shape appropriately distributed within the particle size range of 0.1 to 150 μm, it is optimal for uses such as electromagnetic shielding. In this case, it is flexible for use after pulverizing or classifying if necessary.

Furthermore, the isoelectric granular phenolic resin used in the present invention has a low specific gravity and exhibits excellent conductivity even when the proportion of metal plated is small, making it extremely economical.

The 5i, :I;' (phenolase, 1 fat) used in the present invention can be prepared by known methods, for example, in JP-A-57-1770.
The one manufactured by No. 1, q'& No. 17114/1986 can be used, and its synchronization is shown below.

At room temperature, 15 to 22 times i=! Mixed water consisting of t% hydrochloric acid and 7-15% formaldehyde? ;;G F&
Phenol or phenol and urine Li, while stirring
A mixture consisting of melamine and a W"A'i compound of anilink 5 was added to the mixed aqueous solution at a ratio of 1/15 or less □゛, and white δ was produced in the reaction system. ] Stop stirring and let the mixture stand still.While the reaction system is left standing, pink granular phenol resin is generated and precipitated in the reaction system.

Next, the entire reaction system was heated and raised to a temperature of 60 to 70°C while stirring again to complete the reaction, and then washed with water.
Subsequently, the product is neutralized with a 0.1 to 1% ammonia aqueous solution, followed by washing with water, dehydration, and drying.

Most of the granular phenolic resins have a particle size of 0.1 to 15
It consists of 0μ primary particles or their secondary 118 particles, and at least 50% by weight, preferably 90% by weight of the gold body is 10
The size is large enough to pass through 6b of the 0 tiler mesh, but it is distributed so as to have a peak between 1 and 50μ. In the present invention, resin 1jd with a particle size of less than 0.1 resin is difficult to handle, has no advantage in the purpose or application of the present invention, and
If it exceeds 0μ, it tends to settle when used in adhesives or paints, and has problems with dispersibility or conductivity.

It is important that the amount of the metal-coated granular phenolic resin Q)) is 5 to 800 parts by weight, preferably 10 to 600 parts by weight, based on 100 parts by weight of the thermoplastic follicle mixture. If the amount of (D) is less than 5 parts by weight, the effect of imparting conductivity will be insufficient, and if it exceeds 800 parts by weight, fluidity will decrease, making blending, kneading, and molding extremely difficult. .

In addition, it is preferable to surface-treat the metal-coated granular phenolic resin (DJ) with a known silane-based or titanate-based coupling agent. Coupling treatment increases adhesion with the resin and improves heat distortion temperature and tensile strength. etc. will be further improved, and further changes in 21iJ conductivity will occur due to changes in the environment.

The conductive thermoplastic resin composition of the present invention may include, if necessary,
For example, aluminum fiber, yellow fiber, stainless steel fiber,
Fibrous conductive fillers such as aluminum coated glass fibers and nickel coated carbon fibers, fibrous reinforcing agents such as glass fibers and carbon fibers, inorganic fillers, antioxidants, heat resistance, r@type agents, and lubricants. , ring branching crosslinking agent (epoxy resin,
polyfunctional compounds such as triaryl compounds), and red phosphorus.

Adding @flame agents such as phosphorus compounds and halogen compounds, ya combustion aids such as antimony oxide, zinc 0ide, and porium @zinc, and crystallization promoters such as keraphite, talc, yoki acid, and metal salts. I can do it.

The thermoplastic polyester material of the present invention, aromatic polycarbonate H3), thermoplastic soft resin (C), and metal-coated granular phenolic resin (DJ's blending methods include melt-kneading and pelletizing all at once, or all A blending method during molding in which the resin is blended and molded at the same time, or a metal-coated granular phenolic resin (DJ is pre-contained or (B) or (C)
), any known method can be used, such as a method in which Fg is melt-kneaded with one or more types of Fg, leaving behind a master pellet, and mixed with the remaining resin during molding.

Example The present invention will be explained in more detail below using Examples.

Examples 1 to 11 and Comparative Examples 1 to 7 As the thermoplastic polyester, polyethylene terephthalate (Kanebo % 14 EFG-6), as the aromatic polycarbonate, poly(bisphenol A carbonate) (Kijin Kasei Panlite ni-1300) thermoplastic As soft resins, ethylene-vinyl acetate copolymer (Mitsui Polychemical Evaflex-150), styrene-
Butadiene block copolymer (Denka S)
TR160'-propylene copolymer (Japan Synthetic Rubber EPOIPX), acrylic rubber-acrylonitrile-styrene copolymer (Hitachi Chemical Pitax V)
6101AP), metal coated granular phenol fi'JI
Ilf? nickel-coated Bell Pearl (Kanebo test product), yellow aim fiber (fiber diameter 30 μm) for conductivity.
, 1.5 fibers (Kobe Foundry Co., Ltd. KC Metal Fiber 2600) were blended into the compositions shown in Table 1.
Furthermore, antioxidant (Ciba Geigy Irganox 101
0) Add 1 part of 0.1 weight ff, diameter 25 fi single screw extruder (screw rotation speed 10 Orpm, discharge ff 1ll') 0 to 12 (1 weight, cylinder temperature 25
0 to 265° C.) and extruded into strands, and pellets were produced using a pelletizer. The pellets were then injection molded under commonly used molding conditions for reinforced polyethylene terephthalate resin, and their physical properties were measured. The results are shown in Table-2.

Table 1 Note) Unit 2g unit 1゛ Polyethylene terephthalate 2) Poly(bisphenol-carbonate) 3) Two-handed resin-vinegar iυ vinyl co-M combination 4) Styrene-butadiene block copolymer 5) Ethylene-propylene copolymer Coalescence 6) Acrylic rubber-acrylonitrile-styrene copolymer 1) ASTR4D638 2) Tensile strength ratio with/without weld line 3) ASTM
D256 (with notch 1/4) 4) A S
TM D 64 B (18,6 Qi E) 5) AS
TM D257 6) ◎: Very smooth O: Smooth ×: Rough 7) Spiral flow test (cross section 6IIllI x 3 mist).

Injection pressure 660/9/d, cylinder temperature 265°C.

Mold temperature: 110°C) 8) 3 cods
) 35 parts by weight, polyester elastomer (Toyobo Co., Ltd.)
Belprene P-150M) 15x, g: parts, nickel-coated Belpearl 100i parts, and Irganox 0.
13t (fi part was blended, 25 diameter single screw extruder (screw rotation speed 100 rpm, discharge! 10
The pellets were 'kW' using 5F/min, cylinder temperature 260°C. Next, to 150 parts of this pellet, 30 parts of poly(bisphenol A carbonate) (Kijin Kasei Panrai l-ni-1100) 30 weight τi8:S,
and 0 fully aromatic polyester (Unitika U Polymer U-
100) 20 heavy bearing parts are blended during molding and injection molded (
The cylinder temperature was 290°C and the mold temperature was 110°C), and the physical properties were measured. The results are shown in 4-3.

Example 13 Copolyethylene terephthalate (Kanebo Gosei IFG-
8) (50 parts, copolyester carbonate 2ov<qG, produced by interfacial condensation of a blend of bisphenol A, phosgene, and terephthaloyl chloride, inphthal chloride, ionomer (Nii Polychemical Co., Ltd.)
Hymiran 1554) 2 ogfi part, 1 part of nickel footbell pearl 100 nails ff, and Irganox (11-layer Ea part) were blended during molding, and injection molded (cylinder temperature 265°C, mold temperature 80°C) to determine the physical properties. Measurements were taken.

The results are shown in Table-3.

Examples 14-16 Polybutylene terephthalate (Polyplastics Duranex 2o11) 5 (1: fi part, poly(bisphenol A carbonate) (Kijin Kasei Panlite -1
:'100) 3OfflJR Department, Styrene-Butadiene Brothol Copolymer (Denka Kagaku Kogyo Denka S TR160
2) 20 parts and Irganox 0.1πr:
For m 1a≦, Example 13 uses 100 weight ff 1 part of nickel-coated Bell Pearl, and Example 15 uses coupling-treated nickel-coated Bell Pearl (Nippon Unicar A18).
7 Surface treatment was carried out so that γ-glycidioxypropyltrimethoxysilane was contained in an amount of 0.51 parts % based on the nickel-coated Bell Pearl. ) to 100. s heavy fi”;
Each part was blended and pelletized in the same manner as in Examples 1 to 11, then injection molded under the usual molding conditions for reinforced polybutylene terephthalate, and the physical properties were measured. The results are shown in Table 4. Example row 16 shows 200 pdf of the pellets produced in Example 14 (with respect to tV), a bisphenol A-based epoxy resin (manufactured by polymerization of bisphenol A diglycidyl ether and bisphenol A).
0.53 portions of was added before forming a, injection molding was carried out under the same conditions as in Example 14.15, and the physical properties were measured. The results are shown in Table 4.

Example 17 Polybutylene terephthalate (Polyplastics Geranex 2011) 50 heavy bearing parts, poly(bisphenol A carbonate) (Kijin Kasei Panlite -130
0) 30 heavy claw part, styrene-butadiene block copolymer (Denka Kagaku Kogyo Denka 5rR16o2) zo heavy melon part,
and Irganox 0.1? ! ! For part f1, nickel coated Bell Pearl xnr)! rtM part, and 2 parts of reactive methylol foundation 1fG-based phenolic resin (FFL Bose Bell Pearl S-930) 50[,in],
The pellets were made into pellets in the same manner as in Examples 14 to 16, and then injection molded and the physical properties were measured. The results are shown in Table-5.

Example 18 - The test piece injection molded in Example 17 was heat treated at 150°C for 3 days, and its physical properties were measured. As a result, the conductive thermoplastic resin composition claimed in the claims of the present invention has excellent 7C decomposition properties, good moldability,
It has smooth molding surface, high cup impact strength, heat deformation temperature, welt strength, etc.

Kanebo Gosen Co., Ltd. Procedural Amendment Date November 1981 1, Description of the case 1982 Patent Application No. 171095 2, Name of the invention Conductive n-plastic resin composition 8, Person making the amendment Relationship to the case Patent Applicant Address: 5-17-4 Guta, Ta-ku, Tokyo Contact Address: 1-5-90, Tomobuchi-cho, Bejima-ku, Osaka 584 Details of the "Claims" and "Details of the Invention" Explanation 6, Contents of amendment (1) The statement in the claims section of the specification is amended as shown in the attached sheet.

(2) The description in the description shall be amended as shown in the table below.

Patented closed cage (1) Thermoplastic polyester (A15-94 heavy foot part, aromatic polycarbonate (Bl 5-94 ffl E<
part, thermoplastic soft resin (C) 1 to 40 heavy claw part and goldstone coated granular phenolic resin (D) 5 to 800fflffi
(A), (B), (C)
and (DJ's respective combination nails (8 parts heavy) are as follows (I),
[Conductive thermoplastic resin composition satisfying n1 formula.

A+B-1-C=100...[I]D/40≦
C≦D/40 + 80 ... 1111 (2
) (A) 15 to 80 parts by weight, (B) 15 to 80 parts by weight.

The composition according to claim 1, containing 5 to 80 parts by weight of (C).

(3) Claim 1, wherein the thermoplastic polyester is a polymer obtained by a synthesis reaction of an aromatic dicarboxylic acid or an ester-forming derivative thereof, an aliphatic glycol having 2 to 6 carbon atoms, or an ester-forming derivative thereof. Compositions as described.

(4) A polymer in which the thermoplastic polyester is obtained by a condensation reaction of a thermoplastic wholly aromatic polyester alone or an aromatic dicarboxylic acid or an ester-forming derivative thereof, and an aliphatic glycol having 2 to 6 carbon atoms or an ester-forming derivative thereof. The composition according to claim 1, which is a mixture with.

(5) the aromatic dicarboxylic acid or its ester-forming derivative is terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, or an ester-forming derivative thereof;
b) is ethylene glycol.

The composition according to claim 8 or 4, which is tetramethylene glycol, hexamethylene glycol, or an ester-forming 8-conductor thereof.

(6) A patent claim in which the wholly aromatic polyester contains terephthalic acid and isophthalic acid as dicarboxylic acid components and bis-(hydroxyphenyl)-alkane and/or bis-(hydroxyphenyl)-sulfone as the diol component. A composition according to scope item 4.

(7) The composition according to claim 1, wherein the aromatic polycarbonate is a bis-(hydroxyphenyl)-alkane polycarbonate.

(8) The aromatic polycarbonate is bis-(hydroxyphenyl)-alkane-based copoly(ester-carbonate) alone or bis-(hydroxyphenyl)-7゛alkane-based polycarbonate and bis-(hydroxyphenyl)
1211. The composition of claim 1, which is a mixture with -alkane-based copoly(ester-carbonate).

(9) The composition according to claim 1, wherein the thermoplastic soft resin is a thermoplastic soft fat having a glass transition temperature of 0° C. or lower and exhibiting rubber elasticity at room temperature.

α0 Thermoplastic soft fat is a polymer made of one or more vinyl monomers, polyurethane, polyester elastomer, polyamide elastomer Claim 1
Compositions as described in Section.

αη Vinyl spinning wheel m body is olefin body, ha C1/7”
vinyl monocrylate, diene monomer, aromatic vinyl monomer, acrylic acid or methacrylic acid derivative.

Claim 10, which is a vinyl Nisder monomer, a vinyl ether 1Jiffi form, and an unsaturated dibasic acid derivative.
Compositions as described in Section.

11. The composition according to claim 10, wherein the polyester elastomer comprises a polyethylene terephthalate block or a polybutylene terephthalate block and a polyether block or an aliphatic polyester block.

The composition according to claim 1, wherein the α1 metal-coated granular phenolic resin is a nickel-coated granular phenolic resin.

6. The composition according to claim 1, wherein the metal-coated granular phenolic resin is surface-treated with a silane-based or titanate-based coupling agent.

a9 The blending amount of metal coated granular phenolic resin is 10
600 parts by weight of the composition of claim 1.

QO: The composition according to the scope of Patent W+1, item 1, further containing one or more fibrous conductive fillers.

Claims (16)

[Claims] (1) 5 to 94 parts by weight of thermoplastic polyester (A), 5 to 94 parts by weight of aromatic polycarbonate (B), 1 to 40 parts by weight of soft thermoplastic resin (C), and 5 to 40 parts by weight of metal coated granular phenolic resin (D) 800 parts by weight is blended (
A conductive thermoplastic resin composition in which the blending amounts (parts by weight) of A), (B), (C), and (D) satisfy the following formulas [I] and [II]. A+B+C=100...[I] D/40≦C≦D/40+30...[II] (2) The composition according to claim 1, which contains (A) 15 to 80 parts by weight, (B) 15 to 80 parts by weight, and (C) 5 to 30 parts by weight. (3) Claim 1, wherein the thermoplastic polyester is a polymer obtained by a condensation reaction of an aromatic dicarboxylic acid or its ester-forming derivative, an aliphatic glycol having 2 to 6 carbon atoms, or its ester-forming derivative. Compositions as described. (4) A polymer in which the thermoplastic polyester is obtained by a condensation reaction of a thermoplastic wholly aromatic polyester alone or with an aromatic dicarboxylic acid or an ester-forming derivative thereof and an aliphatic glycol having 2 to 6 carbon atoms or an ester-forming derivative thereof. The composition according to claim 1, which is a mixture with. (5) the aromatic dicarboxylic acid or its ester-forming derivative is terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, or an ester-forming derivative thereof;
5. The composition according to claim 3 or 4, wherein b) is ethylene glycol, tetramethylene glycol, hexamethylene glycol or an ester-forming derivative thereof. (6) Claims in which the wholly aromatic polyester contains terephthalic acid and isophthalic acid as the dicarboxylic acid component and bis-(hydroxyphenyl)-alkane and/or bis-(hydroxyphenyl)-sulfone as the diol component. The composition according to item 4. (7) The composition according to claim 1, wherein the aromatic polycarbonate is a bis-(hydroxyphenyl)-alkane polycarbonate. (8) The aromatic polycarbonate is bis-(hydroxyphenyl)-alkane copoly(ester-carbonate) alone or bis-(hydroxyphenyl)-alkane polycarbonate and bis-(hydroxyphenyl)-
The composition according to claim 1, which is a mixture with an alkane-based copoly(ester-carbonate). (9) The composition according to claim 1, wherein the thermoplastic soft resin is a thermoplastic soft resin having a glass transition temperature of 0° C. or lower and exhibiting rubber elasticity at room temperature. (10) Claim 1 in which the thermoplastic soft fat is a polymer consisting of one or more vinyl monomers, polyurethane, polyester elastomer, or polyamide elastomer.
Compositions as described in Section. (11) The vinyl monomer is an olefin, a halogenated vinyl monomer, a diene monomer, an aromatic vinyl monomer, an acrylic acid or methacrylic acid derivative, a vinyl ester monomer, a vinyl ether monomer, and The composition according to claim 10, which is an unsaturated dibasic acid derivative. (12) The composition according to claim 10, wherein the polyester elastomer comprises a polyethylene terephthalate block or a polybutylene terephthalate block and a polyether block or an aliphatic polyester block. (13) The composition according to claim 1, wherein the metal-coated granular phenolic resin is a nickel-coated granular phenolic resin. (14) The composition according to claim 1, wherein the metal-coated granular phenolic resin is surface-treated with a silane-based or titanate-based coupling agent. (15) The amount of metal coated granular phenolic resin is 10
600 parts by weight of the composition of claim 1. (16) The composition according to claim 1, further comprising one or more fibrous conductive fillers.