JPH115219A - Method of molding resin molded article and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin molded article and a heat resistant tray for IC, which is excellent in the balance among electrical conductivity, heat resistance and heat aging characteristics and, at the same time, excellent in shape stability at elevated temperature. SOLUTION: A resin composition, which includes 1-50 pts.wt. of electrical conductive carbon to 100 pts.wt. of a mixture consisting of 1-99 wt.% of a styrene-based polymer having a syndiotactic stereoregularity and 99-1 wt.% of one or more different polymer except the polymer just mentioned above, is melted at 27-370 deg.C and molded with a mold having a molding cavity, the wall temperature of which covered with an insulating material having a heat conductivity at 20 deg.C of 0.01 ca/cm.sec. deg.C or less is set to be 20-150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a conductive material, heat-resistant material,
The present invention relates to a resin molded article having an excellent balance of heat aging resistance and excellent shape stability even in a process under a high temperature, and a method of molding a heat resistant tray for IC.

[0002]

2. Description of the Related Art When an IC component absorbs moisture, when it is heated to 100.degree.
During heating, steam is generated inside, causing blisters or cracks and causing breakage. Therefore, baking is performed at a temperature of 100 ° C. or more. At this time, an IC tray made of a conductive material having a resistance of 108Ω or less is used to protect the IC.

Conventionally, this tray has been made of a polypropylene resin, an atactic three-dimensional polystyrene resin, or the like. Due to the problem, reuse from the conventional disposable is being promoted, and a higher temperature type is required. As a molding material for IC members, Japanese Patent Application Laid-Open No. 2-175754 discloses that a heat deformation temperature is 130 ° C.
As described above, the melt flow index was 3 g / 10 min (JI
S-K7210 compliant, 300 ° C, 10kg load) or more,
A molding material having a molded article having a surface resistance of 107Ω or less and containing at least 50% by weight of a polyphenylene ether resin has been proposed. Specifically, as means for satisfying these physical properties, two methods have been proposed in which an acid imide compound is added to a polyphenylene ether resin / conductive carbon system or a polyphenylene ether resin having a low intrinsic viscosity is used.

Japanese Patent Application Laid-Open No. 2-180958 discloses an IC for an IC molded from a resin composition obtained by adding an ABA ′ type hydrogenated block copolymer elastomer to a polyphenylene ether resin / conductive carbon system. Heat resistant trays have been proposed. However, these materials
The surface of heat aging at high temperature required for high temperature type 1C tray, peeling of molded products, etc. has not been sufficiently solved,
Also, the improvement of the fluidity is insufficient.

[0005] Japanese Patent Application Laid-Open No. 2-285302 has a similar proposal. On the other hand, JP-A-63-15262
No. 8 discloses a polyphenylene ether resin containing carbon-
In the presence of a compound having a carbon double bond, a method for producing a polyphenylene ether resin having an excellent color tone has been proposed by melt-kneading the glass transition temperature of the polyphenylene ether resin or higher in the absence of a radical generator. .

Further, Japanese Patent Publication No. 57-56941 discloses that the impact resistance can be improved by adding a hydrogenated styrene-butadiene-styrene block copolymer to a polyphenylene ether resin. However, the composition shown in this article has problems such as insufficient compatibility, a problem of peeling, and a decrease in fluidity.

Japanese Patent Application Laid-Open No. 2-276823 discloses a polyphenylene ether resin having a cyclized terminal group.
Further, a resin composition comprising this resin and a polystyrene resin has been proposed. Further, JP-A-4-288363
In JP-A-2003-189, conductive carbon was added to a composition comprising a polyphenylene ether resin having a cyclized terminal group, and a block copolymer consisting of two different types of vinyl aromatic compound polymer blocks and olefin compound polymer blocks. A heat-resistant tray material for IC and a heat-resistant tray for IC have been proposed.

However, even in these proposals,
The balance of conductivity, heat resistance, and heat aging, which are the characteristics required for heat-resistant trays for ICs, cannot be sufficiently satisfied, or even if they can be satisfied, the shape stability in high-temperature processes must be satisfied. Is not done.

[0009]

DISCLOSURE OF THE INVENTION The present invention relates to a method for forming a resin molded article and a heat resistant tray for ICs, which have an excellent balance between conductivity, heat resistance and heat aging resistance and have excellent shape stability even in a process under a high temperature. The purpose is to provide.

[0010]

SUMMARY OF THE INVENTION In view of the above-mentioned situation, the present inventors have found that the balance of conductivity, heat resistance, and heat aging resistance is excellent, and that the shape stability is improved even in a process performed at a high temperature. As a result of intensive studies to obtain an excellent resin molded product and a heat resistant tray for IC, the present invention has been achieved.

That is, the present invention relates to (A) a styrenic polymer having a syndiotactic stereoregularity of 1 to 9;
9% by weight and 100 parts by weight of a mixture of 99% to 1% by weight of one or more polymers other than the component (B) (A), and 1 to 50 parts by weight of the conductive carbon (C) The resulting resin composition is heated and melted in the range of 270 to 370 ° C, and has a thermal conductivity of 0.01 cal / cm · at 20 ° C.
A resin molded product and a heat-resistant tray for ICs, wherein a mold cavity coated with a heat insulating material having a temperature of not more than sec · ° C. is heated to a temperature of 20 to 150 ° C. and molded using a mold having the mold cavity. It relates to a molding method.

Hereinafter, the present invention will be described in detail. The (A) styrenic polymer having syndiotactic stereoregularity (hereinafter also referred to as syndiotactic polystyrene) used in the present invention has a phenyl group or a substituent on a main chain formed from carbon-carbon bonds. A phenyl group having a three-dimensional structure alternately located in the opposite direction,
The tacticity is quantified by nuclear magnetic resonance (13C-NMR) using isotope carbon. 13C-NM
Tacticity measured by the R method can be represented by the existence ratio of a plurality of continuous structural units, for example, a dyad for two, a triad for three, and a pentad for five.

The syndiotactic polystyrene referred to in the present invention is generally a racemic pentad having a syndiotacticity of 50% or more, preferably 80% or more, more preferably 90% or more of the following general formula (I):

[0014]

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(In the formula, R represents a hydrogen atom, a halogen atom or a substituent containing at least one of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom. , M represents an integer of 1 to 3. However, when m is plural, each R may be the same or different.) Or a polymer comprising an aromatic vinyl compound represented by It is a combined hydrogenated polymer.

Preferred aromatic vinyl compounds used herein include styrene, α-methylstyrene, methylstyrene, ethylstyrene, isopropylstyrene, tertiary butylstyrene, phenylstyrene, vinylstyrene, chlorostyrene, bromostyrene, and fluorostyrene. Styrene, chloromethylstyrene, methoxystyrene,
There are ethoxystyrene and the like, which are used alone or in combination of two or more. Among these, more preferred aromatic vinyl compounds include styrene, p-methylstyrene,
m-methylstyrene, p-tert-butylstyrene, p-chlorostyrene, m-chlorostyrene and p-fluorostyrene.

This syndiotactic polystyrene is not particularly limited in its molecular weight.
The weight average molecular weight is 10,000 or more, preferably 50,
000 or more. Here, the weight average molecular weight is 10,000.
If it is less than 00, the thermal properties and mechanical properties of the obtained molded article tend to decrease. Furthermore, there is no restriction on the molecular weight distribution, and various types can be applied.

Such syndiotactic polystyrene can be produced, for example, by referring to the technique disclosed in Japanese Patent Application Laid-Open No. 63-268709.
That is, it can be produced by polymerizing a styrenic monomer in an inert hydrocarbon solvent or in the absence of a solvent, using alumoxane which is a condensation compound of a titanium compound and water with a trialkylaluminum as a catalyst. .

The syndiotactic polystyrene may be modified with a polar group-containing modifying agent. The modifier having a polar group is not particularly limited, and the polar group is not particularly limited. As the polar group, for example, acid hydride, carbonyl group,
Acid anhydrides, acid amides, carboxylic esters, acid azides,
Examples include a sulfone group, a nitrile group, a cyano group, an isocyanate ester, an amino group, a hydroxyl group, an imide group, a thiol group, an oxazoline group, and an epoxy group. Particularly preferred polar groups are an acid anhydride and an epoxy group, and the acid anhydride is particularly preferably a maleic anhydride group.

As the one or more kinds of polymers other than the components (B) and (A) used in the present invention, one or more kinds can be selected from all kinds of thermoplastic resins and elastomers as long as the object of the present invention is not impaired. There is no particular limitation on the thermoplastic resin. Styrene polymers such as styrene polymers having an atactic three-dimensional structure, styrene polymers having an isotactic three-dimensional structure, acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin) Copolymers, polyphenylene ether, polycarbonate, polysulfone, polyether polymers such as polyethersulfone, polyethylene terephthalate, polyester polymers such as polybutylene terephthalate, polyamide, polyphenylene sulfide, condensation polymers such as polyoxymethylene, Acrylic polymers such as polyacrylic acid, polyacrylate and polymethyl methacrylate, polyethylene, polypropylene, polybutene, poly-4-methylpentene-1, ethylene-propylene Polyolefin polymers such as polymers, or polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, and the like halogen-containing vinyl compounds such as polyvinylidene fluoride.

Further, these thermoplastic resins may be modified by a modifier having a polar group. The modifier having a polar group is not particularly limited, and the polar group is not particularly limited. As a polar group,
For example, acid hydride, carbonyl group, acid anhydride, acid amide, carboxylic acid ester, acid azide, sulfone group, nitrile group, cyano group, isocyanate ester, amino group, hydroxyl group, imide group, thiol group, oxazoline group, epoxy And the like. Particularly preferred polar groups are an acid anhydride and an epoxy group, and the acid anhydride is particularly preferably a maleic anhydride group.

The elastomer is not particularly limited.
Styrene butadiene copolymer elastomer (SBR),
Styrene-butadiene-styrene copolymer elastomer (SBS), styrene-butadiene-styrene block copolymer elastomer (SEBS) partially or entirely hydrogenated in butadiene portion, styrene-isoprene block copolymer elastomer (SIR) , Styrene-isoprene-styrene block copolymer elastomer (S
IS), styrene-isoprene-styrene block copolymer elastomer (SEPS) partially or entirely hydrogenated with butadiene portion, acrylonitrile-butadiene-styrene copolymer elastomer (ABS rubber), acrylonitrile-alkyl acrylate-butadiene-
Styrene-based elastomers such as styrene copolymer elastomer (ABS rubber), methyl methacrylate-alkyl acrylate-styrene copolymer elastomer (MAS rubber), methyl methacrylate-alkyl acrylate-butadiene-styrene copolymer elastomer (MABS rubber) , Ethylene, propylene, 1-butene, olefin elastomers composed of mutual copolymers of α-olefins such as 1-hexene, natural rubber, polyamide elastomer, polybutadiene, polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, silicone rubber, Examples include epichlorohydrin rubber, polyether / ester rubber, polyester / ester rubber, and the like.

Further, these elastomers may be modified by a modifier having a polar group. The modifier having a polar group is not particularly limited, and the polar group is not particularly limited. As a polar group,
For example, acid hydride, carbonyl group, acid anhydride, acid amide, carboxylic acid ester, acid azide, sulfone group, nitrile group, cyano group, isocyanate ester, amino group, hydroxyl group, imide group, thiol group, oxazoline group, epoxy And the like. Particularly preferred polar groups are an acid anhydride and an epoxy group, and the acid anhydride is particularly preferably a maleic anhydride group.

The component (B) is selected from one or more of these thermoplastic resins and elastomers, and is selected from at least one or more of styrene-based polymers, polyether-based polymers, and styrene-based elastomers. Preferably. Among the styrene-based polymers, a styrene-based polymer having an atactic three-dimensional structure (hereinafter, referred to as atactic polystyrene) is preferable. This atactic polystyrene, in the presence or absence of a rubbery polymer, solution polymerization, bulk polymerization, suspension polymerization,
The following general formula (II) obtained by a polymerization method such as bulk-suspension polymerization

[0025]

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(Wherein, R represents a hydrogen atom, a halogen atom or a substituent containing at least one of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom) , M represents an integer of 1 to 3. However, when m is plural, each R may be the same or different.) A polymer comprising one or more aromatic vinyl compounds Or copolymers with one or more other vinyl monomers copolymerizable with one or more aromatic vinyl compounds, hydrogenated polymers of these polymers, and mixtures thereof.

Preferred aromatic vinyl compounds used herein include styrene, α-methylstyrene, methylstyrene, ethylstyrene, isopropylstyrene, tertiary butylstyrene, phenylstyrene, vinylstyrene, chlorostyrene, bromostyrene and fluorostyrene. Styrene, chloromethylstyrene, methoxystyrene,
There are ethoxystyrene and the like, which are used alone or in combination of two or more. Among these, more preferred aromatic vinyl compounds include styrene, p-methylstyrene,
m-methylstyrene, p-tert-butylstyrene, p-chlorostyrene, m-chlorostyrene and p-fluorostyrene.

Other copolymerizable vinyl monomers include:
Acrylonitrile, vinylcyan compounds such as methacrylonitrile, methyl acrylate, ethyl acrylate,
Propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, alkyl acrylates such as benzyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, Amyl methacrylate, hexyl methacrylate,
Octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, alkyl methacrylates such as benzyl methacrylate, maleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N
Maleimide compounds such as -laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and N- (p-bromophenyl) maleimide;

Examples of the rubbery polymer include polybutadienes, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, diene rubbers such as polyisoprene, ethylene-α-olefin copolymers, ethylene-
α-olefin-polyene copolymer, non-diene rubber such as polyacrylate, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, ethylene-propylene elastomer, styrene-grafted ethylene-propylene elastomer, Examples include an ethylene-based ionomer resin and a hydrogenated styrene-isoprene block copolymer.

The molecular weight of the atactic polystyrene is not particularly limited, but generally has a weight average molecular weight of 10,000 or more, preferably 50,000 or more. Here, when the weight average molecular weight is less than 10,000, the thermal properties and mechanical properties of the obtained molded article tend to decrease. Furthermore, there is no restriction on the molecular weight distribution, and various types can be applied.

Preferred among the polyether-based polymers are polyphenylene ether-based polymers. As the polyphenylene ether polymer, the following general formula (III-a) or (III-b):

[0032]

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[0033]

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(Wherein R1, R2, R3, R4, R5
R6 is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, hydrogen and the like, and R5 and R6 are not simultaneously hydrogen. ) Is a repeating unit, and a homopolymer or a copolymer having a structural unit represented by the general formula (III-a) or (III-b) can be used. Representative examples of the homopolymer of the polyphenylene ether-based polymer include poly (2,6-dimethyl-1,4-phenylene) ether,
Poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-)
1,4-phenylene) ether, poly (2,6-di-n)
-Propyl-1,4-phenylene) ether, poly (2
-Methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-)
Phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl) -1, 4
And homopolymers such as (phenylene) ether.

Examples of the polyphenylene ether copolymer include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of o-cresol, and a copolymer of 2,3,6-trimethyl A polyphenylene ether copolymer mainly composed of a polyphenylene ether structure, such as a copolymer with phenol and o-cresol, is included.

In the polyphenylene ether-based polymer, various other phenylene ether units which have been proposed to be allowed to exist in the polyphenylene ether-based polymer without departing from the gist of the present invention are used. It may be included as a partial structure. Japanese Patent Application Laid-Open (JP-A) No. 63-3012 discloses an example in which coexistence in a small amount is proposed.
No. 22, a 2- (dialkylaminomethyl) -6-methylphenylene ether unit;
2- (N-alkyl-N-phenylaminomethyl) -6
-Methylphenylene ether unit and the like.
Also included are polyphenylene ether-based polymers having a small amount of diphenoquinone or the like bonded in the main chain.

Further, for example, JP-A-2-276823, JP-A-63-108059,
Also included are polyphenylene ethers modified with compounds having a carbon-carbon double bond described in, for example, JP-A-59724. The molecular weight of the polyphenylene ether polymer is 1,000 to 100,000 in terms of number average molecular weight.
A range of 0 is preferred, and a more preferred range is 6,000.
~ 60,000.

As the styrene-based elastomer, a block copolymer of a styrene-based compound and a conjugated diene is preferred. The general formula of these block copolymers is (A
-B) _{n + 1} , or A- (BA) _n , or B- (A
-B) The _one represented by _{n + 1} is most preferable (where A is a polymer block composed of a styrene compound, B is a conjugated diene polymer block, n is an integer of 1 to 20, The ratio of the A block to the whole molecule is 1 to 50% by weight.) The average molecular weight of these copolymers is 1
0.00-1,000,000, preferably 30,0
00 to 500,000. Specific examples of these styrene-based elastomers, styrene-butadiene random copolymer, styrene-isoprene random copolymer,
Styrene-butadiene-styrene triblock copolymer, styrene-isoprene-styrene triblock copolymer, styrene-isoprene radial block copolymer terminated with polystyrene block, styrene-butadiene multi-block copolymer, styrene-isoprene multi-block Examples include styrene-conjugated diene block copolymers such as block copolymers, and products obtained by hydrogenating them.

The conductive carbon (C) used in the present invention comprises:
It is used for the purpose of dispersing in the composition to impart conductivity and greatly reducing the surface resistance of the resin molded article, and acetylene black, furnace black and the like can be used. Specific examples of furnace black include Ketjen Black EC and EC600JD (manufactured by Akzo),
Asahi HS-500 (made by Asahi Carbon Co., Ltd.), Palkan XC72
(Manufactured by CABOT).

The resin composition used in the present invention (A)
The blending amount of the components (B) and (C) depends on the heat resistance I obtained.
In consideration of the conductivity, heat resistance, heat aging resistance, and shape stability at high temperatures of the C tray, the following relationship must be satisfied. The amount of the component (A) is 99 to 1% by weight, preferably 90 to 10% by weight, and more preferably 8 to 8% by weight in the mixture of the components (A) and (B).
0 to 20% by weight. When the amount is more than 99% by weight or less than 1% by weight, the balance of various properties required for an IC tray is inferior.

The amount of the component (B) is from 1 to 99% by weight, preferably from 10 to 90% by weight, and more preferably from 2 to 99% by weight in the mixture of the components (A) and (B).
0 to 80% by weight. When the amount is less than 1% by weight or more than 99% by weight, the balance of various properties required for an IC tray is inferior. (C) The amount of the component is
1 to 100 parts by weight of the total of components (A) and (B)
５０50 parts by weight, preferably 3-40 parts by weight, more preferably 5-30 parts by weight. Less than 1 part by weight (C)
There is no effect of blending the components, and if it exceeds 50 parts by weight, there is no effect corresponding to the blending amount, but rather the moldability of the obtained composition is impaired.

The resin composition used in the present invention comprises (A)
It can be obtained by blending the component (B) with a polymer of the component or a mixture of the components (A) and (C) and melt-kneading the mixture. For the melt kneading, a known melt kneading apparatus such as a single screw extruder and a twin screw extruder can be used, but a vented twin screw extruder is preferable. The melt-kneading temperature when each component is melt-kneaded is usually set in the range of 270 to 370 ° C, preferably in the range of 280 to 330 ° C. If the melt-kneading temperature is lower than 270 ° C., the raw materials will be insufficiently melted, so that a uniform composition may not be obtained.
If the melt-kneading temperature is higher than 370 ° C., decomposition of the raw material tends to occur.

The resin composition used in the present invention includes:
When melt-kneading the components (A), (B) and (C), other components such as an inorganic filler, a pigment, a dye, a heat stabilizer, an antioxidant, a weathering agent, and the like, as long as the physical properties are not impaired.
Nucleating agents, lubricants, antistatic agents, thermoplastic resins, elastomers, flame retardants, flame retardant auxiliaries and the like can be added. The other thermoplastic resin is not particularly limited. Styrene polymers such as styrene polymers having an atactic three-dimensional structure, styrene polymers having an isotactic three-dimensional structure, acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin) Copolymers, polyphenylene ether, polycarbonate, polysulfone, polyether polymers such as polyethersulfone, polyethylene terephthalate, polyester polymers such as polybutylene terephthalate,
Condensation polymers such as polyamide, polyphenylene sulfide and polyoxymethylene, acrylic polymers such as polyacrylic acid, polyacrylate and polymethyl methacrylate, polyethylene, polypropylene, polybutene, poly 4-methylpentene-1, ethylene- Examples thereof include polyolefin-based polymers such as propylene copolymers, and halogen-containing vinyl compounds such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, and polyvinylidene fluoride.

Further, these thermoplastic resins may be modified by a modifier having a polar group. The modifier having a polar group is not particularly limited, and the polar group is not particularly limited. As a polar group,
For example, acid hydride, carbonyl group, acid anhydride, acid amide, carboxylic acid ester, acid azide, sulfone group, nitrile group, cyano group, isocyanate ester, amino group, hydroxyl group, imide group, thiol group, oxazoline group, epoxy And the like. Particularly preferred polar groups are an acid anhydride and an epoxy group, and the acid anhydride is particularly preferably a maleic anhydride group.

The other elastomer is not particularly limited. Styrene butadiene copolymer elastomer (SB
R), styrene-butadiene-styrene copolymer elastomer (SBS), styrene-butadiene-styrene block copolymer elastomer (SEBS) partially or wholly hydrogenated with butadiene, and styrene-isoprene block copolymer elastomer (SIR), styrene-isoprene-styrene block copolymer elastomer (SIS), styrene-isoprene-styrene block copolymer elastomer partially or wholly hydrogenated (SEPS), acrylonitrile-butadiene-styrene copolymer Polymer elastomer (ABS rubber), acrylonitrile-alkyl acrylate-butadiene-styrene copolymer elastomer (ABS rubber), methyl methacrylate-alkyl acrylate-styrene copolymer elastomer (MAS rubber), styrene-based elastomers such as methyl methacrylate-alkyl acrylate-butadiene-styrene copolymer elastomer (MABS rubber) and α-olefins such as ethylene, propylene, 1-butene and 1-hexene. Olefinic elastomers, natural rubbers, polyamide elastomers, polybutadienes, polysulfide rubbers, thiochol rubbers, acrylic rubbers, urethane rubbers, silicone rubbers, epichlorohydrin rubbers, polyether ester rubbers, polyester ester rubbers, etc., which are formed by coalescence.

These elastomers may be modified with a modifier having a polar group. The modifier having a polar group is not particularly limited, and the polar group is not particularly limited. Examples of the polar group include acid hydride, carbonyl group, acid anhydride, acid amide, carboxylic acid ester, acid azide, sulfone group, nitrile group, cyano group, isocyanate ester, amino group, hydroxyl group, imide group, and thiol group. Oxazoline group, epoxy group and the like. Particularly preferred polar groups are an acid anhydride and an epoxy group, and the acid anhydride is particularly preferably a maleic anhydride group.

Various flame retardants are used, and there is no particular limitation. However, considering the kneading and molding temperatures, it is important that the process has excellent heat resistance, and an organic halogen-based flame retardant is particularly preferred. Examples of the halogen-based flame retardant include brominated polystyrene such as halogenated epoxy compound, pentabromobenzyl acrylate, halogenated amide compound, poly (dibromophenylene oxide), polytribromostyrene and polydibromostyrene, tetrabromobisphenol A, Tetrabromophthalic anhydride, hexabromobenzene, tribromophenyl allyl ether, pentabromotoluene, pentabromophenol, tribromophenyl-2,3-dibromo-propyl ether, tris (2,3-dibromopropyl) phosphate, tris (2 -Chloro-3-bromopropyl)
Phosphate, octabromodiphenyl ether, decabromodiphenyl ether, octabromobiphenyl,
Pentachloropentacyclodecane, hexabromocyclododecane, hexachlorobenzene, pentachlorotoluene, hexabromobiphenyl, decabromobiphenyl,
Tetrabromobutane, decabromodiphenyl ether,
Hexabromodiphenyl ether, ethylene-bis-
(Tetrabromophthalimide), tetrachlorobisphenol A, tetrabromobisphenol A, oligomers of tetrachlorobisphenol A or tetrabromobisphenol A, halogenated polycarbonate oligomers such as brominated polycarbonate oligomers, polychlorostyrene, bis (tribromophenoxy) ethane And the like.

Among these, brominated polystyrene and poly (dibromophenylene oxide) are particularly preferable. Brominated polystyrene may be polydibromostyrene, polytribromostyrene, or a copolymer thereof. The brominated polystyrene may be produced by brominating polystyrene or may be obtained by polymerizing brominated styrene. The bromine content of these flame retardants is preferably at least 50%.

When a flame retardant is blended, it is preferable to blend a flame retardant auxiliary. Here, there are various flame retardant assistants, and there is no particular limitation. For example, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, metal antimony, antimony trichloride, antimony pentachloride , Antimony trisulfide, antimony pentasulfide and the like. In addition to these, zinc borate, barium metaborate, zirconium oxide, and the like can be given. Among these, antimony trioxide is particularly preferred.

The inorganic filler is not particularly limited, and may be any of fibrous, granular, and powdery materials. Examples of the fibrous filler include, for example, glass fiber, carbon fiber, whisker, and the like, and the shape is a cloth shape, a mat shape,
There are a bundle cut shape, a short fiber, a filament shape, a whisker, and the like. In the case of a bundle cut shape, the length is 0.05 to 50.
mm and a fiber diameter of 5 to 20 μm are preferred.

On the other hand, as the granular or powdery filler, for example, talc, graphite, titanium dioxide, silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, calcium oxysulfate, oxide Examples include tin, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flake, and glass beads.

Among these fillers, glass fillers, such as glass powder, glass flake, glass beads, glass filament, glass fiber, glass lobing, and glass mat, are particularly preferable. Further, as the above-mentioned filler, those subjected to a surface treatment with a coupling agent are preferable. The coupling agent used for the surface treatment is used to improve the adhesiveness between the filler and the resin, and is a so-called silane-based coupling agent, a titanium-based coupling agent, or any of conventionally known coupling agents. Any one can be selected and used. Among them, γ-aminopropyltrimethoxysilane, N-β- (aminomethyl) -γ-aminopropyltrimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, β- (3,
Preferred are aminosilanes such as 4-epoxycyclohexyl) ethyltrimethoxysilane, epoxysilane, and isopropyltri (N-amidoethyl, aminoethyl) titanate. The above-mentioned inorganic filler may be used alone or in combination of two or more.

The resin molded product obtained by the molding method of the present invention is prepared by heating and melting the above-mentioned composition in the range of 270 to 370 ° C., preferably in the range of 280 to 330 ° C.
At a mold temperature of 0 ° C., preferably 30 to 145 ° C., more preferably 40 to 140 ° C., the thermal conductivity at 20 ° C. on the wall of the mold forming the mold cavity is 0.01 cal / c.
It can be obtained by molding using a mold coated with a heat insulating material having a temperature of m · sec · ° C. or less.

If the heat melting temperature is lower than 270 ° C., the composition is insufficiently melted, so that a molded article having uniform physical properties cannot be obtained. When the heat melting temperature is higher than 370 ° C,
It is not preferable because the decomposition of the composition occurs. If the mold temperature exceeds 150 ° C., the crystallization of syndiotactic polystyrene can proceed sufficiently, but the cooling time must be long or the releasability of the molded product will be poor. If the mold temperature is below 20 ° C., the syndiotactic polystyrene can no longer be crystallized.

The molding method may be appropriately selected according to the molded product to be molded. Various molding methods such as a thermoforming method employed in the conventional molding of atactic polystyrene, and specific molding methods may be used. Injection molding, blow molding, press molding, extrusion molding, vacuum molding, injection molding, casting molding, etc. may be used, but among them, injection molding, blow molding, and press molding are particularly preferable.

The thermal conductivity of the heat insulating material used in the present invention must be 0.01 cal / cm · sec · ° C. or less, preferably 0.005 cal / cm · sec · ° C. or less. Thermal conductivity is 0.01 cal / cm · sec
If the temperature is higher than ° C., the mold temperature must be 150 ° C. or higher in order to sufficiently promote the crystallization of syndiotactic polystyrene, so that the molding cycle becomes longer and the releasability of the molded product deteriorates. However, suitable materials for the heat insulating material used in the present invention include resins and ceramics. In particular, the resin has a thermal conductivity of 0.002c.
Al / cm · sec · ° C. or less is preferable because the heat insulating effect is large. Further, among resins, polyimide is particularly preferable in terms of thermal conductivity and durability. Since the thermal conductivity of ceramic is slightly higher than that of resin, the coating layer must be somewhat thicker in order to exhibit the same heat insulating effect as resin.

Further, in addition to the above requirements, the heat insulating material for coating the mold according to the present invention is excellent in heat resistance, resistant to heat and cold cycles, excellent in wear resistance, and capable of covering the mold body. It is desirable that properties such as good performance, good adhesion to the mold body, and surface polishing be provided. Regarding the coating thickness of the heat insulating material, it is preferable that the heat insulating material is substantially in the outermost layer of the mold and is a thin layer since the increase in cooling time can be suppressed. The preferable thickness of the heat insulating material to be able to sufficiently promote crystallization and not to impair the molding efficiency varies depending on the molding conditions such as the thermal conductivity of the heat insulating material used, the melting temperature during molding, and the mold temperature. Therefore, it is better to determine them in consideration of these conditions and the molding cycle.

The use of polyimide as a heat insulating material is particularly advantageous when coating the surface of a mold having a complicated shape used in injection molding, blow molding and the like. The heat insulating material used in the present invention is preferably firmly adhered to the mold surface so as to withstand repeated molding many times,
For this purpose, it is desirable to coat the mold surface with a highly durable film that adheres sufficiently to the mold. In order to coat the complex mold surface with polyimide and firmly adhere, polyamic acid, a precursor of polyimide, is dissolved in a solvent such as N-methylpyrrolidone and applied to the mold surface, and then heated to form the polyimide. It can be carried out preferably by a method of forming. Since the polymer of the polyimide precursor is a polar group such as a carboxyl group, it has good adhesion to the mold, and a polyimide thin layer adhered to the mold surface can be obtained by reacting and forming polyimide on the mold surface.

In the step of supplying the heat-plasticized resin or resin composition into a mold and cooling it under pressure to obtain a molded body, the temperature of the mold surface reaches 100 ° C. for each molding. The difference heating and cooling are repeated. Generally, since the thermal expansion coefficient of the heat insulating material is significantly different from that of the metal, severe stress occurs at the interface between the metal and the heat insulating material. As a heat insulating material capable of withstanding this stress for tens of thousands of times, it is required that both the breaking strength and the breaking elongation are large and the adhesion to metal is large. Polyimide meets these requirements and is convenient. Among them, a tough linear high molecular weight polyimide containing no substance that inhibits adhesion to a metal such as fluorine is most preferable.

In order to obtain heat resistance, the glass transition temperature (Tg) of the polyimide used is preferably higher. Although the Tg of the linear polyimide varies depending on the constituent components,
g is preferably 200 ° C. or higher, more preferably 230 ° C. or higher, and most preferably 270 ° C. or higher. The smaller the thermal conductivity of the polyimide is, the more preferable it is. However, those having a thermal conductivity of 0.002 cal / cm · sec · ° C. or less can be particularly preferably used.

The thickness of the polyimide layer is 0.01 to 2 mm
Moderately selected in the range. If the thickness is less than 0.01 mm, the mold temperature must be increased to obtain a molded product with sufficiently advanced crystallization, and the molding efficiency is reduced. Conversely, when the mold temperature is lowered, the molding efficiency increases, but a molded product with sufficiently advanced crystallization cannot be obtained. If it exceeds 2 mm, the cooling effect is reduced and the molding efficiency is reduced. Further, the preferable thickness of the polyimide layer differs depending on the molding technique. When the molding technique is injection molding, the thickness is preferably from 0.01 to 0.5 mm, more preferably from 0.03 to 0.2 mm. When the molding technique is blow molding or press molding, a thickness of 0.1 to 1 mm is preferable. In addition,
The “thickness of the polyimide” mentioned here means the maximum thickness when the layer thickness is not uniform.

Further, the strength and elongation of the straight-chain high molecular weight polyimide used in the present invention are preferably high, and particularly, high elongation at break is advantageous for the cold-heat resistance cycle. Is at least 10%, preferably at least 20%. ASTM D6 for elongation at break
38. As a preferred example of the high molecular weight polyimide that can be used in the present invention, Kapton (trademark, Toray Industries, Inc.)
Tg = 428 ° C), Novax (trademark, manufactured by Mitsubishi Chemical Corporation, Tg = 399 ° C), Iupirex R (trademark, manufactured by Ube Industries, Ltd., Tg = 303 ° C), Iupirex S (trademark, Ube Industries) (Tg = 359 ° C)
LarcTPI (trademark, manufactured by Mitsui Toatsu Chemicals, Inc., Tg =
256 ° C.).

[0063]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described more specifically below with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist thereof.
The following molds were used in Examples and Comparative Examples of the present invention. Die I: Made of steel (S55C), 100mm × 10
The surface of a mold having a square cavity of 0 mm and a flat cavity having a thickness of 2 mm was subjected to mirror-like hard chrome plating to a thickness of 0.02 mm by electrolysis to obtain a mold I for injection molding.

Mold II: The surface of mold I was sufficiently degreased, and a linear polyimide precursor, polyimide varnish “Trenice # 3000” (trade name, manufactured by Toray Industries, Inc., Tg = 3 after curing)
00 ° C, thermal conductivity 0.0005 cal / cm · sec ·
° C, elongation at break of 60%)
Heat and cure in the order of 290 ° C. This coating and heat curing are repeated three times to form a polyimide layer. Next, a diamond paste was applied to the buff and polished with an electric grinder to form a mirror-like linear polyimide coating layer having a thickness of 0.05 mm to obtain an injection mold II.

Various physical properties used in Examples and Comparative Examples of the present invention were measured based on the following test methods. (1) Heat resistance A test piece was cut into a size of 5 mm × 5 mm × 2 mm, and the softening temperature was measured in accordance with JIS K7196.

(2) Conductivity The surface resistivity was measured according to ASTM D-257. (3) Thermal aging property After aging for 1 week in a hot air oven at 150 ° C,
A tensile test was performed to determine a tensile strength retention before and after aging.

(4) Shape stability at high temperature Twenty IC-molded 300 mm × 135 mm IC trays were stacked, quickly placed in a 130 ° C. hot air oven, taken out of the oven after 10 minutes, and cooled at room temperature for 3 hours.
After leaving for 0 minute and cooling, the gap amount between the trays was measured. The components (A), (B) and (C) used in the examples of the present invention were as follows.

(A) Syndiotactic polystyrene 1,2,4-trichlorobenzene as a solvent at 130 ° C.
The weight average molecular weight measured by gel permeation chromatography was 310,000, and the weight average molecular weight /
The number average molecular weight is 2.6, and the syndiotacticity in racemic pentad by 13C-NMR analysis is 97%.
Is syndiotactic polystyrene.

(B) Polymer other than the component (A) B-1: Weight average molecular weight measured by gel permeation chromatography at 40 ° C. using chloroform as a solvent at 270,000, weight average molecular weight / number average molecular weight Is atactic polystyrene which is polymerized by thermal polymerization, wherein is 2.2. B-2: Polycarbonate (trademark: Panlite L-12)
25, Teijin Chemicals Ltd.) B-3: Polyethylene terephthalate (trademark: Pyropet RY533, manufactured by Toyobo Co., Ltd.) B-4: Nylon 66 (trademark: 2015B, manufactured by Ube Industries, Ltd.) B-5 : 2,6 in the presence of dibutylamine according to the method described in U.S. Patent 4,788,277.
-Xylene is oxidatively coupled and polymerized, η (sp
/C)=0.42 poly (2,6-dimethyl-1,1)
4-phenylene) ether.

B-6: Maleic anhydride-modified polyphenylene ether obtained by modifying the polyether of A-5 with maleic anhydride. B-7: Styrene-hydrogenated butadiene block copolymer elastomer (trade name: TUFTEC H1272, manufactured by Asahi Kasei Kogyo Co., Ltd.) B-8: Maleic anhydride-modified styrene-hydrogenated butadiene block copolymer elastomer (trade name: TUFTEC
(M1913, manufactured by Asahi Kasei Kogyo Co., Ltd.) (C) Conductive carbon Ketjen Black EC600JD (Conducted carbon, manufactured by Akzo)

[0071]

Example 1 Components (A), (B) and (C) were dry-blended and adjusted in predetermined amounts shown in Table 1. this,
Co-rotating twin screw extruder with vent (40 mm inner diameter, L /
D = 46), and melt-kneaded at a barrel setting temperature of 330 ° C. to form pellets. In addition, at the time of melt kneading, 0.1 parts by weight of (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite as an antioxidant and tetrakis [methylene-3- (3 ′, 5'-
Di-t-butyl-4'-hydroxyphenyl)].
1 part by weight, methylene bis (2,4-di-t-
0.5 parts by weight of sodium butylphenol) acid phosphate were added.

The obtained pellets were injection-molded using a mold II at a molding temperature of 330 ° C. and a mold temperature of 80 ° C.
mm × 100mm × 2mm test piece and 300mm ×
A 135 mm IC tray was obtained. Table 1 shows the measurement results.

[0073]

Examples 2 to 5 Except that the composition was as shown in Table 1, melt-kneading was performed at a barrel setting temperature of 330 ° C. to form pellets, and injection molding was performed at a molding temperature of 300 ° C. and a mold temperature of 80 ° C.
This is similar to the first embodiment.

[0074]

Examples 6 and 7 Except that the composition was as shown in Table 1, melt-kneading was performed at a barrel setting temperature of 300 ° C. to form pellets, and injection molding was performed at a molding temperature of 300 ° C. and a mold temperature of 80 ° C.
This is similar to the first embodiment.

[0075]

Example 8 The composition was as shown in Table 1, and the mixture was melt-kneaded at a barrel setting temperature of 330 ° C. to form a pellet.
It is the same as Example 1 except that injection molding was performed at 0 ° C. and a mold temperature of 80 ° C.

[0076]

EXAMPLE 9 The composition was as shown in Table 1, and the mixture was melt-kneaded at a barrel setting temperature of 300 ° C., pelletized, and formed at a molding temperature of 30 ° C.
It is the same as Example 1 except that injection molding was performed at 0 ° C. and a mold temperature of 80 ° C.

[0077]

Examples 10 and 11 Example 1 was repeated except that the composition was as shown in Table 1, melt-kneaded at a barrel setting temperature of 330 ° C., pelletized, and injection-molded at a molding temperature of 330 ° C. and a mold temperature of 80 ° C. Is the same as

[0078]

Comparative Examples 1 to 11 As shown in Table 2, the same procedures as in Examples 1 to 11 were carried out except that the mold I was used.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

The resin molded article and the IC tray obtained by the present invention show good heat resistance and heat aging,
Since the conductivity is as good as 108Ω or less and the shape stability under high temperature is also excellent, it is excellent as a heat-resistant IC tray.

Claims (4)

[Claims] (A) 1 to 99% by weight of a styrene polymer having syndiotactic stereoregularity, and
(B) For 100 parts by weight of a mixture of 99 to 1% by weight of one or more polymers other than the component (A),
(C) A heat insulating material having a thermal conductivity of 0.01 cal / cm · sec · ° C. or less at 20 ° C. by heating and melting a resin composition containing 1 to 50 parts by weight of conductive carbon in a range of 270 to 370 ° C. The mold cavity coated with
A method for molding a resin molded article, comprising: molding at a temperature of 0 ° C. using a mold having the mold cavity. 2. A resin molded article molded by the molding method according to claim 1. 3. The molding method according to claim 1, wherein the resin molded product is a heat-resistant tray for IC. 4. An I molded by the molding method according to claim 3.
Heat-resistant tray for C.