CN1091454C - Thermoplastic resin composition, molded product and method for its production - Google Patents
Thermoplastic resin composition, molded product and method for its production Download PDFInfo
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- CN1091454C CN1091454C CN97112737A CN97112737A CN1091454C CN 1091454 C CN1091454 C CN 1091454C CN 97112737 A CN97112737 A CN 97112737A CN 97112737 A CN97112737 A CN 97112737A CN 1091454 C CN1091454 C CN 1091454C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
A thermoplastic resin composition comprises (A),(B),(C),(D) and (E), in which (A) is maleimide copolymer; (B) is vinyl copolymer; (C) is graft copolymer; (D) is polyamide resin; (E) is elastomer copolymer comprising an ethylene-alpha-olefin. The melting fluidity rate (MFR) is 3 to 40 g/10 min under 265 DEG C and 10 Kg charge.
Description
The present invention relates to the thermoplastic resin composition, thermoplastic resin molded article and preparation method thereof.Be particularly related to a kind of thermoplastic resin composition, it comprises according to a certain percentage, maleimide copolymer, graft copolymer, polyamide resin, and ethene-2-olefin elastomer basal component, maleimide copolymer comprises the residue of unsaturated dicarboxylic acid anhydride monomer and the residue of unsaturated dicarboxylic acid dant monomer substantially, graft copolymer comprises rubbery polymer substantially, the residue of aromatic vinyl monomer and vinyl cyanide monomer residue, the ethylene-alpha-olefin elastomerics contains unsaturated dicarboxylic acid monomer residue and/or unsaturated dicarboxylic acid anhydride monomer residue, and such thermoplastic resin composition can give a kind of ABS resin good chemically-resistant agent.The invention still further relates to a kind of thermoplastic resin molded article, it comprises such thermoplastic resin composition and ABS resin, it has thermotolerance and chemically-resistant agent, particularly thermoplastic resin molded article has good shock-resistance, thermotolerance and chemically-resistant agent, also can obtain such goods with the method for mould machine molding (referring to direct molding later on) by such thermoplastic resin composition and ABS resin is provided simultaneously.
In the past, prepared so-called ABS resin,, and had various uses because of it has good shock-resistance, mouldability and surface luster by the rubbery polymer of the mixture graft copolymerization of vinylbenzene and vinyl cyanide.On the other hand, the material that has the chemically-resistant agent according to special purposes needs.Object particularly to contacting with chemical agent, oil or organic solvent as sanitising agent, as parts, heating installation, kitchen utensils, refrigerator parts, bathtub parts, shower set parts, water cleaning equipment parts or the toilet seats coil component of trolley part, electric power and electronic unit, office appliance, need the safety and the wearing quality of chemically-resistant agent.
A kind of method of improving the chemically-resistant agent of ABS resin in the past is to add acrylic rubber shaped polymer or polyamide resin in ABS resin.
Yet the problem that contains the ABS resin of acrylic rubber shaped polymer is, although it has high chemically-resistant agent and shock-resistance, its thermotolerance and poor heat stability.On the other hand, the shortcoming that contains the resin combination that is blended into the polyamide resin in the ABS resin is that the consistency between the blending resin is not enough, when forming moulded parts, layering takes place most probably, and is difficult to obtain the goods that existing good shock-resistance has good chemically-resistant agent.
When acrylic rubber shaped polymer or polyamide resin and ABS resin kneading, the general kneader that uses as single screw extrusion machine, twin screw extruder or Banbury, to obtain resin particle with required chemically-resistant agent or other physical propertiess, and adopt the resin particle that comes molding to obtain as injection moulding process, produce layered product.
For adopting such usual way to obtain to have the physicals of different grades, as chemically-resistant agent and stable on heating layered product, must obtain to correspond respectively to the resin particle of desired physical properties grade, by this point as can be known, the quality control meeting is very inconvenient.
Also have, for obtaining the resin particle of corresponding physicals, need independent kneading operation, and like this, ABS resin is deterioration especially easily, thereby cause the impact strength variation.And kneading operation needs certain cost, and it also is disadvantageous economically.
An object of the present invention is to provide a kind of thermoplastic resin composition, it can give ABS resin good chemically-resistant agent, and solve above-mentioned in obtaining layered product involved problem, a kind of layered product with thermoplastic resin of good chemically-resistant agent also is provided, product comprises thermoplastic resin composition of the present invention and ABS resin, particularly thermoplastic resin molded product has good shock-resistance, thermotolerance and chemically-resistant agent, and it obtains by direct molding thermoplastic resin composition of the present invention and ABS resin.The present invention also provides the method for preparing product.
Personnel of the present invention have carried out big quantity research, to develop a kind of thermoplastic resin composition, it can give the agent of layered product chemically-resistant when the injection moulding ABS resin, found that, by the blend maleimide copolymer, graft copolymer, polyamide resin, ethylene-alpha-olefin elastomerics and optional ethylenic copolymer can reach this purpose, this maleimide copolymer comprises the residue of unsaturated dicarboxylic acid anhydride monomer and the residue of unsaturated dicarboxylic acid dant monomer by a certain percentage, this ethene-alpha-olefin elastomerics contains the residue of unsaturated dicarboxylic acid residues of monomers and/or unsaturated dicarboxylic acid anhydride monomer by a certain percentage, and this ethylenic copolymer comprises the residue of aromatic vinyl monomer and the residue of vinyl cyanide monomer substantially by a certain percentage.The present invention has been finished on basis in these discoveries.
Promptly, the invention provides a kind of thermoplastic resin composition, it comprises five kinds of components (A), (B), (C), (D) and (E), the total amount of component (A)-(E) is 100 weight parts, the component of 3-50 weight part (A), be maleimide copolymer, it comprises the residue of the unsaturated dicarboxylic acid anhydride monomer of the residue of 40-80 weight % aromatic vinyl monomer, maximum 20 weight % (not comprising 0 weight %), minimum 10 weight % but less than the residue of the unsaturated dicarboxylic acid imide derivative of 60 weight % and the 0-20 weight % vinyl monomer residue of copolymerization with it; The component of 0-50 weight part (B) is an ethylenic copolymer, and residue, 20-40 weight % vinyl cyanide monomer residue and the 0-20 weight % that it comprises 60-80 weight % aromatic vinyl monomer be the residue of the vinyl monomer of copolymerization with it; The component of 3-50 weight part (C), it is graft copolymer, it is to obtain to 35-65 parts by weight of rubber shaped polymer by a kind of monomer mixture graft polymerization with the 35-65 weight part, and aromatic vinyl monomer, 20-40 weight % vinyl cyanide monomer and the 0-30 weight % that this monomer mixture comprises 50-80 weight % be the vinyl monomer of copolymerization with it; Greater than 20 weight parts but the component (D) that is no more than 56 weight parts is a polyamide resin; Greater than 12 weight parts but be no more than the component (E) of 40 weight parts, be the ethene-alpha-olefin elastomer copolymer; It contains unsaturated dicarboxylic acid monomer residue and/or the unsaturated dicarboxylic acid anhydride monomer residue of maximum 5 weight % (not comprising 0 weight %); Described thermoplastic resin composition's melt flow rate (MFR) (MFR) restrains/10 minutes for 3-40 under 265 ℃, 10 kilograms loads.
Thermoplastic resin composition's of the present invention characteristics are when it forms layered product, under the various physicalies as thermotolerance and shock-resistance of the basic ABS resin of not obvious reduction, just can give its chemically-resistant agent with very low cost.
The maleimide copolymer of the component (A) that is used for thermoplastic resin composition of the present invention is described below.
The aromatic vinyl monomer of forming component (A) is that at least one is selected from the styrene monomer as vinylbenzene, alpha-methyl styrene, Vinyl toluene, t-butyl styrene and chloro-styrene.Wherein, optimization styrene.
Being prepared as of multipolymer that comprises the vinyl monomer of aromatic vinyl monomer, unsaturated dicarboxylic acid imide derivative, unsaturated dicarboxylic acid acid anhydride and optional copolymerization with it, but the vinyl monomer copolymerization of the copolymerization that makes unsaturated dicarboxylic acid acid anhydride and aromatic vinyl monomer and choose wantonly, with ammonia and/or primary amine reaction, obtain to contain the maleimide copolymer of unsaturated dicarboxylic acid anhydride monomer residue and unsaturated dicarboxylic acid dant monomer residue subsequently.In addition, at least a dant monomer that is selected from maleimide, N-methyl maleimide, N-ethyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-naphthyl maleimide and glutarimide can be directly and the vinyl monomer copolymerization of aromatic vinyl monomer, unsaturated dicarboxylic acid anhydride monomer and optional copolymerization with it, obtains a kind of maleimide copolymer.The unsaturated dicarboxylic acid acid anhydride is a kind of acid anhydride that is selected from toxilic acid, methylene-succinic acid, citraconic acid and equisetic acid at least.Wherein preferred maleic anhydride.The ammonia or the primary amine that are used to form imido reaction can be the anhydrous state or the aqueous solution.Primary amine is a kind of alkylamine that is selected from as methylamine, ethamine and hexahydroaniline at least, reaches the arylamine as aniline, Tolylamine and naphthylamines.
When in solution or suspension, forming imido reaction, preferably select common response device as autoclave.When the body molten state is reacted, use the forcing machine of being furnished with degasser.
Form imido temperature of reaction and be generally 80-350 ℃, be preferably 100-300 ℃.If temperature is lower than 80 ℃, speed of response can be slow excessively, and reaction needs for a long time, and is in fact infeasible.On the other hand, if temperature surpasses 350 ℃, because polymkeric substance thermolysis meeting makes deterioration in physical properties.In forming imido reaction, can use catalyzer, at this moment preferably use tertiary amine as triethylamine as catalyzer.
The residue that is used for the aromatic vinyl monomer of component (A) is 40-80 weight %, is preferably 45-60 weight %.If less than 40 weight %, its molding processability can be poor, if surpass 80 weight %, thermoplastic resin composition's thermotolerance can reduce, and is therefore undesirable like this.The unsaturated dicarboxylic acid imide derivative residue that is used for component (A) is at least 10 weight % but less than 60 weight %.If less than 10 weight % or be at least 60 weight %, the thermoplastic resin composition's who obtains consistency can variation, and shock-resistance can reduce greatly.The residue of unsaturated dicarboxylic acid imide derivative is preferably 25-55 weight %.
In addition, the residue of unsaturated dicarboxylic acid anhydride monomer mostly is 20 weight % (not comprising 0 weight %) most, is preferably 0.5-15 weight %.If do not add the residue of unsaturated dicarboxylic acid acid anhydride, the consistency of the polyamide resin of the maleimide copolymer of component (A) and component (D) meeting variation, this not only can cause the cracking of layered product, and can make the shock strength variation.If surpass 20 weight %, will take place with the end amino of component (D) polyamide resin crosslinked, thereby the flowability of making (melt flow rate (MFR)) reduces, the infringement appearance, molding processability can the meeting variation simultaneously.But the residue of copolyethylene monomer is 0-20 weight %, is 0-10 weight % preferably.If surpass 20 weight %, with the consistency variation of other components, thereby deterioration of impact resistance, and when forming layered product, layering very easily takes place.
Weight-average molecular weight to the maleimide of component (A) has no particular limits, but with 70,000-160,000 is advisable, and better is 80,000-150,000.
The ethylenic copolymer (B) that is used for thermoplastic resin composition of the present invention is described below.
The aromatic vinyl monomer that is used for component of the present invention (B) is a kind of styrene monomer that is selected from as vinylbenzene, alpha-methyl styrene, Vinyl toluene, t-butyl styrene and chloro-styrene at least.Optimization styrene.Vinyl cyanide monomer is a kind of vinyl cyanide, methacrylonitrile and α-Lv Bingxijing of being selected from least.Wherein preferred vinyl cyanide.
The vinyl monomer of copolymerization is a kind of acrylate that is selected from as methyl acrylate, ethyl propenoate and butyl acrylate at least with it, methacrylic ester as methyl methacrylate, Jia Jibingxisuanyizhi, vinyl carboxylic acid monomer as vinylformic acid and methacrylic acid, acrylic acid amides, methacrylic acid acid amides and N-vinylcarbazole.Wherein, preferably as the monomer of methacrylic ester, acrylic or methacrylic acid.
The residue of the aromatic vinyl monomer in the component (B) is 60-80 weight %, is 68-78 weight % preferably.If less than 60 weight % or greater than 80 weight %, molding processability can variation.The residue of vinyl cyanide monomer is 20-40 weight %, is 22-32 weight % preferably.If less than 20 weight % or greater than 40 weight %,, cause the layering or the shock strength variation of layered product with the consistency variation of component (A).But the residue of copolyethylene monomer is 0-20 weight %, is 0-10 weight % preferably.If surpass 20 weight %, with the consistency variation of other components, thereby make deterioration of impact resistance, and when forming layered product, layering takes place most probably.Also can adopt common polymerization process to prepare component (B).For example, can adopt polymerization process as suspension polymerization, solution polymerization or letex polymerization.
The graft copolymer of the component (C) that is used for thermoplastic resin composition of the present invention is described below.
The rubbery polymer that is used for component (C) is a kind of multipolymer, ethylene-propylene copolymer and ethylene-propylene-diene copolymer that is selected from butadiene polymer, divinyl and polymerisable vinyl monomer at least.
The aromatic vinyl monomer that is used for component (C) can be a kind of styrene monomer that is selected from as vinylbenzene, alpha-methyl styrene, Vinyl toluene, t-butyl styrene and chloro-styrene at least.Optimization styrene.Vinyl cyanide monomer is a kind of vinyl cyanide, methacrylonitrile and α-Lv Bingxijing of being selected from least.Wherein preferred vinyl cyanide.
In addition, the vinyl monomer of copolymerization can be a kind of acrylate that is selected from as methyl acrylate, ethyl propenoate and butyl acrylate at least with it, methacrylic ester as methyl methacrylate, Jia Jibingxisuanyizhi, vinyl carboxylic acid monomer as vinylformic acid and methacrylic acid, acrylic acid amides, methacrylic acid acid amides and N-vinylcarbazole.Wherein, preferably as the monomer of acrylate, methacrylic acid, acrylic or methacrylic acid.
Can adopt any common polymerization technique to be used to prepare the graftomer of component (C).For example, the heterogeneous polymerization that can mention, mass polymerization, solution polymerization or the polymkeric substance sedimentary heterogeneous polymerization in poor solvent that wherein forms, or and combination as the water of suspension polymerization or letex polymerization.
Weight-average molecular weight to the graft copolymer of rubber particle size, percentage of grafting and component (C) has no particular limits.Yet from the shock-resistance angle, rubber particle size is preferably in the scope of 0.1-0.6 micron.And percentage of grafting is that 20-80% is advisable, and better is 30-50%, and the weight-average molecular weight of non-graft copolymer is 50 preferably, 000-200 is in 000 the scope, better 60,000-100, in 000 the scope, the over-all properties of shock-resistance and molding processability all is good like this.
The graft copolymer of component (C) can be by monomer mixture graft copolymerization preparation in the presence of 35-65 parts by weight of rubber shaped polymer of 35-65 weight part, aromatic vinyl monomer, 20-40 weight % vinyl cyanide monomer and the 0-30 weight % that monomer mixture comprises 50-80 weight % be the vinyl monomer of copolymerization with it, and the total amount of rubbery polymer and monomer mixture is 100 weight parts.Preferred a kind of monomer mixture comprises 65-72 weight % aromatic vinyl monomer, 22-32 weight % vinyl cyanide monomer and the 0-13 weight % vinyl monomer of copolymerization with it.If aromatic vinyl monomer is less than 50 weight %, the direct molding processability energy variation of thermoplastic resin composition of the present invention and ABS resin is if surpass 80 weight %, thermoplastic resin composition's of the present invention thermotolerance variation.If vinyl cyanide monomer is less than 20 weight % or surpass 40 weight %,, can cause the layering or the shock strength variation of the moulded parts of thermoplastic resin composition of the present invention and ABS resin with the consistency variation of component (A).If but copolyethylene monomer surpasses 30 weight %, with the consistency variation of other components, deterioration of impact resistance, when forming layered product, layering can take place.And, as the rubbery polymer in the fruit component (C) less than 35 weight parts, thermoplastic resin composition's of the present invention deterioration of impact resistance, if surpass 65 weight parts, thermoplastic resin composition's of the present invention thermotolerance variation, the direct molding processability of thermoplastic resin composition of the present invention and ABS resin can variation.
In graft polymerization reaction, general be difficult to all are monomer-grafted to rubbery polymer, can produce the by product of non-graft copolymer.Among the present invention, certainly use and separate and remove the real graft copolymer of so non-graft copolymer really, or contain the graftomer of so non-graft copolymer.These two kinds can be as the graft copolymer of the object of the invention.
The polyamide resin of thermoplastic resin composition's of the present invention component (D) is described below.
The polyamide resin of component (D) can be, as nylon-6, nylon-6, and 6, nylon-4,6, nylon-6,10, PA-12 or Ni Long11.These resins can use or be combined as mixture separately and use.
The ethene-alpha-olefin elastomerics of thermoplastic resin composition's of the present invention component (E) is described below.To the ethene-alpha-olefin elastomerics that contains unsaturated dicarboxylic acid and/or its acid anhydride of component (E), preferred a kind of number-average molecular weight is 10,000-1, and in 000,000 scope, ethylene content is the elastomerics of 50-80 mole %.Alpha-olefin is a kind of alkene that is selected from propylene, 1-butylene and 1-amylene at least.Wherein preferred propylene.
Unsaturated dicarboxylic acid residues of monomers and/or the unsaturated dicarboxylic acid anhydride monomer residue as the functional group of component (E) that are used for modification can be a kind of monomer that is selected from toxilic acid, methylene-succinic acid, citraconic acid and equisetic acid and these sour acid anhydrides at least.Wherein preferred maleic anhydride.
The content of unsaturated dicarboxylic acid monomer residue and/or unsaturated dicarboxylic acid anhydride monomer residue mostly is 5 weight % (not comprising 0 weight %) most, is 0.5-5 weight % preferably.If content surpasses 5 weight %, gelling or similar situation can take place in the composition.On the other hand, if less than 0.5 weight %, thermoplastic resin composition's consistency is not enough, thereby when forming layered product, layering takes place very easily, can not obtain enough shock strengths.Adopt the preparation method who is disclosed among the embodiment of JP-B-58-445 can prepare so ethene improved-alpha-olefin elastomerics.
Component among the thermoplastic resin composition of the present invention (A), (B), (C), (D) and blending ratio (E) be, total amount with component (A)-(E) is 100 weight parts, component (A) is the 3-50 weight part, and component (B) is the 0-50 weight part, and component (C) is the 3-50 weight part, component (D) is greater than 20 weight parts but is not more than 56 weight parts, component (E) is greater than 12 weight parts but is not more than 40 weight parts that preferably, component (A) is the 5-30 weight part, component (B) is the 0-30 weight part, component (C) is the 5-20 weight part, and component (D) is the 30-50 weight part, and component (E) is the 20-40 weight part.Less than 3 weight parts, consistency is not enough as fruit component (A), if surpass 50 weight parts, thermoplastic resin composition's shock-resistance and molding processability can deteriorate significantly.And surpassing 50 weight part molding processabilities as fruit component (B) can variation.As fruit component (C) less than 3 weight parts, deterioration of impact resistance, if surpass 50 weight parts, molding processability can variation.(D) is not more than 20 weight parts as fruit component, and the chemically-resistant agent is not enough, surpasses 56 weight parts, the dimensional stability variation.(E) is not more than 12 weight parts as fruit component, and shock-resistance is not enough.If surpass 40 weight parts, molding processability can variation.And, component (E) among the thermoplastic resin composition of the present invention and (D) ratio are had no particular limits, but the weight ratio=30/70-50/50 of (E)/(D) preferably.
Blending ingredients (A)-(E) has no particular limits with the method that obtains thermoplastic resin composition of the present invention, can adopt any general equipment.Such general-purpose equipment is, as Banbury, rotary drum mixer, mixing roll or single screw rod or twin screw extruder.About hybrid mode, just like with the common melting mixing of master batch material, multistage melting mixing or in solution, mix to obtain composition.Particularly, component (D) and (E) melting mixing in advance, all the other components (A)-(C) can be mixed subsequently.Preferably first melting mixing comprises component (D) and resin Composition (E), and then blending ingredients (A), (B) and (C), make component (A), (B) and (C) and component (D) and weight ratio (E) [(A)+(B)+(C)]/[(D)+(E)]=60/40-20/80, be preferably 40/60-20/80, to obtain the thermoplastic resin composition, the thermoplastic resin composition can obtain layered product with the direct molding of ABS resin, thereby further improves thermotolerance, chemically-resistant agent, shock-resistance and the molding processability energy of the layered product that obtains.And the melt flow rate (MFR) (MFR) that requires thermoplastic resin composition of the present invention is 3-25 in the scope of 3-40 preferably, better is 3-10.If melt flow rate (MFR) is lower than 3, by the appearance meeting variation of the product that obtains with the direct molding of ABS resin, if surpass 40, the shock strength of layered product and thermotolerance variation.
According to concrete purposes, also can add stablizer, softening agent, lubricant, ultraviolet absorbers or tinting material among the thermoplastic resin composition of the present invention.
When in mold apparatus, directly adding thermoplastic resin composition of the present invention and ABS resin, add above-mentioned additive.
ABS resin used in the present invention can be, as at least two kinds of monomers by the vinyl monomer that is selected from aromatic vinyl monomer, vinyl cyanide monomer, maleimide monomer and copolymerization with it, be selected from the presence of at least a rubbery polymer of butadiene polymer, butadiene-styrene copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer and acrylic ester polymer the resin that polyreaction obtains.
The vinyl monomer of aromatic vinyl monomer, vinyl cyanide monomer and copolymerization with it can be the aromatic vinyl monomer, vinyl cyanide monomer of the component (B) as above-mentioned thermoplastic resin composition and the vinyl monomer of copolymerization with it.Maleimide monomer can be, as maleimide, N-methyl maleimide, N-ethyl maleimide, N-propyl group maleimide, N-cyclohexyl maleimide or N-phenylmaleimide.
And, for adjusting the amount of the rubber components in the resin, can mix the polymkeric substance that constitutes by the monomer component identical with forming resin monomer.But such polymkeric substance needn't necessarily be made of identical monomer component.For example, when during as monomer component, sneaking into the polymkeric substance of the monomer mixture that comprises vinylbenzene, vinyl cyanide and alpha-methyl styrene with vinylbenzene and acrylonitrile monemer.
The object lesson of ABS resin used in the present invention comprises ABS (acrylonitrile-butadiene-styrene (ABS)) resin, Alpha-Methyl-vinylbenzene thermotolerance ABS (acrylonitrile-butadiene-alpha-methyl styrene; Acrylonitrile-butadiene-alpha-methyl styrene-vinylbenzene) resin, maleimide heat-proof ABS (acrylonitrile-butadiene-N-phenylmaleimide-vinylbenzene) resin, AES (vinyl cyanide-EPDM-vinylbenzene) resin, AAS (acrylonitrile-acrylate-styrene) resin, MBS (methyl methacrylate-acrylonitrile-styrene) resin and MABS (methyl methacrylate-acrylonitrile-butadiene-styrene (ABS)) resin.But ABS resin is not subjected to the restriction of these object lessons.
Blending ratio to thermoplastic resin composition of the present invention and ABS resin has no particular limits.But blend comprises the thermoplastic resin composition of 10-50 weight % preferably, the ABS resin of 50-90 weight %, the thermoplastic resin composition who better comprises 15-40 weight %, the ABS resin of 60-85 weight %, the best thermoplastic resin composition who comprises 15-30 weight %, the ABS resin of 70-85 weight %.
If the thermoplastic resin composition is less than 10 weight %, directly the chemically-resistant agent of the product that obtains of molding is not enough with ABS resin.On the other hand, if surpass 50 weight %, directly molding processability can variation with ABS resin.
In the scope of not damaging purpose of the present invention, the concrete scope that can add the ABS resin amount in thermoplastic resin composition of the present invention in advance is 0-20 weight %.
Mold apparatus used in the present invention can be injection moulding machine, sheet material former, blow moulding machine, injection-blow moulding equipment.But mold apparatus is not limited to these object lessons.
Provide the method for thermoplastic resin composition of the present invention and ABS resin to have to mold apparatus, the common equipment such as the method for rotary drum mixer or V-blending machine premix mixture of adopting is provided, the method that quantitatively adds two kinds of materials at the opening for feed of mold apparatus respectively, or, join the method for mold apparatus then with thermoplastic resin composition and ABS resin pre-fusion kneading formation pellet.But do not limit method of feeding especially.
The design temperature of determining the mold apparatus barrel is the optimum temps that is determined by the thermoplastic resin composition.Specifically, to the present invention, temperature is 240-280 ℃ preferably.
Under the injection moulding situation, can between the barrel of mold apparatus and nozzle, place common static mixer such as Sulzer type, Kenics type or eastern beautiful type, so just can obtain high-quality layered product.
And, to the screw rod of injection-moulding device, can adopt the most frequently used all spiral screw bolt.But also can use Dole McGee formula, pin type or Maddock type screw rod with higher kneading efficient.
Be described in further detail description the present invention below with reference to embodiment.But should understand the restriction that the present invention never is subjected to these specific embodiments.Among below the embodiment and comparative example, unless otherwise indicated, " part " and " % " represents " weight part " and " weight % " respectively.
Experimental example 1 and 2
Component (A) (A-1, maleimide copolymer A-3)
Add 60 parts of vinylbenzene in the autoclave that agitator is housed, 0.05 part of α-Jia Jibenyixierjuwu and 100 parts of methyl ethyl ketones are with the gas of nitrogen replacement internal system.Then, temperature is elevated to 85 ℃, is added in the solution that dissolves 40 parts of maleic anhydrides and 0.15 part of benzoyl peroxide in 200 parts of methyl ethyl ketones in 8 hours continuously.After adding, keep 85 ℃ temperature 3 hours.In the copolymer solution that obtains, add 38 parts of aniline and 0.6 part of triethylamine, and 140 ℃ of reactions 7 hours.Reaction soln is supplied with the exhaust twin screw extruder, and the degassing is to obtain maleimide copolymer.Analyzed as can be known by C-13NMR, it is 92 moles of % that acid anhydrides changes into imido transformation efficiency.This maleimide copolymer contains the 51% N-phenylmaleimide unit as the unsaturated dicarboxylic acid imide derivative, is designated as copolymer A-1.Mode by preparation A-1 prepares maleimide copolymer A-3, and difference joins the ratio of the imide group in the maleic anhydride for adjusting the amount of aniline with adjustment.
Experimental example 3
Component (A) maleimide copolymer (A-2)
In the autoclave that agitator is housed, add 60 parts of vinylbenzene and 100 parts of methyl ethyl ketones, with the gas of nitrogen replacement internal system.Then, temperature is elevated to 85 ℃, under this temperature, fully stirs.Except in autoclave, adding 1 part of α-Jia Jibenyixierjuwu, prepare maleimide copolymer A-2 by the method for preparing A-1.Table 1 has been listed analytical results and the weight-average molecular weight of composition A-1 to A-3.
Table 1
St: vinylbenzene NPMI:N-phenyl maleimide MAH: maleic anhydride
| Form (%) | Weight-average molecular weight (* 10 -4) | |||
| St | NPMI | MAH | ||
| A-1 | 46.5 | 51.0 | 2.5 | 14.5 |
| A-2 | 46.5 | 51.0 | 2.5 | 8.0 |
| A-3 | 47.5 | 46.0 | 6.5 | 14.5 |
" the SHODEX GPR SYSTEM-21 " that uses clear and electrician company to make carries out GPC and measures, and determines weight-average molecular weight, has the calibration curve that the polystyrene of standard molecular weight is drawn by use, obtains press the weight-average molecular weight of polystyrene calculating.
Experimental example 4
The preparation of component (B) ethylenic copolymer (B-1)
In being housed, the reactor of agitator adds 70 parts of vinylbenzene, 30 parts of vinyl cyanide, and 2.5 parts of calcium phosphate, 0.5 part of uncle's dodecyl mercaptans, 0.2 part of benzoyl peroxide and 250 parts of water, elevated temperature to 70 is ℃ with initiated polymerization.When initiated polymerization after 7 hours, temperature is elevated to 75 ℃, and keeps 3 hours to finish polyreaction.Extent of polymerization reaches 97%.With in the hydrochloric acid and the reaction soln that obtains, dehydration and dry back obtain multipolymer white bead.This multipolymer is multipolymer B-1.
Experimental example 5
The preparation of component (C) graft copolymer (C-1)
In being housed, the reactor of agitator adds 143 parts of polybutadiene latex (solids contents: 35%, average particle size: 0.25 micron, gel content: 90%), 1 part of sodium stearate, 0.1 part of sodium formaldehyde sulphoxylate, 0.03 part of tetrasodium ethylenediamine tetraacetate, 0.003 part of ferrous sulfate and 150 parts of pure water are heated to 50 ℃.Added 50 parts of monomer mixtures that comprise 70% vinylbenzene and 30% vinyl cyanide, 0.2 part of uncle's dodecyl mercaptans and 0.15 part of cumene hydroperoxide in 6 hours continuously.After adding, temperature is increased to 65 ℃, the further polymerization of mixture 2 hours.Extent of polymerization reaches 97%.For obtaining latex, add 0.3 part of oxidation inhibitor (Iruganox 1076), with the calcium chloride cohesion, water cleans subsequently, and dry back obtains the graft copolymer white powder.This multipolymer is designated as C-1.
For measuring the non-graft copolymer molecular weight of percentage of grafting and C-1, take by weighing 3 gram C-1, with methyl ethyl ketone solution swelling, centrifugation subsequently, with the molecular weight of the non-graft phenylethene-acrylonitrile copolymer of gel permeation chromatography in supernatant liquid, its weight-average molecular weight is 82,000.By forming of quantitative analysis of Kieldahl nitrogen and the sedimentary gel content of thermolysis gas chromatographic analysis centrifugation, determine the weight of graft copolymer by the amount of vinylbenzene and vinyl cyanide.Use the bromine additive process, analyze polybutadiene rubber, thereby determine the weight of rubbery polymer.Can calculate percentage of grafting by graft copolymer weight and rubbery polymer weight by following formula, the percentage of grafting that obtains like this is 33%.
Percentage of grafting=(graft copolymer weight/rubbery polymer weight) * 100 (%)
Can obtain nylon-6 by the polycondensation of 6-caprolactone is nylon-6 (CM-1017 is produced by Dong Li industrial), and its relative viscosity is 2.65 (with the vitriol oil are solvent, 25 ℃ of concentration determinations with/100 milliliters of 0.5 grams), as D-1.
Experimental example 6
The elastomeric component of ethene improved-alpha-olefin (E) preparation (E-1)
The method that is disclosed according to JP-A-52-49289 (embodiment), maleic anhydride graft with 1.3% is 500 to number-average molecular weight, (the EPR of modification on 000 the ethylene-propylene copolymer, its MFR is 0.5 gram/10 minutes at 10 kilograms of loads, 230 ℃ the time, Tafmer MP-0430: produced by Mitsui petroleum chemistry company limited), the elastomerics of acquisition is designated as E-1.
Experimental example 7
Component (D) and mixing (E)
With 60 parts of components (D) and 40 parts of components (E) blend, extrude this blended product at 280 ℃ of twin screw extruders by 35 millimeters identical sense of rotation of deflated, and granulation, obtain resin combination (F-1).By same way as, obtain to comprise the resin combination (F-2) of 80 parts of components (D) and 20 parts of components (E).
Experimental example 8
Thermoplastic resin composition's preparation
In the ratio blend components (A) in the table 2, component (B), component (C) and F-1 or F-2, extrude this blended product and granulation at 280 ℃ of twin screw extruders by the identical sense of rotation of 35mm deflated, obtain thermoplastic resin composition MB-1 to MB-9.The melt flow rate (MFR) of measuring the thermoplastic resin composition is listed in table 2.
Table 2
| MB-1 | MB-2 | MB-3 | MB-4 | MB-5 | MB-6 | MB-7 | MB-8 | MB-9 | |
| A-1 | 5 | 5 | |||||||
| A-2 | 5 | ||||||||
| A-3 | 10 | 5 | 5 | 10 | 20 | 30 | |||
| B-1 | 40 | 25 | 10 | 10 | 10 | 10 | 20 | 10 | 0 |
| C-1 | 20 | 10 | 5 | 5 | 5 | 5 | 10 | 10 | 10 |
| F-1 | 30 | 60 | 80 | 80 | 80 | 60 | 60 | 60 | |
| F-2 | 80 | ||||||||
| MFR | 43 | 9.4 | 2.2 | 8.9 | 7.5 | 10 | 7.0 | 3.2 | 0.8 |
To ABS resin, use the ABS resin GT-R (to call ABS-1 in the following text) of Denki Kagaku Kogyo kabushiki's production or the thermotolerance ABS resin K-090 (to call ABS-2 in the following text) that Denki Kagaku Kogyo kabushiki produces.
Embodiment 1-7
The ratio of listing in table 3 adds thermoplastic resin composition MB-2 respectively by doser in injection moulding machine, MB-4, and MB-5, MB-7 or MB-8 and ABS resin ABS-1 or ABS-2 are with molded sample.Static kneader (mixing nozzle) TMN-16-06 (being made by Dong Li engineering corporation) is connected to injection moulding machine K-125 last (being made by ironworker company of Kawaguchi) carries out molding.Other condition of moulding is as follows.
Barrel temperature: 260 ℃
Injection pressure: minimum filling pressure+5 kilograms per centimeter
2G
Injection moulding speed: 70%
Molding temperature: 60 ℃
Screw rod: all spiral screw bolt
The various physicalies of the sample that mensuration obtains above the results are shown in table 3.Estimate the ABS-1 and the ABS-2 that do not add the thermoplastic resin composition,, the results are shown in table 4 as a reference example 1 and 2.
Embodiment 8
At 260 ℃, extrude 20 parts of thermoplastic resin composition MB-2 and 80 parts of ABS resin ABS-2 by the single screw extrusion machine of 40 millimeters of diameters, obtain pellet.Use this pellet, prepare sample by the condition of moulding identical with embodiment 1.Measure its physicals, the results are shown in table 3.
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| ABS-1 | 80 | |||||||
| ABS-2 | 80 | 85 | 85 | 80 | 80 | 70 | 80 | |
| MB-2 | 20 | 20 | ||||||
| MB-4 | 15 | 20 | ||||||
| MB-5 | 15 | |||||||
| MB-7 | 20 | |||||||
| MB-8 | 20 | 30 | ||||||
| Cantilever beam impact strength (kilogram cm/) | 26 | 25 | 25 | 20 | 26 | 25 | 27 | 23 |
| HDT(℃) | 97 | 97 | 97 | 91 | 97 | 97 | 98 | 97 |
| MFR (restraining/10 minutes) | 65 | 65 | 70 | 58 | 65 | 60 | 52 | 68 |
| Critical strain (%) | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 | 1.1 |
| Dimensional stability | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Appearance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Table 4
| Reference example 1 | Reference example 2 | |
| ABS-1 | 100 | |
| ABS-2 | 100 | |
| Cantilever beam impact strength (kilogram cm/) | 20 | 25 |
| HDT(℃) | 91 | 97 |
| Critical strain (%) | 0.6 | 0.6 |
Comparative example 1-8
Mode by embodiment is operated, and difference is used thermoplastic resin composition MB-1, MB-3, MB-6, MB-9 or F-1 and ABS resin ABS-1 or ABS-2 for the ratio of listing in table 5.
Table 5
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| ABS-1 | 60 | 85 | 85 | |||||
| ABS-2 | 60 | 85 | 90 | 85 | 80 | |||
| MB-1 | 40 | 40 | ||||||
| MB-3 | 15 | 15 | ||||||
| MB-6 | 15 | 15 | ||||||
| MB-9 | 20 | |||||||
| F-1 | 10 | |||||||
| Cantilever beam impact strength (kilogram cm/) | 15 | 14 | 15 | 14 | 7 | 12 | 13 | 24 |
| HDT(℃) | 90 | 91 | 95 | 97 | 97 | 91 | 97 | 98 |
| MFR (restraining/10 minutes) | 73 | 60 | 80 | 80 | 80 | 72 | 88 | 55 |
| Critical strain (%) | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 1.1 | 1.1 | 1.1 |
| Dimensional stability | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Appearance | ○ | × | ○ | × | ○ | ○ | ○ | × |
Measure the testing method of physical properties
1) HDT (heat-drawn wire): according to ASTM D-648, in 18.6 kilograms per centimeter
2Load measure down.
2) cantilever beam impact strength: according to ASTM-D-256, mensuration thickness is 1/4 inch notched specimen.
3) MFR:, under 265 ℃, 10 kilograms loads, measure according to ASTM-D-6874.
4) critical strain (chemically-resistant agent): specimen shape is 330 * 20 * 2 millimeters, is 248 millimeters by major radius, and short radius is that 148 millimeters one 1/4 oval method is determined at 23 ℃ of critical strains after 24 hours.For getting rid of the influence of molding stress, under 270 ℃, prepare, and be cut into sample by the press molding pellet.Use salad oil as reagent.
5) dimensional stability: according to ASTM-D-368, with 1
#Dumbbell specimen immerses 80 ℃ of hot water and reaches 24 hours, measures to immerse before and after the hot water dimensional change of the long axis direction of dumbbell.
Symbol zero expression dimensional change is no more than 0.5%, and symbol * expression dimensional change surpasses 0.5%.
6) outward appearance: under above-mentioned injecting condition,, be of a size of 127 * 127 * 2 millimeters by square plate of side gate (2 points) molding, the outward appearance of visual control layered product, and by following standard evaluation.
Zero: do not observe defective (as fault, silver bar line, overlap) on the surface.
*: arrive defective (as fault, silver bar line, overlap) at surface observation.
Shown in the embodiment of table 3, directly molding thermoplastic resin composition of the present invention and ABS resin under the various physicals situations of not damaging as the ABS resin of basic material, can obtain to have the layered product of chemically-resistant agent and high-quality apperance.
Shown in the comparative example of table 5,, can not obtain to have the layered product of such premium properties if the thermoplastic resin composition who uses has exceeded scope of the present invention.
As previously mentioned, the layered product of molding thermoplastic resin composition of the present invention and ABS resin acquisition has good chemically-resistant agent and thermotolerance.Thermoplastic resin composition particularly of the present invention can be with the direct molding of ABS resin, do not damaging under the various physicals situations of basic ABS resin, the product of molding has good chemically-resistant agent, thermotolerance and shock-resistance, also has the good plastic-molded workability energy.According to direct molding of the present invention, by changing concrete thermoplastic resin composition and need giving the blending ratio of the basic ABS resin of chemically-resistant agent, just can not damage under the performance situation of basic ABS resin, obtain to have given the layered product of required chemically-resistant agent.And, can use the excellent process preparation of the direct molding of such economy, and, has very big industrial application value as the material that is used for trolley part, electric power and electronic unit, office accommodations parts, heating installation, kitchen utensils, refrigerator parts, bathtub parts, shower set parts, water cleaning equipment parts or toilet seats coil component.
Claims (6)
1. thermoplastic resin molded product, it is by the ABS resin of 10-50 weight % thermoplastic resin composition and 50-90 weight % is provided to pattern device, and obtain by the mold apparatus molding, described thermoplastic resin composition comprises component (A), (B), (C), (D) and (E), the total amount of component (A)-(E) is 100 weight parts, the component of 5-30 weight part (A), be maleimide copolymer, it comprises the residue of 40-80 weight % aromatic vinyl monomer, residue greater than the unsaturated dicarboxylic acid anhydride monomer of 0 weight % to 20 weight %, 10 weight % are to less than the residue of the unsaturated dicarboxylic acid imide derivative of 60 weight % and the 0-20 weight % vinyl monomer residue of copolymerization with it; The component of 0-30 weight part (B) is an ethylenic copolymer, and residue, 20-40 weight % vinyl cyanide monomer residue and the 0-20 weight % that it comprises 60-80 weight % aromatic vinyl monomer be the residue of the vinyl monomer of copolymerization with it; The component of 5-20 weight part (C), it is graft copolymer, it is to obtain to 35-65 parts by weight of rubber shaped polymer by a kind of monomer mixture graft polymerization with the 35-65 weight part, and aromatic vinyl monomer, 20-40 weight % vinyl cyanide monomer and the 0-30 weight % that monomer mixture comprises 50-80 weight % be the vinyl monomer of copolymerization with it; The component of 30-50 weight part (D) is a polyamide resin; The component of 20-40 weight part (E) is the ethene-alpha-olefin elastomer copolymer, and it contains greater than the unsaturated dicarboxylic acid monomer residue of 0 weight % to 5 weight % and/or unsaturated dicarboxylic acid anhydride monomer residue; Described thermoplastic resin composition's melt flow rate (MFR) restrains/10 minutes for 3-40 under 265 ℃, 10 kilograms loads.
2. thermoplastic resin molded product as claimed in claim 1, its feature are that also the component (E) and the weight ratio of component (D) are (E)/(D)=30/70-50/50.
3. thermoplastic resin molded product as claimed in claim 1 or 2, its feature is that also it is prepared as first pre-fusion mixing and comprises component (D) and composition (E), add component (A) again, (B) and (C), make component (A), (B) and (C) with component (D) and weight ratio (E) [(A)+(B)+(C)]/[(D)+(E)]=60/40-20/80.
4. thermoplastic resin molded product as claimed in claim 1 or 2 is characterized in that it is obtained by the injection moulding machine moulding.
5. the preparation method of the moulded parts of thermoplastic resin, it is characterized in that it is included under 240-280 ℃ the temperature to mold apparatus provides and simultaneously by the thermoplastic resin composition of mold apparatus molding 10-50 weight % and the ABS resin of 50-90 weight %, described thermoplastic resin composition comprises component (A), (B), (C), (D) and (E), the total amount of component (A)-(E) is 100 weight parts, the component of 5-30 weight part (A), be maleimide copolymer, it comprises the residue of 40-80 weight % aromatic vinyl monomer, residue greater than the unsaturated dicarboxylic acid anhydride monomer of 0 weight % to 20 weight %, 10 weight % are to less than the residue of the unsaturated dicarboxylic acid imide derivative of 60 weight % and the 0-20 weight % vinyl monomer residue of copolymerization with it; The component of 0-30 weight part (B) is an ethylenic copolymer, and residue, 20-40 weight % vinyl cyanide monomer residue and the 0-20 weight % that it comprises 60-80 weight % aromatic vinyl monomer be the residue of the vinyl monomer of copolymerization with it; The component of 5-20 weight part (C), it is graft copolymer, it is to obtain to 35-65 parts by weight of rubber shaped polymer by a kind of monomer mixture graft polymerization with the 35-65 weight part, and aromatic vinyl monomer, 20-40 weight % vinyl cyanide monomer and the 0-30 weight % that monomer mixture comprises 50-80 weight % be the vinyl monomer of copolymerization with it; The component of 30-50 weight part (D) is a polyamide resin; The component of 20-40 weight part (E) is the ethene-alpha-olefin elastomer copolymer, and it contains greater than the unsaturated dicarboxylic acid monomer residue of 0 weight % to 5 weight % and/or unsaturated dicarboxylic acid anhydride monomer residue; Described thermoplastic resin composition's melt flow rate (MFR) restrains/10 minutes for 3-40 under 265 ℃, 10 kilograms loads.
6. the preparation method of the moulded parts of thermoplastic resin as claimed in claim 5 is characterized in that it is by the injection moulding machine moulding.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14897696A JP3652788B2 (en) | 1996-06-11 | 1996-06-11 | Method for producing molded thermoplastic resin |
| JP148976/96 | 1996-06-11 |
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| CN1170017A CN1170017A (en) | 1998-01-14 |
| CN1091454C true CN1091454C (en) | 2002-09-25 |
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| CN97112737A Expired - Fee Related CN1091454C (en) | 1996-06-11 | 1997-06-11 | Thermoplastic resin composition, molded product and method for its production |
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| Country | Link |
|---|---|
| JP (1) | JP3652788B2 (en) |
| KR (1) | KR100364879B1 (en) |
| CN (1) | CN1091454C (en) |
| MY (1) | MY120122A (en) |
| SG (1) | SG54505A1 (en) |
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| JP3694789B2 (en) * | 2001-09-18 | 2005-09-14 | Ｊｓｒ株式会社 | Thermoplastic elastomer composition and molded article |
| DE102005023420A1 (en) * | 2005-05-20 | 2006-11-23 | Ems-Chemie Ag | Polyamide molding compounds with improved flowability, their production and their use |
| WO2008026554A1 (en) * | 2006-08-28 | 2008-03-06 | Denki Kagaku Kogyo Kabushiki Kaisha | Resin composition and molded body thereof |
| JP5363253B2 (en) * | 2009-09-09 | 2013-12-11 | 旭化成ケミカルズ株式会社 | Thermoplastic resin composition and method for producing thermoplastic resin composition |
| JP5466108B2 (en) * | 2010-08-04 | 2014-04-09 | 旭化成ケミカルズ株式会社 | Reinforced thermoplastic resin composition |
| US10308790B2 (en) * | 2017-02-13 | 2019-06-04 | Fuji Xerox Co., Ltd. | Resin composition and resin molding |
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| EP0276512A1 (en) * | 1986-12-20 | 1988-08-03 | Dsm N.V. | Thermoplastic polymer mixtures |
| JPH01234455A (en) * | 1988-03-14 | 1989-09-19 | Kanegafuchi Chem Ind Co Ltd | Thermoplastic resin composition |
| JPH01294756A (en) * | 1988-05-23 | 1989-11-28 | Ube Cycon Ltd | Modified abs resin, its production and polyamide resin composition |
| JPH0317147A (en) * | 1989-06-14 | 1991-01-25 | Daicel Chem Ind Ltd | Thermoplastic resin composition having excellent impact resistance |
| JPH0352953A (en) * | 1989-07-20 | 1991-03-07 | Mitsubishi Gas Chem Co Inc | Polyamide resin composition |
| EP0512472A1 (en) * | 1991-05-06 | 1992-11-11 | G.D. Searle & Co. | Process for preparation of alpha-alkoxy acetic acids and their salts |
| EP0576960A2 (en) * | 1992-06-29 | 1994-01-05 | BASF Aktiengesellschaft | Moulding material with a mat surface |
| JPH07316381A (en) * | 1994-05-24 | 1995-12-05 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition |
| JP3017147B2 (en) * | 1996-11-08 | 2000-03-06 | 三共株式会社 | Optically active sulfoxide derivative |
| JP3052953B1 (en) * | 1999-02-18 | 2000-06-19 | 日本電気株式会社 | Connector for overlapping connection |
-
1996
- 1996-06-11 JP JP14897696A patent/JP3652788B2/en not_active Expired - Fee Related
-
1997
- 1997-05-29 SG SG1997001774A patent/SG54505A1/en unknown
- 1997-05-29 MY MYPI97002350A patent/MY120122A/en unknown
- 1997-06-11 KR KR1019970024149A patent/KR100364879B1/en not_active IP Right Cessation
- 1997-06-11 CN CN97112737A patent/CN1091454C/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5871952A (en) * | 1981-10-23 | 1983-04-28 | Asahi Chem Ind Co Ltd | Novel thermoplastic resin composition |
| EP0276512A1 (en) * | 1986-12-20 | 1988-08-03 | Dsm N.V. | Thermoplastic polymer mixtures |
| JPH01234455A (en) * | 1988-03-14 | 1989-09-19 | Kanegafuchi Chem Ind Co Ltd | Thermoplastic resin composition |
| JPH01294756A (en) * | 1988-05-23 | 1989-11-28 | Ube Cycon Ltd | Modified abs resin, its production and polyamide resin composition |
| JPH0317147A (en) * | 1989-06-14 | 1991-01-25 | Daicel Chem Ind Ltd | Thermoplastic resin composition having excellent impact resistance |
| JPH0352953A (en) * | 1989-07-20 | 1991-03-07 | Mitsubishi Gas Chem Co Inc | Polyamide resin composition |
| EP0512472A1 (en) * | 1991-05-06 | 1992-11-11 | G.D. Searle & Co. | Process for preparation of alpha-alkoxy acetic acids and their salts |
| EP0576960A2 (en) * | 1992-06-29 | 1994-01-05 | BASF Aktiengesellschaft | Moulding material with a mat surface |
| JPH07316381A (en) * | 1994-05-24 | 1995-12-05 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition |
| JP3017147B2 (en) * | 1996-11-08 | 2000-03-06 | 三共株式会社 | Optically active sulfoxide derivative |
| JP3052953B1 (en) * | 1999-02-18 | 2000-06-19 | 日本電気株式会社 | Connector for overlapping connection |
Also Published As
| Publication number | Publication date |
|---|---|
| MY120122A (en) | 2005-09-30 |
| JP3652788B2 (en) | 2005-05-25 |
| KR980002147A (en) | 1998-03-30 |
| KR100364879B1 (en) | 2003-04-21 |
| JPH09328590A (en) | 1997-12-22 |
| SG54505A1 (en) | 1998-11-16 |
| CN1170017A (en) | 1998-01-14 |
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