CN102282209B - Rubber-modified thermoplastic resin composition, injection molded article comprising the same, and washing machine lid using the same - Google Patents

Rubber-modified thermoplastic resin composition, injection molded article comprising the same, and washing machine lid using the same Download PDF

Info

Publication number
CN102282209B
CN102282209B CN2010800046664A CN201080004666A CN102282209B CN 102282209 B CN102282209 B CN 102282209B CN 2010800046664 A CN2010800046664 A CN 2010800046664A CN 201080004666 A CN201080004666 A CN 201080004666A CN 102282209 B CN102282209 B CN 102282209B
Authority
CN
China
Prior art keywords
styrene
quality
analog copolymer
vinylbenzene
polymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2010800046664A
Other languages
Chinese (zh)
Other versions
CN102282209A (en
Inventor
渡边真太郎
野口哲央
户谷英树
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Denka Co Ltd
Original Assignee
Denki Kagaku Kogyo KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Denki Kagaku Kogyo KK filed Critical Denki Kagaku Kogyo KK
Publication of CN102282209A publication Critical patent/CN102282209A/en
Application granted granted Critical
Publication of CN102282209B publication Critical patent/CN102282209B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C08F212/10—Styrene with nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F37/00—Details specific to washing machines covered by groups D06F21/00 - D06F25/00
    • D06F37/26—Casings; Tubs
    • D06F37/28—Doors; Security means therefor
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00 
    • D06F39/12—Casings; Tubs
    • D06F39/14—Doors or covers; Securing means therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Provided is a resin composition having excellent chemical resistance, transparency, color, heat resistance, and impact resistance. A rubber-modified thermoplastic resin composition comprising a predetermined styrene-methacrylic acid ester copolymer, a predetermined styrene-vinyl cyanide copolymer, and a predetermined graft copolymer at a specific mixture ratio and under specific conditions has an excellent balance between the chemical resistance, transparency, color, heat resistance, and impact resistance that are generally difficult to simultaneously satisfy and have a relationship such that improvement of one leads to deterioration of another.

Description

Rubber modified thermoplastic resin composition, its injection-molded article and used the washing machine cover of this injection-molded article
Technical field
The present invention relates to rubber modified thermoplastic resin composition, its injection-molded article and used the washing machine cover of this injection-molded article.
Background technology
Usually, because ABS resin has good shock-resistance, mechanical properties, forming process, therefore be widely used in household appliances, electric/electronic parts, OA equipment, pinball game parts etc., especially in the consideration based on function and design aspect, require to have in the purposes of transparency and use Transparent ABS Resin (patent documentation 1).But, the defect of this Transparent ABS Resin is, insufficient to the patience of the organic solvent of alcohol etc. or washing composition etc., because of its purposes with environment for use is broken or crackle, thereby cause commodity value impaired, thereby need to improve the chemical resistant properties of this Transparent ABS Resin.In addition, the defect of this Transparent ABS Resin also is, due to the hot blast that is exposed to moisture eliminator etc., with around kitchen or hot water, the steam of kitchen and bath facilities contact and produce distortion, thereby need to improve its thermotolerance.
As the chemical-resistant method that improves these ABS resin, the known proportional method that contains that is improved vinyl cyanide, proposed various so-called high-nitrile thermoplastic resin compositions.
For example, the resin combination that multipolymer and grafting analog copolymer by styrene-acrylonitrile-methyl methacrylate form has been proposed in patent documentation 2～4.In addition, the resin combination that the alkyl acrylate that to have proposed by carbonatoms in patent documentation 5 be 1～4 and multipolymer, styrene-acrylonitrile copolymer and the grafting analog copolymer of methyl methacrylate form.And, the resin combination that the multipolymer by acrylic resin, ABS resin, vinyl cyanide and aromatic vinyl forms has been proposed in patent documentation 6.
Patent documentation 1: Japan's Patent Application Publication communique " JP 2001-226547 communique "
Patent documentation 2: Japan's Patent Application Publication communique " JP 2002-179873 communique "
Patent documentation 3: Japan's Patent Application Publication communique " JP 2002-212369 communique "
Patent documentation 4: Japan's Patent Application Publication communique " JP 2005-317093 communique "
Patent documentation 5: Japan's Patent Application Publication communique " Unexamined Patent 2-274747 communique "
Patent documentation 6: Japan's Patent Application Publication communique " JP 2006-2038 communique "
Summary of the invention
But the prior art of above-mentioned document record for example has the following leeway of improving.
The first, in patent documentation 2～4, the defect of the resin combination consisted of multipolymer and the grafting analog copolymer of styrene-acrylonitrile-methyl methacrylate is, its color and luster is variation along with the increase of nitrile content.
Second, in patent documentation 5, the defect of the resin combination that the alkyl acrylate that is 1～4 by carbonatoms and the multipolymer of methyl methacrylate, styrene-acrylonitrile copolymer and grafting analog copolymer form is, its transparency is poor, in addition, in order to improve thermostability, by the alkyl acrylate copolymerization, thereby its thermotolerance is poor.
The 3rd, in patent documentation 6, similarly there are the poor problem of transparency in the resin combination consisted of the multipolymer of acrylic resin, ABS resin, vinyl cyanide and aromatic vinyl and the situation of patent documentation 5.
The inventor has carried out wholwe-hearted research, found that: with specific condition and specific proportioning, form and contain specific vinylbenzene-Polymers, specific styrene-acrylonitrile analog copolymer and the specific resulting rubber modified thermoplastic resin composition of grafting analog copolymer can be realized good chemical resistant properties, transparency, color and luster, thermotolerance and shock-resistance also make it reach good balance, and above-mentioned chemical resistant properties, transparency, color and luster, thermotolerance and shock-resistance are difficult to be met owing to carrying on the back each other inverse relation under normal conditions simultaneously.
That is, according to the present invention, provide a kind of rubber modified thermoplastic resin composition, it contains: vinylbenzene-Polymers (A), styrene-acrylonitrile analog copolymer (B) and grafting analog copolymer (C).And, above-mentioned (A) composition is that vinylbenzene-Polymers is configured to: when the total quality of styrene monomer unit and methyl acrylic ester monomeric unit is 100 quality %, and the methyl acrylic ester monomeric unit of the styrene monomer unit that contains 1～15 quality %, 85～99 quality %.In addition, above-mentioned (B) composition is that the styrene-acrylonitrile analog copolymer is configured to: when the total quality of styrene monomer unit and vinyl cyanide monomeric unit is 100 quality %, and the vinyl cyanide monomeric unit of the styrene monomer unit that contains 80～90 quality %, 10～20 quality %.And, above-mentioned (C) composition is that the grafting analog copolymer is configured to: by making styrene monomer, methyl acrylic ester monomer and vinyl cyanide monomer and rubber-like elastic body copolymerization, obtain, the total light transmittance of described grafting analog copolymer formed body of the thick 2mm of gained after impact briquetting is more than 85%.
And, when when above-mentioned (A) composition, (B) composition and (C) the total quality of composition is 100 quality %, above-mentioned (C) composition of above-mentioned (A) composition that contains 15～54 quality %, above-mentioned (B) composition of 20～63 quality %, 10～50 quality %.In addition, the specific refractory power of the mixture of above-mentioned (A) composition and above-mentioned (B) composition, with the difference of the specific refractory power of above-mentioned (C) composition be below 0.005.And, when (A) composition with (B) when the total quality of composition is 100 quality %, at (A) composition with (B) in the mixture of composition, the content of vinyl cyanide monomeric unit is in the scope of 6～15 quality %.
According to these conditions and proportioning, form, owing to specific condition and specific proportioning, forming and containing specific vinylbenzene-Polymers, specific styrene-acrylonitrile analog copolymer and specific grafting analog copolymer, therefore, can obtain chemical resistant properties, transparency, color and luster, thermotolerance, excellent impact resistance and reach the rubber modified thermoplastic resin composition of good balance, and above-mentioned chemical resistant properties, transparency, color and luster, thermotolerance, shock-resistance are difficult to be met owing to carrying on the back each other inverse relation under normal conditions simultaneously.
In addition, according to the present invention, provide the injection-molded article obtained by the injection moulding of above-mentioned rubber modified thermoplastic resin composition.Owing to having used above-mentioned chemical resistant properties, transparency, color and luster, thermotolerance, excellent impact resistance and having reached well balanced rubber modified thermoplastic resin composition, therefore, the injection-molded article obtained by the injection moulding of above-mentioned rubber modified thermoplastic resin composition can be realized equally good chemical resistant properties, transparency, color and luster, thermotolerance, shock-resistance and make it reach good balance.
And, according to the present invention, provide the washing machine cover as parts by above-mentioned injection-molded article.Above-mentionedly there is good chemical resistant properties, transparency, color and luster, thermotolerance, shock-resistance and make it reach the injection-molded article of good balance owing to having used, therefore, use this injection-molded article can realize equally good chemical resistant properties, transparency, color and luster, thermotolerance, shock-resistance and make it reach good balance as the washing machine cover of parts.
The accompanying drawing explanation
Fig. 1 is the stereographic map that the test method for the resistance to chemical reagents to embodiment/comparative example describes, wherein, in this test method, stamping forming test film (350 * 20 * 2mmt) is placed on Bergen (Bergen) formula 1/4 oval fixture and is tested.
Embodiment
The explanation of<term >
In this explanation, "～" mark mean " more than " and " following ", comprise respectively higher limit and lower value that "～" is represented.For example, more than, the record of " A～B " means A and below B.In addition, " contain " and also comprise " in fact by ... form " and the implication of " comprising ... ".
Below, embodiments of the present invention are elaborated.
<rubber modified thermoplastic resin composition >
According to present embodiment, provide the rubber modified thermoplastic resin composition that contains vinylbenzene-Polymers (A), styrene-acrylonitrile analog copolymer (B) and grafting analog copolymer (C).Because the rubber modified thermoplastic resin composition of present embodiment forms and contains mentioned component (A), composition (B) and composition (C) with aftermentioned specified conditions and proportioning, therefore, can realize good chemical resistant properties, the transparency, color and luster, thermotolerance, shock-resistance and make it reach good balance, and above-mentioned chemical resistant properties, the transparency, color and luster, thermotolerance, shock-resistance are difficult to be met owing to carrying on the back each other inverse relation under normal conditions simultaneously.
(i) (A) composition: vinylbenzene-Polymers
Above-mentioned (A) composition is the vinylbenzene-Polymers that comprises styrene monomer unit and methyl acrylic ester monomeric unit.The structure of this Polymers is not subject to particular restriction, can use the multipolymer of the arbitrary structures that comprises styrene monomer unit and methyl acrylic ester monomeric unit.; with regard to multipolymer; rough classification is random copolymers, alternating copolymer, periodic copolymer, these 4 kinds of structures of segmented copolymer; segmented copolymer a kind of has grafting analog copolymer (being combined with multipolymer different types of graft polymer chain, branched structure becoming on the macromolecular chain of main chain), and the structure of above-mentioned multipolymer can be any one in above-mentioned 4 kinds of structures.
The styrene monomer unit used as above-mentioned (A) composition, can enumerate: vinylbenzene, alpha-methyl styrene, p-methylstyrene, o-methyl styrene, a vinyl toluene, ethyl styrene, p-tert-butylstyrene, chlorostyrene, bromostyrene etc., viewpoint from mixing property and thermolysis stability, optimization styrene, alpha-methyl styrene, particularly preferably vinylbenzene.These styrene monomers can use separately also can be used together two or more.About these styrene monomer unit, for example, can be prepared by the raw material formed by corresponding monomer or be prepared by the raw material that wherein comprises corresponding monomer.
The methyl acrylic ester monomeric unit used as above-mentioned (A) composition, can enumerate: the methacrylic esters such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, from giving resin stable on heating viewpoint, preferably use methyl methacrylate.These methyl acrylic ester monomers can use separately also can be used together two or more.About these methyl acrylic ester monomeric units, can be prepared by the raw material formed by corresponding monomer or be prepared by the raw material that wherein comprises corresponding monomer.
In addition, preferably, in above-mentioned vinylbenzene-Polymers, when the total quality of styrene monomer unit and methyl acrylic ester monomeric unit is 100 quality %, contained styrene monomer unit is in the scope of 1～15 quality %, and the methyl acrylic ester monomeric unit is in the scope of 85～99 quality %.In addition, further preferably, contained styrene monomer unit is in the scope of 2～13 quality %, and the methyl acrylic ester monomeric unit is in the scope of 87～98 quality %.This be because: if the styrene monomer unit below 15 quality %, the styrene monomer unit is fewer, the transparency of the rubber modified thermoplastic resin composition that contains this vinylbenzene-Polymers is just higher.In addition, also because: if the styrene monomer unit is more than 1 quality %, the styrene monomer unit is more, and the thermostability of the rubber modified thermoplastic resin composition that contains this vinylbenzene-Polymers is just better, and transparency, color and luster are just higher.
In addition, above-mentioned (A) composition is that the weight-average molecular weight (Mw) of vinylbenzene-Polymers is preferably 70000～100000, is particularly preferably 80000～90000.If this weight-average molecular weight is more than 70000 or more than 80000, the chemical resistant properties that comprises the rubber modified thermoplastic resin composition of this vinylbenzene-Polymers improves.In addition, if this weight-average molecular weight is below 100000 or below 90000, the melt mass flow rate (MFR) of the rubber modified thermoplastic resin composition that contains this vinylbenzene-Polymers can be maintained to higher level, thereby can maintain well formability.In addition, said weight-average molecular weight is measured by following gel permeation chromatography (GPC) method here.
Device name: SYSTEM-21 Shodex (clear and electrician company system)
Chromatographic column: by 3 PL Gel MIXED-B series connection
Temperature: 40 ℃
Detect: the differential refractometer
Solvent: THF (tetrahydrofuran (THF))
Concentration: 2 quality %
Typical curve: Application standard polystyrene (PS) (PL company system) is made, and weight-average molecular weight (Mw) means with the PS scaled value.
(ii) (B) composition: styrene-acrylonitrile analog copolymer
Above-mentioned (B) composition is the styrene-acrylonitrile analog copolymer that comprises styrene monomer unit and vinyl cyanide monomeric unit.The structure of this styrene-acrylonitrile analog copolymer is not particularly limited, and can use the multipolymer of the arbitrary structures that contains styrene monomer unit and vinyl cyanide monomeric unit.; with regard to multipolymer; rough classification is random copolymers, alternating copolymer, periodic copolymer, these 4 kinds of structures of segmented copolymer; segmented copolymer a kind of has grafting analog copolymer (being combined with multipolymer different types of graft polymer chain, branched structure becoming on the macromolecular chain of main chain), and the structure of above-mentioned multipolymer can be any one in above-mentioned 4 kinds of structures.
The styrene monomer unit used as above-mentioned (B) composition, can enumerate: vinylbenzene, alpha-methyl styrene, p-methylstyrene, o-methyl styrene, a vinyl toluene, ethyl styrene, p-tert-butylstyrene, chlorostyrene, bromostyrene etc., viewpoint from mixing property and thermolysis stability, optimization styrene, alpha-methyl styrene, particularly preferably vinylbenzene.These styrene monomers can use separately also can be used together two or more.About these styrene monomer unit, for example, can be prepared by the raw material formed by corresponding monomer or be prepared by the raw material that wherein comprises corresponding monomer.
The vinyl cyanide monomeric unit used as above-mentioned (B) composition, can enumerate: vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, fumaric acid nitrile etc., from give chemical resistant properties and with the viewpoint of the consistency of vinylbenzene-Polymers, preferably vinyl cyanide.These vinyl cyanide monomers can use separately also can be used together two or more.About these vinyl cyanide monomeric units, for example, can be prepared by the raw material formed by corresponding monomer or be prepared by the raw material that wherein comprises corresponding monomer.
In addition, preferably, at above-mentioned (B) composition, be in the styrene-acrylonitrile analog copolymer, when the total quality of styrene monomer unit and vinyl cyanide monomeric unit is 100 quality %, contained styrene monomer unit is in 80～90% scope, and the vinyl cyanide monomeric unit is in the scope of 10～20 quality %.In addition, further preferably, contained styrene monomer unit is in the scope of 80～88 quality %, and the acrylonitrile monemer unit is in the scope of 12～20 quality %.And, particularly preferably being, contained styrene monomer unit is in the scope of 80～84 quality %, and the acrylonitrile monemer unit is in the scope of 16～20 quality %.This be because, if the acrylonitrile monemer unit below 20 quality %, the acrylonitrile monemer unit is fewer, the transparency of the rubber modified thermoplastic resin composition that contains this styrene-acrylonitrile analog copolymer is just higher.In addition, also because, if the acrylonitrile monemer unit more than 10 quality %, the acrylonitrile monemer unit is more, the chemical resistant properties of the rubber modified thermoplastic resin composition that contains this styrene-acrylonitrile analog copolymer is just higher.
In addition, above-mentioned (B) composition is that the weight-average molecular weight (Mw) of styrene-acrylonitrile analog copolymer is preferably 100000～190000, is particularly preferably 160000～180000.If the weight-average molecular weight of this styrene-acrylonitrile analog copolymer is more than 100000 or more than 160000, can maintain well the shock-resistance of the rubber modified thermoplastic resin composition that contains this styrene-acrylonitrile analog copolymer, if the weight-average molecular weight of this styrene-acrylonitrile analog copolymer, below 190000 or below 180000, can maintain the formability of the rubber modified thermoplastic resin composition that contains this styrene-acrylonitrile analog copolymer well.
(iii) (C) composition: grafting base polymer
Above-mentioned (C) composition is the grafting analog copolymer that styrene monomer, methyl acrylic ester monomer, vinyl cyanide monomer and rubber-like elastic body copolymerization are obtained.The structure of this grafting analog copolymer is not particularly limited, and can use the analog copolymer of grafting arbitrarily by styrene monomer, methyl acrylic ester monomer, vinyl cyanide monomer and rubber-like elastic body copolymerization are obtained.That is, so long as following polymkeric substance get final product: be combined with multipolymer different types of graft polymer chain, branched structure becoming on the macromolecular chain of main chain.
The rubber-like elastic body used as above-mentioned (C) composition, so long as meet the definition of general rubber-like elastic body, even slightly apply, external force also shows larger unit elongation and the macromolecular compound that can restore in the moment of removing external force gets final product, for example can use: polyhutadiene, butadiene-styrene copolymer, perbutan, the butadiene-propylene acid copolymer, styrene-butadiene-styrene block copolymer, polyisoprene, styrene-isoprene copolymer equiconjugate polydiene, and their hydrogen affixture, ethyl propenoate, the acrylic rubbers such as butyl acrylate, ethylene-alpha-olefin-polyene copolymer, ethene-alpha-olefin copolymer, silicone rubber, silicone-acrylic rubber multipolymer etc., these materials can be separately with also combining two or more the use.Wherein, from color and luster and the viewpoint of giving shock-resistance, particularly preferably contain the rubber-like elastic body of styrene-butadiene copolymer as principal constituent.
In addition, when the rubber-like elastic body used at above-mentioned (C) composition adopts styrene-butadiene copolymer, the ratio of vinylbenzene and divinyl is not particularly limited.Preferably, when the total quality of vinylbenzene and divinyl is 100 quality %, styrene content is that 15～50 quality %, butadiene content are 50～85 quality %, and further optimization styrene content is the styrene-butadiene copolymer that 20～45 quality %, butadiene content are 55～80 quality %.The specific refractory power of the mixture of above-mentioned (A) composition and above-mentioned (B) composition, with (C) difference of the specific refractory power of composition be 0.005 when following, in the situation that the styrene content in the styrene-butadiene copolymer that (C) composition is used is more than 20 quality %, containing styrene-butadiene copolymer increases as the specific refractory power of the rubber-like elastic body of principal constituent, therefore can improve the blending ratio of the styrene-acrylonitrile analog copolymer (B) of rubber modified thermoplastic resin composition, chemical resistant properties improves.In addition, in the situation that this styrene content is below 45 quality %, owing to further improving as elastomeric character, so the impact strength of rubber modified thermoplastic resin composition improves.
The styrene monomer used as above-mentioned (C) composition, can enumerate: vinylbenzene, alpha-methyl styrene, p-methylstyrene, o-methyl styrene, a vinyl toluene, ethyl styrene, p-tert-butylstyrene, chlorostyrene, bromostyrene etc., from with above-mentioned (A) composition and the consistency of above-mentioned (B) composition and the viewpoint of mixing property, optimization styrene, alpha-methyl styrene, be particularly preferably vinylbenzene.These styrene monomers can use separately also can be used together two or more.
The methyl acrylic ester monomer used as above-mentioned (C) composition, can enumerate the methacrylic esters such as methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, from consistency and the stable on heating viewpoint with above-mentioned (A) composition and above-mentioned (B) composition, preferably use methyl methacrylate.These methyl acrylic ester monomers can use separately also can be used together two or more.
The vinyl cyanide monomer used as above-mentioned (C) composition, can enumerate: vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, fumaric acid nitrile etc., from the consistency with above-mentioned (A) composition and above-mentioned (B) composition and give the chemical-resistant viewpoint, preferred vinyl cyanide.These vinyl cyanide monomers can use separately also can be used together two or more.
Here, as the total light transmittance of graft copolymer formed body of the thick 2mm of gained after impact briquetting of above-mentioned (C) composition, be preferably more than 85%, more preferably more than 88%.If the total light transmittance of this impact briquetting body is more than 85% or more than 88%, the transparency for the resin combination that makes the body formed material of this impact briquetting also improves.
In addition, for the total light transmittance that obtains the impact briquetting body is more than 85% or 88% above grafting analog copolymer, do not need complicated especially preparation, can easily obtain by the following method: grafting is formed and adjusted, make rubber-like elastic body specific refractory power, with by styrene monomer, methyl acrylic ester monomer and vinyl cyanide monomer copolymerization and the difference of specific refractory power of grafting reduce as far as possible
In addition, in above-mentioned (C) composition, can also be in the scope of the action effect of the rubber modified thermoplastic resin composition that does not damage present embodiment, but and carry out the grafting of rubber-like elastic body with other the vinyl monomer of copolymerization of acrylate, methacrylic ester etc. such as ethyl propenoate, methacrylic ester, propyl methacrylate, butyl methacrylate, methacrylic acid stearyl.
In addition, in above-mentioned (C) composition, the volume average particle size of grafting analog copolymer is preferably 0.25～0.80 μ m, can make thus the rubber modified thermoplastic resin composition that contains this grafting analog copolymer obtain good transparency, shock-resistance, is particularly preferably 0.30～0.70 μ m.If to be 0.25 μ m above or more than 0.30 μ m excellent impact resistance, 0.80 μ m can maintain transparency well with next if, therefore preferably for this volume average particle size.In addition, said volume average particle size refers to here, ethylenic copolymer is disperseed in DMF (DMF) and the median particle diameter of the volume reference measured by scattering of light formula particle size distribution device.
(iv) proportioning of rubber modified thermoplastic resin composition forms
In the rubber modified thermoplastic resin composition of present embodiment, at above-mentioned (A) composition, (B) composition and (C) when the total quality of composition is 100 quality %, in order to obtain chemical resistant properties, transparency, thermotolerance, the rubber modified thermoplastic resin composition of excellent impact resistance, preferably contained above-mentioned (A) composition (vinylbenzene-Polymers) is in the scope of 15～54 quality %, above-mentioned (B) composition (styrene-acrylonitrile analog copolymer) is in the scope of 20～63 quality %, above-mentioned (C) composition (grafting analog copolymer) is in the scope of 10～50 quality %.
In addition, when at above-mentioned (A) composition, (B) composition and (C) the total quality of composition is 100 quality %, in order to obtain the rubber modified thermoplastic resin composition of chemical resistant properties, transparency, thermotolerance, excellent impact resistance, further preferably contained above-mentioned (A) composition (vinylbenzene-Polymers) in the scope of 20～40 quality %, above-mentioned (B) composition (styrene-acrylonitrile analog copolymer) in the scope of 20～40 quality %, above-mentioned (C) composition (grafting analog copolymer) is in the scope of 15～45 quality %.
In addition, in the rubber modified thermoplastic resin composition of present embodiment, the specific refractory power of the mixture of above-mentioned (A) composition (vinylbenzene-Polymers) and above-mentioned (B) composition (styrene-acrylonitrile analog copolymer), with the difference of the specific refractory power of above-mentioned (C) composition (grafting analog copolymer), be preferably below 0.005, be particularly preferably below 0.003.In the situation that this refringence is below 0.005 or is 0.003 following, can maintain well the transparency of gained rubber modified thermoplastic resin composition.In addition, here said specific refractory power obtains as follows: the resin combination that mixture or above-mentioned (C) composition by impact briquetting (A) composition above-mentioned by take and above-mentioned (B) composition is principal constituent, the products formed for preparing thick 2mm, re-use Abbe refractometer and measured.
And, in the rubber modified thermoplastic resin composition of present embodiment, at above-mentioned (A) composition with (B) when the total quality of composition is 100 quality %, the content quality % of the vinyl cyanide monomeric unit in the mixture of above-mentioned (A) composition (vinylbenzene-Polymers) and above-mentioned (B) composition (styrene-acrylonitrile analog copolymer) is preferably in the scope of 6～15 quality %.If the content of this acrylonitrile monemer unit is more than 6 quality %, can maintain well the chemical resistant properties of gained rubber modified thermoplastic resin composition, yellow enhancing can be suppressed if the content of this acrylonitrile monemer unit is 15 quality % with next, therefore color and luster can be maintained well.
(v) preparation method of rubber modified thermoplastic resin composition
Above-mentioned vinylbenzene-the Polymers (A) of the rubber modified thermoplastic resin composition of formation present embodiment and the preparation method of styrene-acrylonitrile analog copolymer (B) are not particularly limited, can use the polymerization of any known such as mass polymerization, suspension polymerization, body-suspension polymerization, solution polymerization process, emulsion polymerization, but in order to obtain thermotolerance, better color and luster and transparency, above-mentioned (A) composition and (B) each multipolymer of composition preferably by the continuous bulk polymerization method, carry out polymerization.
On the other hand, the preparation method of the above-mentioned grafting analog copolymer (C) of the rubber modified thermoplastic resin composition of formation present embodiment is not particularly limited similarly, can use the polymerization of any known such as emulsion polymerization, mass polymerization, body-suspension polymerization, solution polymerization process, wherein, from the viewpoint of the outward appearance of transparency and injection-molded article, be applicable to adopting emulsion polymerization.In addition, in arbitrary preparation method, when preparation grafting analog copolymer (C), even also it doesn't matter for the vinylbenzene-Polymers (A) of the formation of a generation part simultaneously external phase.In addition, can use any method of intermittence type polymerization method, continous way polymerization.
The polymerization of these vinylbenzene-Polymers (A), styrene-acrylonitrile analog copolymer (B) and grafting analog copolymer (C) all can be used the azo-compound of Diisopropyl azodicarboxylate, azo two cyclohexanenitriles etc. or benzoyl peroxide, peroxidized t-butyl perbenzoate, the peroxidation 2 ethyl hexanoic acid tert-butyl ester, ditertiary butyl peroxide, dicumyl peroxide, 3, and the organo-peroxide of 3-bis-(t-butyl peroxy) ethyl butyrate etc. is as polymerization starter.In addition, can also add as required tert-dodecyl mercaptan, positive Dodecyl Mercaptan, 4-methyl-2,4-phenylbenzene-1-amylene, as molecular weight regulator, adds diisobutyl adipate or butyl benzyl phthalate etc. as softening agent.
In the preparation of the rubber modified thermoplastic resin composition of present embodiment, vinylbenzene-Polymers (A), styrene-acrylonitrile analog copolymer (B), and the blending means of grafting analog copolymer (C) be not particularly limited, such as making with the following method: by known mixing devices such as Henschel mixer, tumbler mixers, carry out pre-mixing, afterwards, use the forcing machines such as single screw extrusion machine or twin screw extruder to carry out mixing, evenly mix thus.
In the rubber modified thermoplastic resin composition of present embodiment, except vinylbenzene-Polymers (A), styrene-acrylonitrile analog copolymer (B), and grafting analog copolymer (C), can also mix as required the additive of any known.For example, in order to improve mobility, release property, can plastic binder, lubricant, silicone oil etc.In addition, in order to give weathering resistance, can the mixed light stablizer, UV light absorber.In addition, can the illustration antioxidant, static inhibitor, tinting material, pigment, fuel, lubricant, anti-hard caking agent, whipping agent, frothing aid, linking agent, crosslinking coagent etc.
Usining the rubber-modified styrene resin composition of present embodiment while being processed into the shape of particle etc. as various raw materials, about mixing, melt extruding, be not particularly limited, can utilize known method.Such as following described method is arranged: in advance by tumbler mixer or Henschel mixer etc. by vinylbenzene-Polymers (A), styrene-acrylonitrile analog copolymer (B), and each raw material of grafting analog copolymer (C) etc. evenly mix, resupply to single screw extrusion machine or twin screw extruder etc. and carry out melting mixing, afterwards, as particle, adjusted.As above the rubber-modified styrene resin composition of the present embodiment of gained is such as being processed into various formed bodys and offering practical application by methods such as injection moulding, compressed moulding and extrusion mouldings, because the rubber-modified styrene resin composition of present embodiment can be realized good chemical resistant properties, transparency, color and luster, thermotolerance, shock-resistance and make it reach good balance, the injection-molded article therefore injection moulding of this rubber-modified styrene resin composition formed is very good aspect practical application.
<injection-molded article >
Making above-mentioned rubber modified thermoplastic resin composition molding by injection moulding is predetermined shape, obtains thus the injection-molded article of present embodiment.The injection-molded article of present embodiment is particularly effective when being applied to be required to meet chemical resistant properties, transparency, color and luster, thermotolerance, shock-resistance and make these characteristics reach well balanced container, container cover material.
Need only and made by above-mentioned rubber modified thermoplastic resin composition for the raw material that obtains this injection-molded article, especially shape etc. is not limited, but it is good that the operability when making injection moulding, formability etc. become, and preferably has granular shape.
From the viewpoint of formability and color and luster, the temperature of the injection moulding of above-mentioned rubber modified thermoplastic resin composition is preferably in the scope of 180～280 ℃ for example.If this injection temperature is more than 180 ℃, the mobility of rubber modified thermoplastic resin composition increases easily and is filled in mould, thereby formability improves.In addition, if make this injection temperature below 280 ℃, can suppress injection-molded article and burn phenomenon.
<washing machine cover >
The washing machine cover of present embodiment is to have used the washing machine cover of above-mentioned injection-molded article as parts.In addition, said washing machine refers to the equipment usually washed in semi-automatic or full automatic mode here.But the meaning of not getting rid of the hand-driven washing machine machine that manually carries out the rinse bath rotation.All the time, washing machine cover is used opaque parts usually.Therefore but in recent years,, due to the raising of the requirement to designability, need to make lid there is the material of transparency and good color and luster.In addition, washing machine cover may be due to splashing of the detergent solution in rinse bath etc. and contacts continually chemical solutions, due to the rotation of rinse bath and user's switch washing machine lid and easily impacted, and, also due to the heating of the Mechanical Driven section of washing machine internal and user, use hot water to be washed to contact the detergent solution of high temperature.Therefore, just require washing machine can balance to meet well the characteristic of chemical resistant properties, transparency, colourity, thermotolerance, shock-resistance.To this, above-mentioned injection-molded article can meet chemical resistant properties, transparency, colourity, thermotolerance, shock-resistance and make these characteristics reach good balance, therefore is applicable to this transparent cover.
In addition, the washing machine cover of present embodiment is without all being made by above-mentioned injection-molded article, for example, can make with above-mentioned injection-molded article the parts of the transparent windows of the rinse bath inside that is available for users to observe washing machine.Thus, can be only in needed scope, use above-mentionedly can meet chemical resistant properties, transparency, colourity, thermotolerance, shock-resistance and make these characteristics reach the injection-molded article of good balance, therefore can reduce the preparation cost of washing machine cover.
In addition, the rubber modified thermoplastic resin composition illustrated by above-mentioned form and embodiment etc. does not form limitation of the invention, is for carrying out the disclosed content of illustration.Technical scope of the present invention is limited by the content of claims, carries out various design alterations in the technical scope of the invention that those skilled in the art can put down in writing at claims.
For example, in the above-described embodiment, the rubber modified thermoplastic resin composition comprises vinylbenzene-Polymers (A), styrene-acrylonitrile analog copolymer (B), reaches grafting analog copolymer (C), but does not get rid of resin or the multipolymer that comprises kind in addition.For example, can also be according to purposes of rubber modified thermoplastic resin composition etc., in the scope of not damaging the object of the invention, the resin or the multipolymer that contain other kinds such as polystyrene, MS resin, AS resin, ABS resin, acrylic resin, polycarbonate.
embodiment
Below, by embodiment, the invention will be further described, but the present invention is not subject to the restriction of embodiment.In addition, the present embodiment is put down in writing " section " and " ratio ", as long as no specified otherwise, all mean with quality criteria.
<measuring method >
Below, the measuring method of each physics value of the various measured values that form the vinylbenzene-Polymers, styrene-acrylonitrile analog copolymer, grafting analog copolymer and the rubber modified thermoplastic resin composition that use in the present embodiment and execution is described.
(1) resin of styrene copolymer form, acrylonitrile content: multipolymer is dissolved in to deuterochloroform and is prepared into 2% solution and be used as measuring material, use FT-NMR (NEC company FX-90Q type processed) mensuration 13c, the peak area by vinylbenzene, methyl methacrylate, vinyl cyanide is calculated.
(2) composition of the grafting of grafting analog copolymer: at the temperature of 23 ℃, in methylethylketone, stir the grafting analog copolymer 24 hours, under the condition that is 20000rpm for-9 ℃, rotating speed in temperature, centrifugation by 60 minutes separates Their Insoluble Components, afterwards, and standing 30 minutes.The supernatant liquor of minute getting the solution after centrifugation adds methyl alcohol again, makes not carry out the vinylbenzene of grafting-Polymers precipitation.Collect this throw out, it is dissolved in to deuterochloroform, re-use FT-NMR (NEC company FX-90Q type processed) and obtain composition.In addition, in these grafting analog copolymers, with the composition of the vinylbenzene-Polymers of rubber-like elastic body grafting with the composition of the vinylbenzene-Polymers of rubber-like elastic body grafting, be not considered identical composition, therefore, the composition using this measured value as the vinylbenzene-Polymers with the rubbery polymer grafting.
(3) specific refractory power of multipolymer: prepare the products formed of thick 2mm by impact briquetting, use the Abbe refractometer (DR-M2) of Atago company system to be measured.
(4) specific refractory power of multipolymer: prepare the products formed of thick 2mm by impact briquetting, use the Abbe refractometer (DR-M2) of Atago company system to be measured.
(5) total light transmittance, mist degree: according to ASTM D-1003, use Japanese electric look industrial haze meter processed (NDH-2000) to be measured.If total light transmittance is more than 88%, mist degree is 7% transparency can be judged as well with next.
(6) color and luster: use Japanese electric look company color difference meter processed (∑-80) to measure the b value by light transmission method.If the b value is that 5 to be judged as color and luster good with next.
(7) MFR: use the sample particle, according to JIS K6874, measured under 220 ℃, the load condition that is 10kg in temperature.
(8) Charpy impact intensity: use toshiba machine (strain) company's system (IS-80CNV), under the condition that is 220 ℃ at barrel zone temperature, be shaped to the test film of size 12.7 * 64 * 6.4mm.Use this test film, measured according to ISO 179-2.If Charpy impact intensity is 5kJ/m 2above, can be judged as shock-resistance good.
(9) vicat softening temperature: use toshiba machine (strain) company injection moulding machine processed (IS-80CNV), under the condition that is 220 ℃ at barrel zone temperature, be shaped to the test film of size 12.7 * 64 * 6.4mm.Use this test film, according to JIS K7206, measured under the condition that is 49.0N in load.If vicat softening temperature is more than 100 ℃, thermotolerance can be judged as good.
(10) the rubber volume average particle size of grafting analog copolymer: the counting Ku Erte sreen analysis calculating instrument (LS230) of Beckman Coulter Inc.'s system is measured.
Here said volume average particle size refers to, make grafting analog copolymer (C) and rubber modified thermoplastic resin composition dissolves in N, dinethylformamide (DMF), and the median particle diameter of the volume reference of measuring by scattering of light formula particle size distribution device.
(11) chemical resistant properties: stamping forming test film (350 * 20 * 2mmt) is fixed on the oval fixture of Bergen formula 1/4 shown in Fig. 1 along curvature, evenly be coated with the object chemical substance of 20g, at 23 ℃, under the condition of humidity 55%RH, place after 48 hours, a situation arises to confirm crazing (CRAZE) and crackle (crack), calculate critical strain ε (%) by following formula, critical strain ε is less than to 0.3% sample be denoted as *, the sample of 0.3-0.6% is denoted as △, the sample of 0.6-0.9% is denoted as zero, sample more than 0.9% is denoted as ◎, zero and ◎ mean that chemical resistant properties is good.In addition, chemical substance adopts " ア タ Star Network " (weakly alkaline washing synthetic detergent that Japanese Kao company produces), " マ ジ Network Star リ Application " (alkaline household detergent that Japanese Kao company produces).
&epsiv; = b 2 a 2 { 1 - ( a 2 - b 2 ) X 2 a 4 } - 3 2 &times; t &times; 100
In formula,
ε: critical strain (%)
The major axis (mm) of a:1/4 elliptic method fixture
The minor axis (mm) of b:1/4 elliptic method fixture
T: test film thickness (mm)
X: crackle origination point (mm)
The preparation example of<multipolymer >
(a) preparation method of vinylbenzene-Polymers
Vinylbenzene-Polymers (a-1)
The volume that will possess agitating wing is about tower push flowing (plug flow) the successive reaction groove that the complete mixed type successive reaction groove of 20L, volume be about 11L, the flash-type devolatilization groove that possesses preheater is cascaded.In the solution that the ethylbenzene of the vinylbenzene of the methyl methacrylate by 79.2 quality %, 8.8 quality %, 12.0 quality % forms, mix 0.0073 mass parts t-butyl peroxy sec.-propyl manthanoate, 0.32 mass parts positive Dodecyl Mercaptan and make material solution.This material solution is supplied to the complete mixed type successive reaction groove at the temperature that remains on 125 ℃ with the speed of 3.9kg per hour, and carries out polymerization.The conversion rate control that complete mixed type successive reaction groove is exported is at 55-58%.Then, the gained polymeric solution is supplied to tower push flowing successive reaction groove, and carries out polymerization, wherein, the temperature of above-mentioned tower push flowing successive reaction groove be adjusted to along the liquid flow path direction from 125 ℃ to 144 ℃ the thermograde gradually changed.The conversion rate control that tower push flowing successive reaction groove is exported is at 75-78%.By preheater, the gained polymeric solution is heated to 230 ℃ and it is imported to the flash-type devolatilization groove be decompressed to 1.3kPa, in the groove of 235 ℃, at temperature, removes unreacted monomer.Extract the resin of 232 ℃ by toothed gear pump out, extrude as strand form (strand) cutting, obtain thus the vinylbenzene-Polymers (a-1) of particle shape.
Vinylbenzene-Polymers (a-2)
The monomer solution that use consists of the ethylbenzene of the vinylbenzene of the methyl methacrylate of 79.8 quality %, 2.2 quality %, 18.0 quality %, in addition, similarly operate with (a-1), obtains vinylbenzene-Polymers (a-2).
Vinylbenzene-Polymers (a-3)
The monomer solution that use consists of the ethylbenzene of the vinylbenzene of the methyl methacrylate of 70.0 quality %, 18.0 quality %, 12.0 quality %, in addition, similarly operate with (a-1), obtain vinylbenzene-Polymers (a-3).
Vinylbenzene-Polymers (a-4)
The amount that makes positive Dodecyl Mercaptan is 0.45 mass parts, in addition, with (a-1), similarly operates, and obtains vinylbenzene-Polymers (a-4).
Vinylbenzene-Polymers (a-5)
The amount that makes positive Dodecyl Mercaptan is 0.20 mass parts, in addition, with (a-1), similarly operates, and obtains vinylbenzene-Polymers (a-5).
Polymethylmethacrylate (a-6)
As polymethylmethacrylate, the product " parapet G " that uses Japanese Kuraray company to produce.
Vinylbenzene-Polymers (a-7)
The monomer mixture of the vinyl cyanide of the methyl methacrylate of the vinylbenzene of interpolation 52kg, 38kg and 10kg in the autoclave that is 200L at capacity, and the benzoyl peroxide of interpolation 80g is as polymerization starter, add the tert-dodecyl mercaptan of 300g as chain-transfer agent, when stirring, heating 6 hours under 95 ℃, then heating 2 hours at 130 ℃ of temperature.Afterwards, carry out coolingly, stop suspension polymerization.After reaction finishes, clean, dehydration, dry and obtain the vinylbenzene-Polymers (a-7) of pearl.
Vinylbenzene-Polymers (a-8)
The monomer solution that use consists of the ethylbenzene of the vinylbenzene of the methyl methacrylate of 43.0 quality %, 45.0 quality %, 12.0 quality %, in addition, similarly operate with (a-1), obtain vinylbenzene-Polymers (a-8).
In addition, the composition of vinylbenzene-Polymers (a-1)-(a-8) of explanation is before this gathered to following table 1.
[table 1]
Figure BDA0000076057720000171
(b) preparation method of styrene-acrylonitrile analog copolymer
Styrene-acrylonitrile analog copolymer (b-1)
Complete mixed type successive reaction groove, the volume that the volume that will possess agitator is about 20L is about the tower push flowing successive reaction groove of 40L, the flash-type devolatilization groove that possesses preheater is cascaded.Mix the positive Dodecyl Mercaptan of the t-butyl peroxy sec.-propyl manthanoate of 0.02 mass parts and 0.02 mass parts and make material solution in the solution that the ethylbenzene of the vinyl cyanide of the vinylbenzene by 81 mass parts, 19 mass parts, 10 mass parts forms.This material solution is supplied to the complete mixed type successive reaction groove at the temperature that is controlled at 130 ℃ with the speed of 6.0kg per hour, and carries out polymerization.In addition, the stirring velocity at complete hybrid reactor is to implement polymerization under 180rpm.Then, from complete hybrid reactor, reaction solution is extracted out continuously, and it is supplied to tower push flowing successive reaction groove, and carry out polymerization, wherein, the temperature of above-mentioned tower push flowing successive reaction groove be adjusted to along the liquid flow path direction from 130 ℃ to 160 ℃ the thermograde gradually changed.By preheater, the gained polymeric solution is heated to 230 ℃ and it is imported to the flash-type devolatilization groove be decompressed to 1.0kPa, in the groove of 235 ℃, at temperature, removes unreacted monomer.Extract the gained resin out by toothed gear pump, extrude as strand form cutting, obtain thus the styrene-acrylonitrile analog copolymer (b-1) of particle shape.
Styrene-acrylonitrile analog copolymer (b-2)
To make vinylbenzene be 70 mass parts, make vinyl cyanide is 30 mass parts, in addition, with (b-1), similarly operates, and obtains styrene-acrylonitrile analog copolymer (b-2).
Styrene-acrylonitrile analog copolymer (b-3)
To make vinylbenzene be 88 mass parts, make vinyl cyanide is 12 mass parts, in addition, with (b-1), similarly operates, and obtains styrene-acrylonitrile analog copolymer (b-3).
Styrene-acrylonitrile analog copolymer (b-4)
To make vinylbenzene be 92 mass parts, make vinyl cyanide is 8 mass parts, in addition, with (b-1), similarly operates, and obtains styrene-acrylonitrile analog copolymer (b-4).
Styrene-acrylonitrile analog copolymer (b-5)
Making positive Dodecyl Mercaptan is 0.035 mass parts, in addition, with (b-1), similarly operates, and obtains styrene-acrylonitrile analog copolymer (b-5).
Styrene-acrylonitrile analog copolymer (b-6)
Making positive Dodecyl Mercaptan is 0.04 mass parts, in addition, with (b-1), similarly operates, and obtains styrene-acrylonitrile analog copolymer (b-6).
Styrene-acrylonitrile analog copolymer (b-7)
Making positive Dodecyl Mercaptan is 0.015 mass parts, in addition, with (b-1), similarly operates, and obtains styrene-acrylonitrile analog copolymer (b-7).
In addition, the composition of styrene-acrylonitrile analog copolymer (b-1)-(b-7) of explanation is before this gathered to following table 2.
[table 2]
Figure BDA0000076057720000191
(c) preparation method of grafting analog copolymer
Grafting analog copolymer (c-1)
Weighing be take solids content and is converted that (styrene content is 40 quality % to the styrene-butadiene latex count 36kg, rubber size is 0.3 μ m) and be transferred to the autoclave that volume with agitator is 200L, adding pure water makes the water yield in the water yield and styrene-butadiene latex add up to 100kg, stirred, and be warming up to 50 ℃ under nitrogen atmosphere.To add in autoclave the sodium ethylene diamine tetracetate of 1.8g ferrous sulfate, 3.6g, the rongalite of 108g (rongalite) are dissolved in to pure water and solution, then spend respectively the mixture that 6 hours continuous addings consist of the tert-dodecyl mercaptan of the methyl methacrylate of the vinylbenzene of 13.2kg, 10.8kg, 240g and the potassium oleate of the di-isopropylbenzene hydroperoxide of 48g, 450g is scattered in to the 8kg pure water and solution.After adding end, temperature is warming up to 70 ℃, then adds the di-isopropylbenzene hydroperoxide of 24g, place afterwards 2 hours, polymerization is finished.Add antioxidant in the emulsion of gained, after using pure water that solids component is diluted to 15 quality %, temperature is warming up to 70 ℃, thereby adding dilute sulphuric acid in vigorous stirring is saltoutd, afterwards, after temperature is warming up to 95 ℃, it is solidified, thereby then dewatered, wash, the dry pulverous grafting analog copolymer (c-1) that obtains.
The volume average particle size of the graft copolymer of gained is 0.35 μ m.
Grafting analog copolymer (c-2)
Add the vinyl cyanide of 1.2kg, the vinylbenzene of 12.7kg, the methyl methacrylate of 10.1kg in the styrene-butadiene latex of 36kg, in addition, similarly operate with (c-1), obtain grafting analog copolymer (c-2).
The volume average particle size of the grafting analog copolymer of gained is 0.35 μ m.
Grafting analog copolymer (c-3)
Add the vinyl cyanide of 2.8kg, the vinylbenzene of 11.6kg, the methyl methacrylate of 9.6kg in the styrene-butadiene latex of 36kg, in addition, similarly operate with (c-1), obtain grafting analog copolymer (c-3).
The volume average particle size of the grafting analog copolymer of gained is 0.35 μ m.
Grafting analog copolymer (c-4)
Add the vinylbenzene of 9.6kg, the methyl methacrylate of 14.4kg in the styrene-butadiene latex of 30kg, in addition, similarly operate with (c-1), obtain grafting analog copolymer (c-4).
The volume average particle size of the grafting analog copolymer of gained is 0.35 μ m.
Grafting analog copolymer (c-5)
Use the styrene-butadiene latex that rubber size is 0.2 μ m, in addition, similarly operate with (c-1), obtain grafting analog copolymer (c-5).
The volume average particle size of the grafting analog copolymer of gained is 0.23 μ m.
Grafting analog copolymer (c-6)
Use the styrene-butadiene latex that rubber size is 0.6 μ m, in addition, similarly operate with (c-1), obtain grafting analog copolymer (c-6).
The volume average particle size of the grafting analog copolymer of gained is 0.65 μ m.
Grafting analog copolymer (c-7)
Use the styrene-butadiene latex that rubber size is 0.8 μ m, in addition, similarly operate with (c-1), obtain grafting analog copolymer (c-7).
The volume average particle size of the grafting analog copolymer of gained is 0.82 μ m.
Grafting analog copolymer (c-8)
Use the styrene-butadiene latex that styrene content is 25 quality %, in this styrene-butadiene latex of 36kg, add the vinylbenzene of 9.6kg, the methyl methacrylate of 14.4kg, in addition, similarly operate with (c-1), obtain grafting analog copolymer (c-8).
The volume average particle size of the grafting analog copolymer of gained is 0.35 μ m.
Grafting analog copolymer (c-9)
Add the vinylbenzene of 13.4kg, the methyl methacrylate of 9.4kg, the n-butyl acrylate of 1.2kg in the styrene-butadiene latex of 30kg, in addition, similarly operate with (c-1), obtain grafting analog copolymer (c-9).
The volume average particle size of the grafting analog copolymer of gained is 0.35 μ m.
In addition, the composition of grafting analog copolymer (c-1)-(c-7) of explanation is before this gathered to following table 3.
[table 3]
Figure BDA0000076057720000211
<embodiment 1-15, comparative example 1-13 >
According to the blending ratio shown in table 4-6, vinylbenzene-the Polymers that will be obtained by aforesaid method by Henschel mixer (a-1)-(a-7), styrene-acrylonitrile analog copolymer (b-1)-(b-7), grafting analog copolymer (c-1)-(c-11) mix, afterwards, use twin screw extruder (TEM35B processed of Toshiba Machine Co. Ltd, barrel zone temperature are 220 ℃) melting mixing granulation, thereby obtain the rubber modified thermoplastic resin composition.Then, by this particle injection moulding, obtain formed body.Transparency, color and luster to the formed body of gained are estimated, and are shown in table 4-6.
[table 4]
Figure BDA0000076057720000212
[table 5]
Figure BDA0000076057720000221
[table 6]
Figure BDA0000076057720000222
The investigation of<evaluation result >
As shown in above-mentioned table 4-6, be clear that the rubber modified thermoplastic resin composition of embodiment 1-17 all has good chemical resistant properties, transparency, color and luster, thermotolerance, shock-resistance and makes it reach good balance.Compare to embodiment 1-17, at least one above characteristic of the rubber modified thermoplastic resin composition of comparative example 1-10 is poor, therefore, can't balance realize well chemical resistant properties, transparency, color and luster, thermotolerance, shock-resistance.
Above, based on embodiment, describe the present invention.Those skilled in the art can understand: above-described embodiment is only illustration, various variation can be arranged, and these variation is equally in protection scope of the present invention.
Reference numeral
The major axis of a 1/4 elliptic method fixture
The minor axis of b 1/4 elliptic method fixture
X crackle origination point

Claims (6)

1. the rubber modified thermoplastic resin composition, is characterized in that, contains:
Vinylbenzene-Polymers (A), when the total quality of styrene monomer unit and methyl acrylic ester monomeric unit is 100 quality %, the methyl acrylic ester monomeric unit of the styrene monomer unit that contains 1～15 quality %, 85～99 quality %;
Styrene-acrylonitrile analog copolymer (B), when the total quality of styrene monomer unit and vinyl cyanide monomeric unit is 100 quality %, the vinyl cyanide monomeric unit of the styrene monomer unit that contains 80～90 quality %, 10～20 quality %; With
Grafting analog copolymer (C), styrene monomer, methyl acrylic ester monomer and vinyl cyanide monomer and rubber-like elastic body copolymerization are formed, and, by the total light transmittance of the formed body of the stamping forming thick 2mm of described grafting analog copolymer (C), be more than 85%
When the total quality of vinylbenzene-Polymers (A), styrene-acrylonitrile analog copolymer (B) and grafting analog copolymer (C) composition is 100 quality %, the styrene-acrylonitrile analog copolymer (B) of the vinylbenzene-Polymers that contains 15～54 quality % (A), 20～63 quality %, the grafting analog copolymer (C) of 10～50 quality %
The difference of the specific refractory power of the specific refractory power of the mixture of vinylbenzene-Polymers (A) and styrene-acrylonitrile analog copolymer (B) and grafting analog copolymer (C) is below 0.005,
When the total quality of vinylbenzene-Polymers (A) and styrene-acrylonitrile analog copolymer (B) composition is 100 quality %, the vinyl cyanide monomeric unit that contains 6～15 quality % in the mixture of vinylbenzene-Polymers (A) and styrene-acrylonitrile analog copolymer (B).
The weight-average molecular weight of vinylbenzene-Polymers (A) is in 70000～100000 scope, and the molecular weight of styrene-acrylonitrile analog copolymer (B) is in 100000～190000 scope.
2. rubber modified thermoplastic resin composition as claimed in claim 1, wherein, the volume average particle size of grafting analog copolymer (C) is in the scope of 0.25～0.80 μ m.
3. rubber modified thermoplastic resin composition as claimed in claim 1 or 2, wherein, the preparation method of vinylbenzene-Polymers (A) is continuous bulk polymerization.
4. rubber modified thermoplastic resin composition as claimed in claim 1 or 2, wherein, the preparation method of styrene-acrylonitrile analog copolymer (B) is continuous bulk polymerization.
5. injection-molded article, is characterized in that, any one claim described rubber modified thermoplastic resin composition injection moulding in claim 1 to 4 is obtained.
6. washing machine cover, is characterized in that, right to use requires 5 described injection-molded articles as parts.
CN2010800046664A 2009-01-16 2010-01-15 Rubber-modified thermoplastic resin composition, injection molded article comprising the same, and washing machine lid using the same Active CN102282209B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2009007472 2009-01-16
JP2009-007472 2009-01-16
PCT/JP2010/050375 WO2010082613A1 (en) 2009-01-16 2010-01-15 Rubber-modified thermoplastic resin composition, injection molded article comprising the same, and washing machine lid using the same

Publications (2)

Publication Number Publication Date
CN102282209A CN102282209A (en) 2011-12-14
CN102282209B true CN102282209B (en) 2013-12-11

Family

ID=42339867

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010800046664A Active CN102282209B (en) 2009-01-16 2010-01-15 Rubber-modified thermoplastic resin composition, injection molded article comprising the same, and washing machine lid using the same

Country Status (4)

Country Link
JP (1) JP5688975B2 (en)
KR (1) KR20110115583A (en)
CN (1) CN102282209B (en)
WO (1) WO2010082613A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012046648A (en) * 2010-08-27 2012-03-08 Nippon A&L Inc Thermoplastic resin composition and resin molded article
JP5709258B2 (en) * 2011-05-31 2015-04-30 テクノポリマー株式会社 Thermoplastic resin composition and molded article using the same
TWI604008B (en) * 2016-09-30 2017-11-01 奇美實業股份有限公司 Rubber-modified resin composition and preparation method thereof
JP2024069735A (en) * 2021-03-23 2024-05-22 デンカ株式会社 Thermoplastic resin composition, and production method of the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1121938A (en) * 1994-08-15 1996-05-08 奇美实业股份有限公司 High luster impact-resistance excellent processing fluidity styrene series resin composition
CN1202504A (en) * 1997-05-06 1998-12-23 通用电气公司 Composition containing styrene polymers and copolymers and containing blends of these, and moulded articles, which are resistant to frictional make obtained from these compositions
CN1835999A (en) * 2003-08-14 2006-09-20 第一毛织株式会社 Flameproof thermoplastic resin composition

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06179795A (en) * 1992-12-14 1994-06-28 Japan Synthetic Rubber Co Ltd Flame-retardant resin composition
JPH08239546A (en) * 1995-03-01 1996-09-17 Japan Synthetic Rubber Co Ltd Thermoplastic resin composition
JPH1025398A (en) * 1996-07-11 1998-01-27 Asahi Chem Ind Co Ltd Production of molded article of thermoplastic resin
JP2002060573A (en) * 2000-08-18 2002-02-26 Dainippon Ink & Chem Inc Thermoplastic resin composition and method for producing the same
JP5030325B2 (en) * 2000-11-21 2012-09-19 三菱レイヨン株式会社 Acrylic resin composition, acrylic resin film and laminate
JP4162591B2 (en) * 2001-06-04 2008-10-08 電気化学工業株式会社 Optical disc substrate
JP4860106B2 (en) * 2003-09-25 2012-01-25 電気化学工業株式会社 Cement admixture, cement composition, and cement concrete
JP2006070069A (en) * 2004-08-31 2006-03-16 Konica Minolta Opto Inc Thermoplastic resin material and optical element obtained using the same
JP5002252B2 (en) * 2006-12-06 2012-08-15 電気化学工業株式会社 Adhesive tape and method for producing the same
JP5038007B2 (en) * 2007-04-17 2012-10-03 電気化学工業株式会社 Composition, metal-based circuit board using the composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1121938A (en) * 1994-08-15 1996-05-08 奇美实业股份有限公司 High luster impact-resistance excellent processing fluidity styrene series resin composition
CN1202504A (en) * 1997-05-06 1998-12-23 通用电气公司 Composition containing styrene polymers and copolymers and containing blends of these, and moulded articles, which are resistant to frictional make obtained from these compositions
CN1835999A (en) * 2003-08-14 2006-09-20 第一毛织株式会社 Flameproof thermoplastic resin composition

Also Published As

Publication number Publication date
CN102282209A (en) 2011-12-14
JP5688975B2 (en) 2015-03-25
JPWO2010082613A1 (en) 2012-07-05
KR20110115583A (en) 2011-10-21
WO2010082613A1 (en) 2010-07-22

Similar Documents

Publication Publication Date Title
CN102115564B (en) Thermoplastic resin composition having improved impact strength and melt flow property, products and alloying compound prepared thereby
CN101287793B (en) Improved low gloss mass polymerized rubber-modified monovinylidene aromatic copolymer composition
CN101336255B (en) Thermoplastic resin having uniform composition and narrow molecular weight distribution, and method for preparing the same
KR100837092B1 (en) Transparent Rubber Modified Styrene Resin and Method for Preparing the Same by Continuous Bulk Polymerization
CN102282209B (en) Rubber-modified thermoplastic resin composition, injection molded article comprising the same, and washing machine lid using the same
US7217763B2 (en) Acrylonitrile-butadiene-styrene copolymer transparent resin having superior chemical resistance and transparency and preparation thereof
DK167818B1 (en) THERMOPLASTIC SUBSTANCE MIXTURE
JP5885473B2 (en) Method for producing transparent rubber-modified styrenic resin composition and method for producing molded article
US10329416B2 (en) Thermoplastic resin composition and molded article manufactured from the same
JP4534075B2 (en) Thermoplastic resin composition
JP2001226547A (en) Rubber-modified styrenic resin composition and injection- molded article thereof
JPH08269142A (en) Transparent rubber-modified styrene-based resin composition
JP4514388B2 (en) Resin composition and molded body thereof
JP4318943B2 (en) Resin composition and molded body thereof
JP7145271B1 (en) Transparent rubber-modified styrenic resin composition
JPH07330996A (en) Rubber-modified aromatic vinyl resin composition
JP4727116B2 (en) Rubber-modified copolymer resin composition
US20240239936A1 (en) Acrylic rubber for thermoplastic material with good low temperature impact strength
JPH0920851A (en) Transparent rubber-modified styrenic resin composition
JPH09151292A (en) Rubber-modified aromatic vinyl resin composition
JPH07292192A (en) Rubber-modified aromatic vinyl resin composition
JP2002155186A (en) Rubber modified styrenic resin composition
JPH04224848A (en) High-strength transparent styrene resin
JPS63241015A (en) Dispersion of graft rubber particle
WO2004052988A1 (en) Transparent rubber-modified styrene resin composition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant