CN1659227A - Thermoplastic resin composition - Google Patents

Thermoplastic resin composition Download PDF

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Publication number
CN1659227A
CN1659227A CN038127792A CN03812779A CN1659227A CN 1659227 A CN1659227 A CN 1659227A CN 038127792 A CN038127792 A CN 038127792A CN 03812779 A CN03812779 A CN 03812779A CN 1659227 A CN1659227 A CN 1659227A
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methyl
quality
resin composition
vinylbenzene
acrylate based
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CN1289593C (en
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野口哲央
加藤义明
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • 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
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • 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
    • 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
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention provides a thermoplastic resin composition excellent in transparency and capable of giving molded articles which are excellent in impact resistance and fabrication quality even when they have thin walls. The thermoplastic resin composition comprises a rubber-modified styrene resin composition comprising 60 to 80 % by mass of a continuous phase made of a styrene/(meth)acrylate copolymer and 40 to 20 % by mass of a dispersed phase made of a graft copolymer obtained by grafting a rubbery elastomer with a styrene/(meth)acrylate copolymer wherein the volume-mean particle diameter of the dispersed phase is 0.3 to 0.6 mum and the weight-average molecular weight (Mw) of the continuous phase and the constituent monomer units thereof satisfy a specific relationship and is characterized by containing 0.005 to 0.05 part by mass of an organopolysiloxane and, if necessary, 0.1 to 2.5 parts by mass of an ester lubricant per 100 parts by mass of the rubber-modified styrene resin composition, X=weight average molecular weight (Mw)***(1)120000<=X<=160000(2).

Description

The thermoplastic resin composition
Technical field
The present invention relates to obtain to have good transparency, even and the extremely thin thermoplastic resin composition who also has the moulding product of good impact and shaping processability.
Background technology
In the past, by with MBS based polymer and rubber-modified styrene mixed with polymers, the method that obtains the good thermoplastic resin composition of the shock-resistance and the transparency is people's known (Japan's special permission bulletin communiques clear 46-32748 number), and wherein this MBS based polymer carries out letex polymerization with the gum polymers latex that divinyl and vinylbenzene or the monomeric mixture letex polymerization of acrylonitrile and butadiene are formed and obtains by being selected from the monomer more than 2 kinds in vinylbenzene, methyl methacrylate and the vinyl cyanide.But, though these thermoplastic resin composition's shock-resistance are good really, be subjected to the influence of molding condition when having, can not obtain the shortcoming of the good transparency.
And in recent years along with the thin typeization of moulding product, even also will have high rigidity to thin at present, and the thin type shaping processability is good waits requirement very high.As the means that solve these problems, specially permit the rubber-modified styrene resin composition that has proposed in open communique 2001-226547 number by the disperse phase formation of specific vinylbenzene-external phase of (methyl) acrylate based copolymer and specific graft copolymer in Japan.But the shock-resistance or the shaping processability of moulding product as thin as a wafer are not necessarily enough.
In view of this present situation, the invention provides and to obtain to have the good transparency, even and the extremely thin thermoplastic resin composition who also has the moulding product of good shock-resistance and shaping processability.
Summary of the invention
The present inventor is in order to solve these problems, carried out research in depth repeatedly, found that: utilize the thermoplastic resin composition of containing the organopolysiloxane of specified quantitative in the rubber-modified styrene resin composition that the disperse phase by specific vinylbenzene-external phase of (methyl) acrylate based copolymer and specific graft copolymer is constituted and forming, can solve aforementioned problems, and finally finish the present invention thus.
That is, the present invention has the technology main idea of following feature:
1. thermoplastic resin composition, it is a rubber-modified styrene resin composition, said composition contains external phase 60～80 quality % of (I) vinylbenzene-(methyl) acrylate based copolymer and (II) disperse phase 40～20 weight % of graft copolymer; Vinylbenzene wherein-(methyl) acrylate based copolymer be styrenic monomers, (methyl) acrylic ester monomer and use as required can and the multipolymer of the vinyl monomer of these monomer copolymerizations; Graft copolymer is wherein formed by vinylbenzene-(methyl) acrylate based copolymer and gluey elastomerics grafting, and vinylbenzene wherein-(methyl) acrylate based copolymer is a styrenic monomers, (methyl) acrylic ester monomer, and use as required can with the multipolymer of the vinyl monomer of these monomer copolymerizations, it is characterized in that, the volume average particle size of disperse phase is 0.3～0.6 μ m, constitute the X of the formula (1) that monomeric unit tries to achieve in formula (2) scope by the weight-average molecular weight (Mw) of external phase and its, and with respect to these resin combination 100 mass parts, contain organopolysiloxane 0.005～0.05 mass parts
Figure A0381277900051
120000≤X≤160000?????????????????(2)。
2. above-mentioned 1 described thermoplastic resin composition, it is characterized in that, above-mentioned rubber-modified styrene resin composition contains external phase 60～70 quality % of (I) vinylbenzene-(methyl) acrylate based copolymer and (II) disperse phase 40～30 weight % of graft copolymer.
3. above-mentioned 1 or 2 described thermoplastic resin compositions is characterized in that, with respect to rubber-modified styrene resin composition 100 mass parts, contain ester base lubricant 0.1～2.5 mass parts.
4. above-mentioned 3 described thermoplastic resin compositions is characterized in that, the ester base lubricant is to solidify Viscotrol C.
5. each described thermoplastic resin composition is characterized in that in above-mentioned 1～4, and organopolysiloxane is a polydimethylsiloxane.
6. each described thermoplastic resin composition in above-mentioned 1～5, it is characterized in that, external phase is vinylbenzene-(methyl) acrylate based copolymer, wherein this multipolymer be styrenic monomers unit 20～70 quality %, (methyl) acrylic ester monomeric unit 30～80 quality % and use as required can with the multipolymer of vinyl monomer unit 0～10 quality % of these monomer copolymerizations.
7. each described thermoplastic resin composition in above-mentioned 1～5, it is characterized in that the graft copolymer that disperse phase forms for the gluey elastomerics grafting by the multipolymer of the polyhutadiene of vinylbenzene-(methyl) the acrylate based copolymers of 20～70 mass parts and 30～80 mass parts and/or styrene butadiene; Aforementioned vinylbenzene-(methyl) acrylate based copolymer be styrenic monomers unit 20～70 quality %, (methyl) acrylic ester monomeric unit 30～80 quality % and use as required can with the multipolymer of vinyl monomer unit 0～10 quality % of these monomer copolymerizations.
8. each described thermoplastic resin composition is characterized in that in above-mentioned 1～5, and external phase is vinylbenzene-(methyl) acrylate based copolymer; Wherein this multipolymer be styrenic monomers unit 20～70 quality %, (methyl) acrylic ester monomeric unit 30～80 quality % and use as required can with the multipolymer of vinyl monomer unit 0～10 quality % of these monomer copolymerizations; And disperse phase is the graft copolymer that the gluey elastomerics grafting by the multipolymer of the polyhutadiene of the vinylbenzene of 20～70 mass parts-(methyl) acrylate based copolymer and 30～80 mass parts and/or styrene butadiene forms; Aforementioned vinylbenzene-(methyl) acrylate based copolymer be styrenic monomers unit 20～70 quality %, (methyl) acrylic ester monomeric unit 30～80 quality % and use as required can with the multipolymer of vinyl monomer unit 0～10 quality % of these monomer copolymerizations.
Embodiment
Below describe the present invention in detail.Vinylbenzene-(methyl) acrylate based copolymer that constitutes the external phase of rubber-modified styrene resin composition of the present invention be styrenic monomers, (methyl) acrylic ester monomer and use as required can and the multipolymer of the vinyl monomer of these monomer copolymerizations.
The graft copolymer that constitutes the disperse phase of rubber-modified styrene resin composition of the present invention is the graft copolymer that is formed by vinylbenzene-(methyl) acrylate based copolymer and gluey elastomerics grafting, aforementioned vinylbenzene-(methyl) acrylate based copolymer be styrenic monomers, (methyl) acrylic ester monomer and use as required can and the multipolymer of the vinyl monomer of these monomer copolymerizations.
Can exemplify vinylbenzene, alpha-methyl styrene, p-vinyl toluene, o-vinyl toluene, m-vinyl toluene in external phase of the present invention and the employed styrenic monomers of disperse phase, ethyl styrene, p-t-butyl styrene etc. are preferably vinylbenzene.These styrenic monomers both can be used separately, also can more than two kinds and use.
(methyl) used in the present invention acrylic ester monomer can exemplify: methacrylic esters such as methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic acid 2-ethylhexyl; Acrylate such as methyl acrylate, ethyl propenoate, n-butyl acrylate, the own ester of vinylformic acid 2-methyl, 2-EHA, decyl acrylate.Be preferably methyl methacrylate, or n-butyl acrylate, good especially is methyl methacrylate.These (methyl) acrylic ester monomers both can use separately, also can more than two kinds and use.
That uses as required can exemplify with the vinyl monomer of these monomer copolymerizations: vinylformic acid, methacrylic acid, vinyl cyanide, methacrylonitrile, N-phenylmaleimide, N-cyclohexyl maleimide etc.
Gluey elastomerics used in the present invention can exemplify polyhutadiene, styrene-butadiene block copolymer and styrene butadiene random copolymer etc.
Styrene monomer quantity of units in styrene-butadiene block copolymer and the styrene butadiene random copolymer is more fortunately below the 60 quality %, the spy is 25 quality % following (not comprising 0) fortunately, and this is more satisfactory amount to the good shock-resistance and the transparency that obtains rubber-modified styrene resin composition.
Rubber-modified styrene resin composition of the present invention contains the external phase of 60～80 quality % vinylbenzene-(methyl) acrylate based copolymer, disperse phase with 40～20 quality % graft copolymers, be preferably the vinylbenzene-external phase of (methyl) acrylate based copolymer that contains 60～70 quality % and the disperse phase of the graft copolymer of 40～30 weight %.If the disperse phase of graft copolymer is less than 20 quality %, then the shock-resistance of thin type moulding product is insufficient, and if surpass 40 quality %, then shaping processability is insufficient, and is therefore undesirable.
The quality of external phase and disperse phase than measuring method is, with rubber-modified styrene resin composition (being decided to be quality A) in methylethylketone (MEK), stirred 24 hours with 23 ℃ temperature, with separating centrifuge separate the composition that be insoluble to MEK thereafter, amount of substance after the quality determination vacuum-drying (being decided to be quality B), try to achieve by following formula (3), formula (4):
Figure A0381277900072
The volume average particle size of the disperse phase of aforementioned graft copolymer is preferably 0.3～0.6 μ m, particularly preferably 0.3～0.45 μ m.If volume average particle size is less than 0.3 μ m, then the shock-resistance of thin type moulding product is insufficient, and if surpass 0.6 μ m, then the transparency is poor, so undesirable.
Weight-average molecular weight (Mw) and its X that constitutes the formula (1) of trying to achieve the unit by the external phase of aforementioned vinylbenzene-(methyl) acrylate based copolymer must be in the scope of formula (2).Annotate, the weight-average molecular weight of external phase described here is the weight-average molecular weight with the polystyrene conversion of the solvable composition gained of MEK of the aforementioned rubber-modified styrene resin composition of gel permeation chromatography (GPC method) mensuration,
Figure A0381277900073
120000≤X≤160000??????????????(2)。
If X is less than 120000, then the shock-resistance of thin type moulding product is insufficient, and if surpass 160000, then shaping processability is insufficient, and is therefore undesirable.Good especially is 12500≤X≤15500.
The amount of each monomeric unit of vinylbenzene-(methyl) acrylate based copolymer of formation external phase is so long as satisfy aforementioned condition, then have no particular limits, but the styrenic monomers unit is preferably 20～70 quality %, 20～40 quality % particularly preferably, (methyl) acrylic ester monomeric unit is preferably 30～80%, 60～80 quality % particularly preferably, that uses as required can be preferably 0～10 quality %, particularly preferably 0～5 quality % with the vinyl monomer unit of these monomer copolymerizations.
The gluey elastomerics of the graft copolymer of formation disperse phase and the amount of each monomeric unit are so long as satisfy aforementioned condition, then have no particular limits, but better be amount shown below, promptly, with the 30-80 mass parts, be preferably the 50-75 mass parts, the gluey elastomerics of 50-70 mass parts particularly preferably, grafting 20-70 mass parts, be preferably the 25-50 mass parts, particularly preferably the vinylbenzene of 30-50 mass parts-(methyl) acrylic acid esters co-polymer forms graft copolymer, wherein, this vinylbenzene-contained styrene monomer unit of (methyl) acrylic acid esters co-polymer is preferably 20-70 quality %, 20-40 quality % particularly preferably; Contained (methyl) acrylic ester monomeric unit is preferably 30～80 quality %, 60～80 quality % particularly preferably; Contained use as required can be preferably 0～10 quality %, particularly preferably 0～5 quality % with the vinyl monomer unit of these monomer copolymerizations.
Rubber-modified styrene resin composition of the present invention can utilize technique known such as mass polymerization, solution polymerization process, suspension polymerization, body-suspension polymerization, emulsion polymerization to make.Intermittence type polymerization method, continous way polymerization can adopt in addition.
Thermoplastic resin composition of the present invention is contained organopolysiloxane.Organopolysiloxane can exemplify polydimethylsiloxane, PSI, poly-diphenyl siloxane etc., is preferably polydimethylsiloxane.Can also use as required in the end of organopolysiloxane or molecule and import the modification class organopolysiloxane that epoxy group(ing), amino, carboxyl, hydroxyl, methacrylic acid group etc. form.These organopolysiloxanes both can use separately, also can more than two kinds and use.
Among the thermoplastic resin composition of the present invention, and with aforementioned organopolysiloxane and ester base lubricant, the transparency, shock-resistance and shaping processability are balanced to have more satisfactory effect on good making, the ester base lubricant can exemplify fatty acid polyglycol diol esters such as fatty low-carbon-ester, polyethylene glycol mono stearate such as solidifying castor-oil plant wet goods aliph polyols ester, butyl stearate etc., and good especially is to solidify Viscotrol C.
With respect to rubber-modified styrene resin composition 100 mass parts, the content of organopolysiloxane is 0.005～0.05 mass parts, be preferably 0.01～0.03 mass parts.If less than 0.005 mass parts, then the shock-resistance of thin type moulding product is insufficient, if surpass 0.05 mass parts, then transparency deterioration is therefore undesirable.
With respect to rubber-modified styrene resin composition 100 mass parts, the content of ester base lubricant is preferably 0.1～2.5 mass parts, more preferably 0.5～2 mass parts.If less than 0.1 mass parts then the combined effect of organopolysiloxane and ester base lubricant is little, if surpass 2.5 mass parts then the transparency reduces significantly.
Only otherwise can damage thermoplastic resin composition's of the present invention performance, can mix known oxidation inhibitor, weather resisting agent, lubricant, softening agent, tinting material, anti-live agent, mineral wet goods additive among the thermoplastic resin composition of the present invention.
The thermoplastic resin composition of the present invention of Huo Deing can be processed to various formed bodys by methods such as for example injection molding, compressed moulding and extrusion mouldings like this, for practicality.Mixing when using thermoplastic resin composition of the present invention to make various formed body (mixing) melt extrudes method and has no particular limits, and can adopt known method.For example, high speed agitator) etc. in advance with cylinder or Henschel mixer (Henschel mixer: with each raw material uniform mixing, send into single shaft forcing machine or biaxial extruder then and carry out melting mixing, the particle of modulation shaping usefulness is made various moulding product with this shaping particles.
Embodiment
Below the present invention will be described in more detail with embodiment, but the present invention is not limited to these embodiment.
At first the manufacturing from material resin begins explanation.
(1) manufacturing of vinylbenzene-(methyl) acrylate based copolymer
Reference example 1: vinylbenzene-(methyl) acrylic ester copolymer A-1
In capacity is 250 liters autoclave, add 100kg pure water, 0.5g Sodium dodecylbenzene sulfonate, 250g calcium phosphate, 23kg vinylbenzene, 73kg methyl methacrylate, 4kg vinyl cyanide, add the peroxidation tert-butyl isobutyrate of the polymerization starter of 100g, the t-dodecyl mercaptans of 650g again, under the stirring of revolution 150rpm, mixed solution is disperseed.Then, make this mixed solution, 130 ℃ of heated polymerizables 2.5 hours 90 ℃ temperature heated polymerizable 8 hours.Reaction finishes the back cleans, and drying is carried out in dehydration then, has obtained vinylbenzene-(methyl) acrylic ester copolymer A-1 of pearl.
Reference example 2: vinylbenzene-(methyl) acrylic ester copolymer A-2
Except the amount with the t-dodecyl mercaptans in the reference example 1 changed 800g into, other and vinylbenzene-(methyl) acrylic ester copolymer A-1 were same, have made vinylbenzene-(methyl) acrylic ester copolymer A-2.
Reference example 3: vinylbenzene-(methyl) acrylic ester copolymer A-3
Except the amount with the t-dodecyl mercaptans in the reference example 1 changed 500g into, other and vinylbenzene-(methyl) acrylic ester copolymer A-1 were same, have made vinylbenzene-(methyl) acrylic ester copolymer A-3.
Reference example 4: vinylbenzene-(methyl) acrylic ester copolymer A-4
Except the amount with the t-dodecyl mercaptans in the reference example 1 changed 900g into, other and vinylbenzene-(methyl) acrylic ester copolymer A-1 were same, have made vinylbenzene-(methyl) acrylic ester copolymer A-4.
Reference example 5: vinylbenzene-(methyl) acrylic ester copolymer A-5
In capacity is 250 liters autoclave, add 100kg pure water, 0.5g Sodium dodecylbenzene sulfonate, 250g calcium phosphate, 42kg vinylbenzene, 58kg methyl methacrylate, add the t-dodecyl mercaptans of 100g polymerization starter peroxidation tert-butyl isobutyrate, 300g again, under the stirring of revolution 150rpm, mixed solution is disperseed.Then, make this mixed solution, 130 ℃ of heated polymerizables 2.5 hours 90 ℃ temperature heated polymerizable 8 hours.Reaction finishes the back cleans, and drying is carried out in dehydration then, has obtained vinylbenzene-(methyl) acrylic ester copolymer A-5 of pearl.
Reference example 6: vinylbenzene-(methyl) acrylic ester copolymer A-6
Except the amount with the t-dodecyl mercaptans in the reference example 5 changed 600g into, other and vinylbenzene-(methyl) acrylic ester copolymer A-5 were same, have made vinylbenzene-(methyl) acrylic ester copolymer A-6.
(2) manufacturing of gluey elastomer latices
Reference example 7: gluey elastomer latices G-1
In volume is 200 liters autoclave, add the Potassium Persulphate of 56kg pure water, 400g potassium oleate, 1200g roseolic acid potassium, 1.2kg salt of wormwood, 400g, under agitation with they uniform dissolution.Then, add t-dodecyl mercaptans, the 80kg divinyl of 400g, 60 ℃ temperature polyase 13 0 hour, be warming up to 70 ℃ again and placed 30 hours while stirring, finish polymerization, obtained gluey elastomer latices G-1.
Reference example 8: gluey elastomer latices G-2
In volume is 200 liters autoclave, add 56kg pure water, 400g potassium oleate, 1200g roseolic acid potassium, 1.2kg salt of wormwood, 400g Potassium Persulphate, under agitation with they uniform dissolution.Then, add t-dodecyl mercaptans, 23.6kg vinylbenzene, the 56.4kg divinyl of 400g, 60 ℃ temperature polymerization 24 hours, be warming up to 70 ℃ again and placed 24 hours while stirring, finish polymerization, obtained gluey elastomer latices G-2.
Reference example 9: gluey elastomer latices G-3
In volume is 200 liters autoclave, add 64kg pure water, 400g potassium oleate, 1200g roseolic acid potassium, 1.2kg salt of wormwood, 400g Potassium Persulphate, under agitation with they uniform dissolution.Then, add t-dodecyl mercaptans, 23.6kg vinylbenzene, the 56.4kg divinyl of 400g, 60 ℃ temperature polymerization 16 hours, be warming up to 70 ℃ again and placed 12 hours while stirring, finish polymerization, obtained gluey elastomer latices G-3.
Reference example 10: gluey elastomer latices G-4
In volume is 200 liters autoclave, add 115kg pure water, 500g potassium oleate, 75g potassium pyrophosphate, 1.5g ferrous sulfate, 2.2g sodium ethylene diamine tetracetate, 22g rongalite, under agitation with they uniform dissolution.Then, add 14.5kg vinylbenzene, 35.5kg divinyl, the t-dodecyl mercaptans of 148g, 30g Vinylstyrene, 96g hydrogen peroxide diisopropyl benzene, carry out 16 hours reaction while stirring 50 ℃ temperature, finish polymerization, obtained gluey elastomer latices.The 45g sodium sulfosuccinate is added in gluey elastomer precursor gum Ruzhong at gained, after the sufficient stabilization, add 0.2 quality % aqueous hydrochloric acid and 2 quality % aqueous sodium hydroxide solutions from nozzle separately, the pH of latex is remained on 8～9, make the emulsion condensation hypertrophyization, having obtained volume average particle size is the gluey elastomer latices G-4 of 0.6 μ m.
(3) contain the manufacturing of the polymkeric substance of graft copolymer
Reference example 11: the polymer B-1 that contains graft copolymer
By the solid gluey elastomer latices G-1 that divides the metering 30kg reference example 7 that converts that forms, move in the autoclave that volume is 200L, add the 90kg pure water, under nitrogen gas stream, be warming up to 50 ℃ while stirring.Add therein by 1.5g ferrous sulfate, 3g sodium ethylene diamine tetracetate, 100g rongalite and be dissolved in the formed solution of 2kg pure water, mixture and 60g hydrogen peroxide diisopropyl benzene, the 450g potassium oleate that constitutes with the t-dodecyl mercaptans that added continuously respectively in 6 hours by 7.5kg vinylbenzene, 22.5kg methyl methacrylate, 60g is scattered in the formed lysate of 8kg pure water then.After interpolation finishes, be warming up to 70 ℃, add 30g hydrogen peroxide diisopropyl benzene again, placed then 2 hours, finished polymerization.
In the emulsion of gained, add oxidation inhibitor, make solid formation be divided into 15 quality % with the pure water dilution, be warming up to 70 ℃ then, the limit excitation is stirred limit adding dilute sulphuric acid and is saltoutd, be warming up to 95 ℃ thereafter, it is solidified, and then dehydration, washing, drying have obtained pulverous polymer B-1 that contains graft copolymer.
Reference example 12: the polymer B-2 that contains graft copolymer
By the solid gluey elastomer latices G-2 that divides the metering 30kg reference example 8 that converts that forms, move in the autoclave that volume is 200L, add 90kg pure water, 1.8kg vinylbenzene, 4.2kg methyl methacrylate, under nitrogen gas stream, be warming up to 50 ℃ while stirring.Add therein by 1.5g ferrous sulfate, 3g sodium ethylene diamine tetracetate, 100g rongalite and be dissolved in the formed solution of 2kg pure water, mixture and 60g hydrogen peroxide diisopropyl benzene, the 450g potassium oleate that constitutes with the t-dodecyl mercaptans that added continuously respectively in 6 hours by 10.5kg vinylbenzene, 13.5kg methyl methacrylate, 90g is scattered in the formed lysate of 8kg pure water then.After interpolation finishes, be warming up to 70 ℃, add 30g hydrogen peroxide diisopropyl benzene again, placed then 2 hours, finished polymerization.
In the emulsion of gained, add oxidation inhibitor, make solid formation be divided into 15 quality % with the pure water dilution, be warming up to 70 ℃ then, high degree of agitation limit, limit adds dilute sulphuric acid and saltouts, be warming up to 95 ℃ thereafter, it is solidified, and then dehydration, washing, drying have obtained pulverous polymer B-2 that contains graft copolymer.
Reference example 13: the polymer B-3 that contains graft copolymer
Except the gluey elastomer latices in the reference example 12 being changed into gluey elastomerics G-3, other is same with the polymer B-2 that contains graft copolymer, has made pulverous polymer B-3 that contains graft copolymer.
Reference example 14: the polymer B-4 that contains graft copolymer
Except the gluey elastomer latices in the reference example 12 being changed into gluey elastomerics G-4, other is same with the polymer B-2 that contains graft copolymer, has made pulverous polymer B-4 that contains graft copolymer.
Embodiment 1～11 and comparative example 1～9
Press proportioning shown in table 1, the table 2, cooperate vinylbenzene-(methyl) acrylate based copolymer, the polymkeric substance that contains graft copolymer, polydimethylsiloxane (newly chemical industry (strain) is made KF-96 more), curing Viscotrol C (flower king (strain) makes カ オ one ワ Star Network ス (Kao Wax) 85-P), the ethylenebisstearamide (flower king (strain) makes カ オ one ワ Star Network ス (KaoWax) EB-P) of reference example 1～6 manufacturing in reference example 11～14 manufacturings.Then, after with Henschel mixer this mixture being mixed, with biaxial extruder (East sesame machinery (strain) system TEM-35B) under 220 ℃ of barrel temperatures, carry out melting mixing, make its granulating.With the sample particle of gained, various physical property measurements have been carried out according to following physical property measurement method.Measurement result is shown in table 1, table 2.
(1) shaping processability of thin type shaping
Using Sumitomo heavy-duty machine tool industry (strain) corporate system injection machine (NEOMAT515/150), following condition 1 and condition 2 times, is the square plate of 200 * 200 * 1.5mm size with the sample shaping particles, has estimated the shaping processability that thin type is shaped.
Condition 1: 190 ℃ of barrel temperatures, 40 ℃ of die temperatures
Condition 1: 200 ℃ of barrel temperatures, 60 ℃ of die temperatures
◎ can both obtain the good moulding product of outward appearance for 2 times in condition 1 and condition.
Can obtain the good moulding product of outward appearance under zero a certain condition in condition 1 or condition 2.
* the not good situations that are shaped such as filling is not good, gas burn, undulatory flow marks take place, all can not obtain the good moulding product of outward appearance for 2 times in condition 1 and condition.
It is qualified that ◎ and zero is judged to be.
(2) shock-resistance of thin type moulding product
Use Sumitomo heavy-duty machine tool industry (strain) corporate system injection machine (SYCAP165/75), under the condition of 220 ℃ of barrel temperatures, 60 ℃ of die temperatures,, make the square plate test film of 90 * 90 * 1mm size the sample shaping particles.With Du Pont (dupont) formula drop hammer impact testing machine, making quality is that 50g and quality are that the hammer of 100g falls from the eminence of 50cm, has estimated the shock-resistance of thin type moulding product.
The A quality is that the hammer of 100g does not have destructive rate more than 80%.
The B quality is that the hammer of 50g does not have destructive rate more than 80%.
The C quality is that the hammer of 50g does not have destructive rate less than 80%.
It is qualified that A and B are judged to be.
(3) transparency (turbidity)
Shi Yong East sesame machinery (strain) corporate system injection machine (IS-50EP) under the condition of 220 ℃ of barrel temperatures, 60 ℃ of die temperatures, with the sample shaping particles, is made the square plate test film of 55 * 90 * 3mm size.According to ASTM D1003, measured the turbidity (unit: %) of this test film.
The analysis of rubber-modified styrene resin composition, the particle of the rubber-modified styrenic resin composition that preparation is mixed according to the proportioning of table 1, table 2 by vinylbenzene-(methyl) acrylate based copolymer and the multipolymer that contains graft copolymer in advance, use it according to following measuring method, carried out each analytical value and measured.Each analytical value is shown in table 1, table 2.
(1) mensuration of the mass ratio of external phase and disperse phase
The sample particle (being decided to be quality A) of measuring quality in advance in methylethylketone (MEK), was stirred 24 hours under 23 ℃ temperature, separate the composition that is insoluble to MEK with separating centrifuge thereafter, after the centrifugation operation, left standstill 30 minutes.The operational condition of separating centrifuge is as follows.
Temperature :-9 ℃
Revolution: 20000rpm
Time: 60 minutes
Separate the supernatant liquor and the throw out of centrifugalled solution, use the Vacuumdrier dry sediment, quality measurement (being decided to be quality B) has then been obtained the mass ratio of external phase and disperse phase by following formula (3), formula (4).
Figure A0381277900141
(2) weight-average molecular weight of external phase is measured
Divide the supernatant liquor of getting aforementioned centrifugalled solution, add methyl alcohol, make vinylbenzene-(methyl) acrylate based copolymer (external phase) precipitation.Take this throw out, under following GPC condition determination, measure.
Device name: SYSTEM-21 Shodex (clear and electrician's corporate system)
Post: with 3 PL gel MIXED-B series connection
Temperature: 40 ℃
Detect: the differential refraction rate
Solvent: tetrahydrofuran (THF)
Concentration: 2 quality %
Inspection amount line: adopt polystyrene standard (PS) (PL corporate system) to make, weight-average molecular weight is represented with the PS scaled value.
(3) mensuration of the formation monomeric unit of external phase
The external phase (the solvable composition of MEK) that is made of vinylbenzene-(methyl) acrylate based copolymer of gained in the pre-treatment of measuring in front is dissolved in heavy chloroform, uses FT-NMR (NEC corporate system FX-90Q type), tried to achieve the formation monomeric unit.
(4) volume average particle size of disperse phase is measured
With the N of about 1g sample particle at 100g, stirred 24 hours in the dinethylformamide (DMF), add DMF again and dilute the concentration that reaches suitable, use laser diffraction and scattering method particle size distribution measuring machine (LS230 of COULTER company type), measure.
(5) the unitary ratio of the component unit of disperse phase
Each sample powder of the multipolymer that contains graft copolymer that will make at reference example 11～14 is in methylethylketone (MEK), under 23 ℃ temperature, stirred 24 hours, with separating centrifuge separate the composition that be insoluble to MEK, left standstill 30 minutes after the centrifugation operation thereafter.The operational condition of separating centrifuge is with aforementioned identical.
Take out the supernatant liquor of centrifugalled solution, add methyl alcohol, making does not have grafted vinylbenzene-(methyl) acrylate based copolymer precipitation.Collect this throw out, make it be dissolved in heavy chloroform, use FT-NMR (NEC corporate system FX-90Q type), tried to achieve the formation monomeric unit.
Because in the multipolymer that contains graft copolymer that reference example 11～14 is made, ratio with the formation monomeric unit of gum polymers grafted vinylbenzene-(methyl) acrylate based copolymer, with the ratio that does not have grafted vinylbenzene-(methyl) acrylate based copolymer can think identical, therefore just with this measured value as with the ratio of the formation monomeric unit of gum polymers grafted vinylbenzene-(methyl) acrylate based copolymer.
(6) the gluey elasticity scale of construction of disperse phase and the mensuration of grafted monomer amount
The throw out of the aforementioned centrifugalled solution of filtered and recycled, with after the Vacuumdrier drying as the mensuration sample of disperse phase.The sample swelling that makes gained is used FT-NMR (NEC corporate system FX-90Q type) in heavy chloroform, has tried to achieve the formation monomeric unit.
(the unitary ratio of styrene monomer is that the ratio of a, (methyl) acrylate monomeric units is b by the mass ratio of the formation monomeric unit of the vinylbenzene of trying to achieve in the mensuration of aforementioned (5)-(methyl) acrylate based copolymer.The total amount that constitutes monomeric unit is 100) and the mass ratio of the formation monomeric unit of the disperse phase sample of trying to achieve here (ratio of butadiene monomer unit is that c, the unitary ratio of styrene monomer are that the ratio of d, (methyl) acrylate monomeric units is e.The total amount that constitutes monomeric unit is 100), according to following formula (5) and formula (6), tried to achieve the gluey elasticity scale of construction and grafted monomer amount,
Figure A0381277900161
In addition,, tried to achieve the formation monomeric unit with FT-NMR to made the sample of the throw out (disperse phase) of pre-treatment in aforementioned (1), all consistent with the formation monomeric unit of above-mentioned gained.
The shaping processability that thermoplastic resin composition's of the present invention embodiment is shaped at thin type, the shock-resistance of thin type moulding product and transparent aspect all very good, and the shock-resistance of the shaping processability that the comparative example that does not meet the thermoplastic resin composition of condition of the present invention is shaped at thin type, thin type moulding product and transparent aspect, always have certain rerum natura relatively poor.
Usability on the industry
Adopt the present invention, have the good transparency and products formed as thin as a wafer also has good resistance to impact and the thermoplastic resin composition of shaping processability even can provide.
Table 1
Implement Implement Implement Implement Implement Implement Implement Implement Embodiment Implement Implement
Cooperate Vinylbenzene-(methyl) acrylate based copolymer A-1 (mass parts) ?70 ???70 ???70 ??70 ??65 ???65 ????65 ????65
A-2 (mass parts) ????60 ????60
A-5 (mass parts) ????65
The polymkeric substance that contains graft copolymer B-1 (mass parts) ?30 ???30 ???30 ??30 ??35 ???35 ????40 ????40 ????35 ????35
B-2 (mass parts) ????35
Organopolysiloxane (mass parts) ?0.005 ??0.015 ??0.045 ??0.015 ??0.015 ???0.015 ??0.015 ??0.015 ????0.015 ????0.015 ????0.015
Solidify Viscotrol C (mass parts) ??0.5 ???1.5 ??2 ????3
Ethylenebisstearamide (mass parts) ????1.5
The analytical value of rubber phenylethylene resin series External phase The mass ratio of external phase Quality % ????????????????73 ????68 ????????64 ????70 ????????68
Constitute the ratio (quality %) of monomeric unit ??MMA ????????????????72.6 ????72.7 ????????72.8 ????57.5 ????????72.7
??St ????????????????23.8 ????23.8 ????????23.8 ????42.5 ????????23.8
??AN ????????????????3.6 ????3.5 ????????3.4 ????0 ????????3.5
Weight-average molecular weight (Mw) ????????????????85000 ????86000 ????????71000 ????113000 ????????86000
The X value ????????????????148000 ????150000 ????????124000 ????131000 ????????150000
Disperse phase The mass ratio of disperse phase Quality % ????????????????27 ????32 ????????36 ????30 ????????32
Gluey elastomerics Mass parts ????????????????55 ????55 ????????55 ????58 ????????55
The grafted monomer amount Mass parts ????????????????45 ????45 ????????45 ????42 ????????45
Constitute the ratio (quality %) of monomeric unit ??MMA ????????????????74.8 ????74.8 ????????74.8 ????57.8 ????????74.8
??St ????????????????25.2 ????25.2 ????????25.2 ????42.2 ????????25.2
Volume average particle size ??μ?m ????????????????0.40 ????0.40 ????????0.40 ????0.39 ????????0.40
The moulding product The shaping processability of thin type moulding product ?○ ??○ ??○ ??◎ ??○ ???◎ ????○ ????◎ ????○ ????◎ ????○
The shock-resistance of thin type moulding product ?B ??B ??B ??B ??A ???A ????A ????A ????A ????A ????A
Turbidity (%) ?1.6 ??2.0 ??2.8 ??2.2 ??2.2 ???2.8 ????2.5 ????3.5 ????2.9 ????4.4 ????4.9
MMA: methyl methacrylate, St: vinylbenzene, AN: vinyl cyanide
Table 2
Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example
Cooperate Vinylbenzene-(methyl) acrylate based copolymer A-1 (quality ????70 ????70 ????80
A-2 (quality ????50
A-3 (quality ????70
A-4 (quality ????60
A-5 (quality ????65 ????65
A-6 (quality ????65
The polymkeric substance that contains graft copolymer B-1 (quality ????30 ????30 ????20 ????50 ????30 ????40
B-2 (quality ????35
B-3 (quality ????35
B-4 (quality ????35
Organopolysiloxane (mass parts) ????0 ????0.1 ????0.015 ????0.015 ????0.015 ????0.045 ????0.015 ????0.015 ????0.015
Rubber modified styrene series resin External phase The mass ratio of external phase Quality % ????73 ????82 ????55 ????73 ????64 ????70 ????71 ????70
Constitute the ratio (quality %) of monomeric unit ????MMA ????72.6 ????72.6 ????72.6 ????72.7 ????72.5 ????57.5 ????57.5 ????57.3
????St ????23.8 ????23.8 ????23.9 ????23.8 ????24.0 ????42.5 ????42.5 ????42.7
????AN ????3.6 ????3.6 ????3.2 ????3.5 ????3.5 ????0 ????0 ????0
Weight-average molecular weight (Mw) ????85000 ????85000 ????72000 ????101000 ????60000 ????111000 ????114000 ????81000
The X value ????148000 ????148000 ????126000 ????177000 ????104000 ????129000 ????133000 ????94000
Disperse phase The mass ratio of disperse phase Quality % ????27 ????18 ????45 ????27 ????36 ????30 ????29 ????30
The gluey elasticity scale of construction Mass parts ????55 ????55 ????55 ????55 ????55 ????58 ????60 ????58
The grafted monomer amount Mass parts ????45 ????45 ????45 ????45 ????45 ????42 ????40 ????42
Constitute the ratio of monomeric unit ????St ????25.2 ????25.2 ????25.2 ????25.2 ????25.2 ????42.2 ????41.9 ????42.6
????MMA ????74.8 ????74.8 ????74.8 ????74.8 ????74.8 ????57.8 ????58.1 ????57.4
Volume average particle size ????μm ????0.40 ????0.40 ????0.40 ????0.40 ????0.40 ????0.25 ????0.65 ????0.39
The moulding product The shaping processability of thin type moulding product ????○ ????○ ????○ ????× ????× ????◎ ????○ ????× ????◎
The shock-resistance of thin type moulding product ????C ????B ????C ????A ????B ????C ????C ????B ????C
Turbidity (%) ????1.6 ????5.1 ????1.5 ????3.3 ????3.5 ????2.3 ????1.8 ????4.8 ????2.8
MMA: methyl methacrylate, St: vinylbenzene, AN: vinyl cyanide

Claims (8)

1, thermoplastic resin composition, it is a rubber-modified styrene resin composition, said composition contains external phase 60～80 quality % of (I) vinylbenzene-(methyl) acrylate based copolymer and (II) disperse phase 40～20 weight % of graft copolymer; Vinylbenzene wherein-(methyl) acrylate based copolymer be styrenic monomers, (methyl) acrylic ester monomer and use as required can and the multipolymer of the vinyl monomer of these monomer copolymerizations; Graft copolymer is wherein formed by vinylbenzene-(methyl) acrylate based copolymer and gluey elastomerics grafting, and vinylbenzene wherein-(methyl) acrylate based copolymer is a styrenic monomers, (methyl) acrylic ester monomer, and use as required can with the multipolymer of the vinyl monomer of these monomer copolymerizations, it is characterized in that, the volume average particle size of disperse phase is 0.3～0.6 μ m, constitute the X of the formula (1) that monomeric unit tries to achieve in the scope of formula (2) by the weight-average molecular weight (Mw) of external phase and its, and with respect to these resin combination 100 mass parts, contain organopolysiloxane 0.005～0.05 mass parts
120000≤X≤160000??????????????????(2)。
2, thermoplastic resin composition according to claim 1, it is characterized in that, above-mentioned rubber-modified styrene resin composition contains external phase 60～70 quality % of (I) vinylbenzene-(methyl) acrylate based copolymer and (II) disperse phase 40～30 weight % of graft copolymer.
3, thermoplastic resin composition according to claim 1 and 2 is characterized in that, with respect to rubber-modified styrene resin composition 100 mass parts, contains ester base lubricant 0.1～2.5 mass parts.
4, thermoplastic resin composition according to claim 3 is characterized in that, the ester base lubricant is to solidify Viscotrol C.
According to each described thermoplastic resin composition in the claim 1～4, it is characterized in that 5, organopolysiloxane is a polydimethylsiloxane.
6, according to each described thermoplastic resin composition in the claim 1～5, it is characterized in that, external phase is vinylbenzene-(methyl) acrylate based copolymer, wherein this multipolymer be styrenic monomers unit 20～70 quality %, (methyl) acrylic ester monomeric unit 30～80 quality % and use as required can with the multipolymer of vinyl monomer unit 0～10 quality % of these monomer copolymerizations.
7, according to each described thermoplastic resin composition in the claim 1～5, it is characterized in that the graft copolymer that disperse phase forms for the gluey elastomerics grafting by the multipolymer of the polyhutadiene of vinylbenzene-(methyl) the acrylate based copolymers of 20～70 mass parts and 30～80 mass parts and/or styrene butadiene; Aforementioned vinylbenzene-(methyl) acrylate based copolymer be styrenic monomers unit 20～70 quality %, (methyl) acrylic ester monomeric unit 30～80 quality % and use as required can with the multipolymer of vinyl monomer unit 0～10 quality % of these monomer copolymerizations.
According to each described thermoplastic resin composition in the claim 1～5, it is characterized in that 8, external phase is vinylbenzene-(methyl) acrylate based copolymer; Wherein this multipolymer be styrenic monomers unit 20～70 quality %, (methyl) acrylic ester monomeric unit 30～80 quality % and use as required can with the multipolymer of vinyl monomer unit 0～10 quality % of these monomer copolymerizations; And disperse phase is the graft copolymer that the gluey elastomerics grafting by the multipolymer of the polyhutadiene of the vinylbenzene of 20～70 mass parts-(methyl) acrylate based copolymer and 30～80 mass parts and/or styrene butadiene forms; Aforementioned vinylbenzene-(methyl) acrylate based copolymer be styrenic monomers unit 20～70 quality %, (methyl) acrylic ester monomeric unit 30～80 quality % and use as required can with the multipolymer of vinyl monomer unit 0～10 quality % of these monomer copolymerizations.
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