WO2004052988A1 - Composition de resine de styrene transparente modifiee par caoutchouc - Google Patents

Composition de resine de styrene transparente modifiee par caoutchouc Download PDF

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Publication number
WO2004052988A1
WO2004052988A1 PCT/JP2003/015369 JP0315369W WO2004052988A1 WO 2004052988 A1 WO2004052988 A1 WO 2004052988A1 JP 0315369 W JP0315369 W JP 0315369W WO 2004052988 A1 WO2004052988 A1 WO 2004052988A1
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mass
component
meth
acrylate
molecular weight
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PCT/JP2003/015369
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English (en)
Japanese (ja)
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Michihiro Kaai
Madoka Furuta
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Toagosei Co., Ltd.
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Priority to AU2003302913A priority Critical patent/AU2003302913A1/en
Publication of WO2004052988A1 publication Critical patent/WO2004052988A1/fr

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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

Definitions

  • the present invention relates to a transparent rubber-modified styrene resin composition having excellent strength, transparency, and balance of moldability.
  • Styrene resins have been widely used as molding materials for food containers, household goods, and electrical products because of their excellent strength, transparency, and moldability.
  • styrene resins have the disadvantage of being relatively brittle, and so-called impact-resistant rubber-modified styrene resins containing a rubber-like elastic material as dispersed particles have been developed.
  • impact resistance has improved, this resin is opaque even when formed into sheets and films, and cannot be used in fields where transparency is required.
  • Transparent rubber-modified styrene resin compositions were developed by reducing the difference in refractive index between the continuous phase and the dispersed phase containing the rubber component. (The Chemical Society of Japan 39, 1998, Transparent Polymer Refractive index control of P213-P218). Such a transparent rubber-modified styrene resin composition has low fluidity, and has problems such as discoloration and a decrease in transparency when molded at an elevated molding temperature.
  • An object of the present invention is to solve the above-mentioned problems in the conventional art and to provide a transparent rubber-modified styrene resin composition having an excellent balance of strength, transparency, and moldability.
  • a transparent rubber-modified styrene resin composition of the present invention has a continuous phase and a dispersed phase, and contains the following components (A), (B) and (C),
  • the ratio of the component (A) and the component (B) is from 99/1 to 60/40 by mass, and the component (A) and the component (B) are based on a total of 100 parts by mass (
  • the amount of C) is 1 to 20 parts by mass, the component (A) is substantially present in the continuous phase, and the component (B) is substantially present in the dispersed phase.
  • Component (A) a monomer unit having a styrene skeleton of 20 to 65% by mass, and a monomer unit selected from the group consisting of alkyl (meth) acrylate and alkyl (meth) acrylate 35 to 8 Styrene polymer containing 0% by mass and 0 to 15% by mass of acrylonitrile unit
  • Component (B) rubbery polymer containing 40 to 100% by mass of butadiene unit and 0 to 60% by mass of a monomer unit having a styrene skeleton
  • the styrene polymer (A) used in the present invention comprises, as essential constituent units, a monomer unit having a styrene skeleton and a monomer unit selected from the group consisting of (meth) acrylic acid and alkyl (meth) acrylate.
  • ⁇ -alkyl-substituted styrenes such as styrene, ⁇ -methylstyrene and ⁇ -methyl- ⁇ -methylstyrene, and halogenated styrenes such as o-chlorostyrene and ⁇ -chlorostyrene can be used.
  • Preferred monomers having a styrene skeleton include styrene, ⁇ -methylstyrene, and ⁇ -methylstyrene, and styrene is particularly preferred. These monomers having a styrene skeleton may be used alone or in combination of two or more.
  • alkyl (meth) acrylate examples include methyl acrylate, ethyl acrylate, ⁇ -butyl acrylate, methyl methacrylate, ethyl methacrylate, and ⁇ -butyl methacrylate. These monomers may be used alone or in combination of two or more. Methyl methacrylate is particularly preferred.
  • the styrene polymer ( ⁇ ) has a monomer unit having a styrene skeleton of 20 to 65% by mass, and a monomer unit selected from the group consisting of (meth) acrylic acid and alkyl (meth) acrylate 35 to 35%. 80% by mass, Atarilonitrile unit 0 to 15% by mass. / 0 .
  • the styrene polymer ( ⁇ ) can be produced using a known polymerization method. However, although the resin obtained by the emulsion polymerization method is transparent, it has a problem that it is colored yellow.In the bulk-one-suspension polymerization method in which the bulk polymerization is further performed, the obtained resin is transparent. There is a problem that the balance between sex and strength is reduced. Therefore, it is preferable to use a bulk polymerization method or a solution polymerization method.
  • a polymerization initiator can be used as needed during the polymerization.
  • ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclylhexanone peroxide, methylhexanone peroxide, and 1,1-bis (t —Butyl peroxy) Cyclohexane, 11-butyl_4,4-bis (t-butyl peroxy) Peroxy ketals such as pallate, cumenehydrido peroxyside, diisopropylbenzene peroxyside, 2,5 —Dimethylhexane-1,
  • Hydroperoxides such as 5-dihydroperoxide, t-butylcumylperoxide, a, '-bis (t-butylperoxy-1m-isopropyl) benzene, 2,
  • the method of adding these polymerization initiators is not particularly limited, and may be a method in which the polymerization initiator is charged all at once in the early stage of polymerization, a method in which the polymerization initiator is dividedly added several times from the initial stage to the latter stage of polymerization, or a method in which the two are added.
  • the methods can be used simultaneously.
  • a chain transfer agent or a solvent can be used as needed during the polymerization.
  • the chain transfer agent include terpinolene, ⁇ -methylstyrene dimer, ⁇ -dodecyl mercaptan, t-dodecyl mercaptan and the like.
  • the solvent include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, aliphatic hydrocarbons, and dialkyl group ketones alone or in a mixture of two or more. The solvent is used in an amount of 0 to 50% by mass based on the whole reaction solution. If it exceeds 50% by mass, the polymerization rate will be remarkably reduced, and the energy for recovering the solvent will be large, resulting in poor economic efficiency.
  • Rubber-like polymer (B) used in the present invention are those containing 6 0 mass% monomer units 0 having a butadiene unit 4 0 1 0 0 mass 0/0 and styrene skeleton, preferably 60 to 100% by mass of a butadiene unit and 0 to 40% by mass of a monomer unit having a styrene skeleton. / 0 .
  • the butadiene unit in the rubber-like polymer is less than 40% by mass, it becomes difficult to maintain a balance between Izod impact strength and transparency.
  • the ratio of the styrene polymer (A) and the rubbery polymer (B) in the transparent rubber-modified styrene resin composition is based on a total of 100 parts by mass of the component (A) and the component (B). 1 to 60/40.
  • the component (A) is substantially in a continuous phase
  • the component (B) is substantially in a dispersed phase.
  • the mass ratio of the rubber-like polymer is less than 1%, the effect of improving the impact strength is hardly observed, and when it exceeds 40%, the moldability and transparency of the rubber-modified styrene resin composition deteriorate. Resulting in.
  • the difference in the refractive index between the continuous phase and the dispersed rubber particle phase is generally 0.01 or less, preferably 0.005 or less. desirable.
  • (meth) containing an acrylic ester unit 8 0-1 0 0 mass 0/0 (meth) acrylic acid ester polymer (C) has a weight average molecular weight of 1 0 0 0-5 0 0 0
  • the molecular weight distribution (Mw / Mn) that is, the value obtained by dividing the weight average molecular weight Mw by the number average molecular weight Mn is 2. 5 or less (meth) acrylate copolymers.
  • Mw / Mn the value obtained by dividing the weight average molecular weight Mw by the number average molecular weight Mn is 2. 5 or less (meth) acrylate copolymers.
  • the weight average molecular weight Mw exceeds 500, transparency is reduced and the effect of improving fluidity is reduced. If Mw is less than 100, volatility will appear, and gas generation and bleeding will easily occur during molding.
  • the preferred Mw is from 1000 to 2500, and the more preferred Mw is from 100 to 2000.
  • the molecular weight distribution (Mw / Mn) of the (meth) acrylate polymer (C) is 2.5 or more, the moldability, transparency and impact properties cannot be balanced. It is more preferably 2.0 or less, and even more preferably 1.8 or less.
  • the (meth) acrylate used as a raw material of the (meth) acrylate polymer (C) used in the present invention is, for example, an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms.
  • the group may be linear or branched), (meth) acrylic acid polyalkylene glycol ester, (meth) acrylic acid alkoxyalkyl ester, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid glycidyl ester, ( (Meth) dialkylaminoalkyl acrylate, benzyl (meth) acrylate, phenoxyalkynole (meth) acrylate, cyclohexyl (meth) acrylate,
  • a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms (the alkyl group may be a straight chain or a branched chain), and the number of carbon atoms forming the alkyl group is 6
  • Copolymers containing 5 to 100% by mass of the above (meth) alkyl acrylate monomer component are preferred.
  • the alkyl group-forming (meth) acrylic acid alkyl ester monomer component having 6 or more carbon atoms is 5 to 70 mass. / 0 is preferred.
  • More preferred is a copolymer in which the (meth) alkyl acrylate monomer component having 6 or more carbon atoms forming an alkyl group is 2-ethylhexyl acrylate.
  • the (meth) acrylate polymer (C) contains (meth) acrylate units in an amount of 80 to 100% by mass.
  • (Meth) preferred ratio of Akuriru acid ester units is 9 0-1 0 0 mass 0/0, and more desirable ratio is 9 5 to 0 0 mass%. If the proportion of (meth) acrylic acid ester units is less than 80%, the effect of improving the fluidity will be reduced, and it will be difficult to maintain impact resistance and transparency.
  • the (meth) acrylate polymer (C) has 20 masses of monomer units other than the (meth) acrylate unit. / 0 or less may be contained.
  • any monomer can be used as long as it can be radically copolymerized with the (meth) acrylic acid ester monomer.
  • examples thereof include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, and ⁇ -methylstyrene.
  • Aromatic bier monomers such as methyl- ⁇ -methylstyrene, ⁇ -methoxystyrene, ⁇ -methoxystyrene, 2,4-dimethylstyrene, chlorostyrene, bromostyrene, etc., (meth) atalylic acid, and maleic anhydride , Fumaric acid, (meth) acrylamide, (meth) acryldialkylamide, butyl esters, butyl ethers, and (meth) aryl ethers. These can be used alone or in combination of two or more.
  • the (meth) acrylate polymer (C) used in the present invention can be obtained by ordinary radical polymerization, but is preferably obtained by a high-temperature continuous polymerization method at 180 to 300 ° C. Things. According to this method, it is difficult to cause a radical branching reaction starting from a hydrogen abstraction reaction from the polymer chain due to high temperature polymerization, and to obtain a polymer having a small number of branched components and a large number of linear components because the cleavage reaction has priority. Can be. In addition, since the cleavage reaction is prioritized, a low-molecular-weight polymer that does not contain impurities such as a large amount of an initiator and a chain transfer agent can be easily produced. Furthermore, if a stirred tank reactor is used as the reactor, a copolymer having a narrow composition distribution and molecular weight distribution can be obtained.
  • Japanese Patent Application Laid-Open No. 57-502171, Japanese Patent Application Laid-Open No. 59-62007, Japanese Patent Application Laid-Open No. 60-210507 Etc. may be followed.
  • a pressurizable reactor is set to a predetermined temperature under pressure
  • a monomer mixture comprising each monomer and, if necessary, a polymerization solvent is supplied to the reactor at a constant supply rate
  • a polymerization initiator can be added to the monomer mixture as needed.
  • the amount of the compound is preferably 0.001 to 3 parts by weight based on 100 parts by weight of the monomer mixture.
  • the pressure depends on the reaction temperature and the boiling point of the monomer mixture and the solvent to be used, and does not affect the reaction, but may be any pressure as long as the reaction temperature can be maintained.
  • the polymerization temperature for producing the polymer (C) used in the present invention is preferably from 180 to 300 ° C. If the temperature exceeds 300 ° C, coloring and thermal deterioration may occur.If the temperature is lower than 180 ° C, a branching reaction occurs to broaden the molecular weight distribution and a large amount of initiator or chain transfer to reduce the molecular weight. The use of chemicals adversely affects weatherability, heat resistance, and durability. In addition, production problems such as heat removal may occur. There is also. More preferably, 200 ° C to 270 ° C.
  • the residence time of the monomer mixture in the reactor that is, the reaction time, is preferably from 1 to 60 minutes, more preferably from 5 to 30 minutes.
  • the residence time is shorter than 1 minute, the monomer may not react sufficiently. If the residence time is longer than 60 minutes, productivity may be poor, and coloring or thermal deterioration may occur. . Further, a process using a continuous stirred tank reactor is more preferable than a tubular reactor because the composition distribution and the molecular weight distribution are narrowed.
  • the mixing ratio of the (meth) acrylate polymer (C) in the transparent rubber-modified styrene resin composition is 1 to 20 parts by mass based on the total of 100 parts by mass of the components (A) and (B). . Preferably it is 1 to 10 parts by mass. When the amount is less than 1 part by mass, no effect of improving the moldability is recognized, and when the amount is more than 20 parts by mass, impact resistance, rigidity and transparency are reduced.
  • the transparent rubber-modified styrene resin composition containing the above components (A), (B) and (C) can be produced, for example, by the following method.
  • composition containing component (A) and component (B) produced by polymerizing the raw material monomer of component (A) in the presence of component (B) is mixed with component (C) and extruded.
  • the component (B) is mixed with the composition containing the component (A) and the component (C) produced by polymerizing the raw material monomer of the component (A) in the presence of the component (C), and is extruded.
  • the composition containing the component (A) and the component (B) has a continuous phase and a dispersed phase, and the ratio of the component (A) and the component (B) is mass.
  • the ratio is 991 to 60/40
  • component (A) is substantially in the continuous phase
  • component (B) is substantially in the dispersed phase
  • HAZ E is less than 20%
  • the resulting transparent rubber-modified styrene resin composition is particularly preferred because it has excellent strength, transparency, and moldability.
  • the transparent rubber-modified styrene resin composition of the present invention may contain, if necessary, a lubricant such as zinc stearate, calcium stearate, or ethylenebisstearyl amide, a phenol-based or phosphorus-based antioxidant, an ultraviolet absorber, a coloring agent, and the like. And an additive or a flame retardant.
  • the polymers C-1 to (16 in the examples contain the component (C), that is, 80 to 100% by mass of the (meth) acrylate unit, and have a weight average molecular weight of 100 to 5%. It is equivalent to a (meth) acrylate polymer having a molecular weight distribution (weight-average molecular weight / number-average molecular weight) of 2.5 or less, and polymers D-1 to D- 3 is a comparative polymer used in place of the component (C).
  • the temperature of the oil jacket of a 1-liter pressurized stirred tank reactor equipped with an oil jacket was kept at 245 ° C.
  • a monomer composed of 100 parts by mass of butyl acrylate (hereinafter referred to as BA), 40 parts by mass of isopropyl alcohol, and 1.0 part by mass of ditertiary monobutyl peroxide (hereinafter referred to as DTBP) as a polymerization initiator was charged into the raw material tank.
  • the polymer is fed continuously from the raw material tank to the reactor at a constant feed rate (48 g Z minute, residence time: 12 minutes), and the mixed liquid mass in the reactor becomes 580 g—constant. It was continuously extracted from the reactor outlet.
  • the temperature inside the reactor was maintained at a desired value of 245 ° C.
  • the extracted reaction product was continuously separated for volatile components by a thin film evaporator kept at a reduced pressure of 30 kPa and a temperature of 250 ° C, and a copolymer containing almost no volatile components was recovered.
  • the weight average molecular weight Mw of the polymer C-11 in terms of polystyrene determined by GPC was 1,600, the number average molecular weight Mn was 1,000, and the molecular weight distribution Mw / Mn was 1.6.
  • the amount of volatile components in the resin by GC was less than 1%.
  • the polymers C _ 2 to 6 and D-1 to 3 are the monomers shown in Table 1, the solvent, the amount of the polymerization initiator, Except for the polymerization temperature conditions, it was obtained by the same operation as in the method for producing polymer C_1.
  • the Mw, Mn, and MwZMii of the polymers C-1 to C-6 and D-1 to C-3 thus obtained were as shown in Table 1. In addition, no problems such as yellowing were observed in the color tone of each polymer.
  • (D-4) is Sumoil P 260 (liquid paraffin manufactured by Matsumura Oil Co., Ltd.). table 1
  • Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were measured using gel permeation chromatography (GPC), using tetrafudrofuran as eluent, and using standard polystyrene.
  • GPC gel permeation chromatography
  • Mw / Mn molecular weight distribution
  • melt flow rate was measured at 220 ° C and a load of 10 kg by the method of JIS K-7210. However, in Examples and Comparative Examples using T-HIPS, measurement was performed at 200 ° C and a load of 5 kg.
  • HAZE evaluation Measure a 100 mm diameter, 2 mm thick disk-shaped test piece according to the method of JIS K-7105.
  • composition (AB) or component (AB) A composition containing the following three types of styrene polymer (A) and rubbery polymer (B) (hereinafter, also referred to as composition (AB) or component (AB)) was used.
  • T-AB S-l T oyl a c-900 (Toray)
  • T-one AB S—2 CT0520 (manufactured by Ce1)
  • T-HIPS SX-100 (A & M Polystyrene)
  • Component (C) that is, a polymer C-1 to C_6 which is a (meth) acrylate polymer or a polymer D-1 to D- which is a comparative polymer used in place of the component (C) 3 and the above composition (AB) were blended in the proportions shown in Tables 2 and 3 and a barrel temperature of 220 ° C and a screw speed of 100 rpm using a 4 Omm ⁇ twin screw extruder. Extruded under the conditions to produce a transparent rubber-modified styrene resin composition. Thereafter, test specimens were prepared using an injection molding machine, and MFR, impact strength, HAZE, Vicat softening point, tensile properties, etc. were evaluated. The results are shown in Tables 2 and 3.
  • Comparative example-1 100 17 0 101.8 14.0 0.0 4.3 40.0 20.0 Comparative example -2 100 19 0 96.4 16.9 0.0 5.7 39.0 16.4 Comparative example-3 100 4 0 91 9.1 0.0 7 43.0 46.0 Comparative example -4 100 3 21 25 99 10- 28.6 35 41.0 40.0 Comparative Example-5 100 3 19 13 98 9 -35.7 30 42.0 35.0 Comparative Example-6 100 5 24 40 98 12 -14.3 9 42.0 33.0 Comparative Example-7 100 7 27 58 97 1 1.5 -17.9 13 43.0 32.0 Comparative example -8 00 9 36 114 96 7 -50.0 60 40.0 32.0 Comparative example -9 100 3 7 68 88.7 5 -45.1 54 42.8 1 1 7.0 Comparative example -10 100 3 5 1 5 89.9 3.6 -60.4 69 41. 0 61.0 Comparative example -11 100 3 5 23 90.5 4.9 -46.2 6 43.0 39.0 Comparative example -12 100 3 6 50 86.4 1 1 2
  • Examples 21 to 27 show the effect on transparent HIPS. Also in this case, the addition of 3 parts shows an effect of improving the fluidity by 40% or more, and furthermore, the impact strength is hardly reduced.
  • Comparative Example 9 the effect of improving the fluidity is relatively high, but the transparency is significantly reduced.
  • Comparative Examples 10 and 11 it can be seen that the effect of improving the fluidity is small and the impact is significantly reduced.
  • Comparative Example 12 shows the results for mineral oil, which is a flow improver generally used for styrene resins. Although excellent in fluidity and impact strength, transparency is remarkably reduced.
  • Examples 5 to 14, Examples 18 to 20, and Examples 24 to 26 using the polymer (C13 to 6) obtained by copolymerizing HA are described in Examples 1 to 4. 4.
  • Examples 15 to 17 and Examples 21 The percentage of reduction in impact strength is smaller than that of Examples 1 to 23.
  • the copolymer of HA and BA also has a high effect of improving fluidity.
  • the transparent rubber-modified styrene resin inherently has excellent transparency and mechanical properties (impact strength, heat resistance, tensile strength, etc.) without impairing its moldability (fluidity, etc.). Can be dramatically improved, and a transparent rubber-modified styrene resin composition having an excellent balance between both properties can be obtained.
  • the transparent rubber-modified styrenic resin composition of the present invention has an excellent balance of transparency, mechanical properties, and moldability, so that the size of molded articles can be increased especially in various fields such as home electric appliances and OA equipment parts. And enables thinning, and its industrial value is great.

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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)

Abstract

Cette invention concerne une composition de résine de styrène transparente modifiée par caoutchouc présentant une phase continue et une phase dispersée. Cette résine se caractérise en ce qu'elle comprend un polymère de styrène spécifique (A) un polymère caoutchouc (B) renfermant des unités butadiène, et un polymère d'ester (meth)acrylique (C) comprenant de 80 à 100 % en poids d'unités d'ester (meth)acrylique et ayant un poids moléculaire moyen de 1000 à 5000 et une distribution du poids moléculaire (poids-poids moléculaire moyen/nombre-poids moléculaire moyen) de 2,5 ou moins. La proportion de l'ingrédient (A) par rapport à l'ingrédient (B) est de 99/1 à 60/40 en poids ; la quantité de l'ingrédient (C) est de 1 à 20 parties en poids par 100 parties en poids de la somme des ingrédients (A) et (B) ; et les ingrédients (A) et (B) sont présents sensiblement dans la phase continue et dans la phase dispersée, respectivement.
PCT/JP2003/015369 2002-12-10 2003-12-02 Composition de resine de styrene transparente modifiee par caoutchouc WO2004052988A1 (fr)

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KR20130074427A (ko) * 2011-12-26 2013-07-04 제일모직주식회사 유동성, 투명성 및 내충격성이 우수한 열가소성 수지 조성물

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JP2001031832A (ja) * 1999-07-23 2001-02-06 Techno Polymer Kk 熱可塑性樹脂組成物
JP2002338777A (ja) * 2001-05-18 2002-11-27 Mitsubishi Rayon Co Ltd 熱可塑性樹脂組成物およびこれを用いた多層押出シート

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001031832A (ja) * 1999-07-23 2001-02-06 Techno Polymer Kk 熱可塑性樹脂組成物
JP2002338777A (ja) * 2001-05-18 2002-11-27 Mitsubishi Rayon Co Ltd 熱可塑性樹脂組成物およびこれを用いた多層押出シート

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