WO2005000959A1 - Thermoplastic resin composition - Google Patents

Abstract

The invention provides a thermoplastic resin composition excellent in weather resistance, impact resistance and surface appearance, specifically, a thermoplastic resin composition comprising (I) 50 to 90 % by mass of a continuous phase made of a styrene/(meth)acrylic ester copolymer consisting of a styrenic monomer, a (meth)acrylic ester monomer, and, if necessary, a vinyl monomer copolymerizable with these monomers and (II) 10 to 50 % by mass of a dispersed phase made of a polymer obtained by grafting a polyolefinic rubbery elastomer having a glass transition temperature of -30°C or below with a styrene/(meth)acrylic ester copolymer consisting of a styrenic monomer, a (meth)acrylic ester monomer, and, if necessary, a vinyl monomer copolymerizable with these monomers, wherein the continuous phase has a weight-average molecular weight of 60,000 to 200,000 and the dispersed phase has a volume-mean particle diameter of 0.3 to 1.5μm and a graft ratio of 20 % or above.

Description

 Description Thermoplastic resin composition Technical field

 The present invention relates to a thermoplastic resin composition having excellent weather resistance, impact resistance, and appearance. Background art

 Conventionally, as a thermoplastic resin composition having excellent weather resistance and impact resistance, AES resin (acrylonitrile-ethylene rubber-styrene copolymer) has been known (for example, see Patent No. 313). Reference is made to No. 1243, Claim 1.) Since these AES resins have good weather resistance, they are often used without painting, and since there is no post-processing such as painting, the appearance of molded products is an extremely important characteristic. However, conventional AES resin did not always provide satisfactory appearance, especially gloss, and the weather resistance was not yet at a sufficient level.

 In addition, an aromatic vinyl monomer unit and a methyl acrylate monomer unit are essential components as a thermoplastic resin composition that has excellent weather resistance and impact resistance, and also has a good balance of gloss and other physical properties. A thermoplastic resin composition of a copolymer obtained by improving a copolymer by introducing a specific vinyl monomer unit and a specific modified polyolefin-based polymer has been proposed (for example, Japanese Patent Application Laid-Open No. (See Japanese Patent Publication No. 26 390, Claim 1). However, even with this method, satisfactory appearance was not always obtained. Disclosure of the invention

 In view of such circumstances, the present invention provides a thermoplastic resin composition having excellent weather resistance, impact resistance, and appearance.

 The present inventors have conducted intensive studies to solve such problems, and as a result, have found that a continuous phase of a specific styrene- (meth) acrylate-based copolymer and a dispersed phase of a specific graft polymer have The present inventors have found that the above-mentioned problems can be solved by a thermoplastic resin composition composed of the above, and have completed the present invention.

 That is, the present invention has the gist characterized by the following.

 (1) Styrene monomers including styrene monomers, (meth) acrylate monomers and, if necessary, vinyl monomers copolymerizable with these monomers.

50-90% by mass of a continuous phase of the (meth) acrylate copolymer,

 A polyolefin-based rubber-like elastic material having a glass transition temperature (Tg) of less than or equal to 30 degrees Celsius is added to a styrene-based monomer, a (meth) acrylate-based monomer, Containing styrene monomer copolymerizable with monomer

(Meth) a dispersed phase of a polymer obtained by grafting an acrylic acid ester-based copolymer in an amount of 10 to 50% by mass,

 A weight average molecular weight of the continuous phase is 60,000 to 200,000, and the volume average particle diameter of the dispersed phase is 0.3 to 1.0. And a graft ratio of at least 20%.

(2) The polyolefin rubber-like elastic material is a polymer or copolymer of an olefin monomer. The thermoplastic resin composition according to the above (1), which is:

 (3) The dispersed phase is a monomer unit having at least one kind of a monomer having a functional group selected from a carboxylic anhydride group, a propyloxyl group, an epoxy group, a hydroxyl group and an amino group. % Styrene- (meth) acrylic acid obtained by copolymerizing 0.1 to 10% by mass of a monomer unit having a functional group capable of reacting with the above functional group on a modified polyolefin rubber-like elastic material modified by The thermoplastic resin composition according to the above (1) or (2), which is a polymer obtained by grafting an ester copolymer by a reaction by melt mixing.

 (4) Modified polyolefin rubber-like elastic body in which the dispersed phase is modified with at least one or more monomer units having a carboxylic anhydride group or a carboxyl group in an amount of 0.1 to 10% by mass. In addition, a polymer obtained by grafting a styrene- (meth) acrylate-based copolymer obtained by copolymerizing 0.1 to 10% by mass of a vinyl monomer unit having an epoxy group by a melt-mixing reaction. A certain thermoplastic resin composition according to the above (1) or (2).

 (5) The thermoplastic resin composition according to any one of the above (1) to (4), comprising 60 to 85% by mass of a continuous phase and 15 to 40% by mass of a dispersed phase.

 (6) The thermoplastic resin composition according to any one of the above (1) to (5), wherein the continuous phase has a weight average molecular weight of 75,000 to 160,000.

 (7) The thermoplastic resin composition according to any one of the above (1) to (6), wherein the dispersed phase has a volume average particle diameter of 0.4 to 1. O ^ m.

 (8) The thermoplastic resin composition according to any one of the above (1) to (7), wherein the graft ratio of the dispersed phase is 30% or more. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail. The styrene- (meth) acrylate-based copolymer constituting the continuous phase of the thermoplastic resin composition of the present invention refers to a styrene-based monomer, a (meth) acrylate-based monomer, and It is a copolymer composed of a vinyl monomer copolymerizable with these monomers used in accordance with the above.

 Further, the graft polymer constituting the dispersed phase of the thermoplastic resin composition of the present invention includes a styrene-based monomer, a (meth) acrylate-based monomer, It is a polymer obtained by grafting a styrene- (meth) acrylate-based copolymer composed of a vinyl monomer copolymerizable with these monomers, which is used in accordance with the above.

 Styrene monomers used in the continuous phase and the dispersed phase of the present invention include styrene, α-methylstyrene, ρ-methylstyrene, o-methylstyrene, m-methylstyrene, ethylstyrene, p-t-butylstyrene, and the like. Among them, styrene is preferred. These styrene monomers may be used alone or in combination of two or more.

Examples of the (meth) acrylate-based monomer used in the present invention include methyl acrylate, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, and ethyl acrylate. Acrylates such as octyl, n-butyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, and decyl acrylate, Methyl methacrylate or n-butyl acrylate is preferred, and methyl methacrylate is particularly preferred. These (meth) acrylate monomers may be used alone or in combination of two or more.

 Further, vinyl monomers that can be copolymerized with these monomers used as needed include glycidyl methacrylate, glycidyl methyl methacrylate, vinyl glycidyl ether, aryl glycidyl ether, and methacryl glycidyl ether. A monomer having a carboxylic acid group, such as maleic anhydride, citraconic anhydride, 1,2-dimethylmaleic anhydride, ethyl maleic anhydride, phenylmaleic anhydride, and itaconic anhydride; Monomers having a carboxylic acid group such as acrylic acid, methacrylic acid, monomethyl itaconate, monoethyl fumarate, cinnamic acid and fumaric acid; monomers having a hydroxyl group such as aryl alcohol and hydroxystyrene; acrylamide , Methacrylamide, arylphenol and other monomers And monomers having an amino group such as arylamine and methylarylamine; and maleimide derivatives such as N-phenylmaleimide and N-cyclohexylmaleimide. These monomers may be used alone. Good, but two or more kinds may be used in combination.

 Examples of the polyolefin rubber-like elastic material used in the present invention include a polymer or copolymer of an olefin monomer and a copolymer of an olefin monomer and a non-conjugated gen monomer. A monomeric polymer or copolymer is preferred for obtaining good weather resistance.

 Examples of the olefin monomer constituting the polyolefin rubber-like elastic material include ethylene, propylene, 1-butene, isobutylene, 2-butene, cyclobutene, 3-methyl-1-butene, 4-methyl-1-butene, and Examples thereof include methyl-1-pentene, cyclopentene, 1-hexene, cyclohexene, 1-octene, 1-decene, and 1-decene. Further, examples of the non-conjugated diene monomer include ethylidene norporene, dicyclopentadiene, and 1,4-hexadiene.

 The polyolefin-based rubber-like elastic material of the present invention has a glass transition temperature (T g) of not more than 30 ° C., preferably not more than −40 ° C. If the glass transition temperature (T g) exceeds 130 degrees Celsius, impact resistance, particularly at low temperatures, becomes insufficient, which is not preferable.

 The thermoplastic resin composition of the present invention comprises: 50 to 90% by mass of a continuous phase of a styrene- (meth) acrylate-based copolymer; and 10 to 50% by mass of a dispersed phase of a graft polymer. contains. Among them, it is preferable to contain 60 to 85% by mass of a continuous phase of a styrene- (meth) acrylate copolymer and 15 to 40% by mass of a dispersed phase of a graft copolymer. . If the disperse phase of the graft polymer is less than 10% by mass, the W impact strength is insufficient, and if it exceeds 50% by mass, the appearance becomes insufficient, which is not preferable.

 The mass ratio between the continuous phase and the dispersed phase was measured by stirring the thermoplastic resin composition (mass A) in methyl ethyl ketone (MEK) at a temperature of 23 ° C for 24 hours and then centrifuging. The insolubles in MEK are separated by a separator and dried in a vacuum to measure the mass (assuming the mass is B), and it is determined by the following equations (1) and (2).

Number 1 Continuous phase (% by mass) = ~~-^ X 100 Equation 2 Dispersed phase (% by mass) = — X 1 0 0

 A The styrene- (meth) acrylate copolymer continuous phase has a weight average molecular weight (Mw) of 60,000 to 200,000, preferably 75,000. 00 0 to 16 0, 00 0. When the weight average molecular weight is less than 60,000, the impact resistance is insufficient, and when the weight average molecular weight exceeds 200,000, the appearance becomes insufficient. However, the weight average molecular weight of the continuous phase described here is the weight average molecular weight in terms of polystyrene obtained by measuring the MEK-soluble content of the thermoplastic resin composition by gel permeation chromatography (GPC). .

 Further, the dispersed phase of the graft polymer has a volume average particle diameter of 0.3 to 1.5 m, preferably 0.4 to 1.0 zm. If the volume average particle size is less than 0.3_im, the impact resistance is insufficient, and if the volume average particle size exceeds 1.5 m, sufficient appearance cannot be obtained, which is not preferable.

 Further, the graft ratio of the dispersed phase of the graft polymer is 20% or more, preferably 25 to 150%, more preferably 30 to 100%. If the graft ratio is less than 20%, the impact resistance is insufficient. However, the graft ratio described here means that the mass ratio of the dispersed phase in the thermoplastic resin composition is X, and the mass ratio of the polyolefin rubber-like elastic material in the thermoplastic resin composition is Y, It is obtained from Equation 3.

 Equation 3 Graft rate (%) =--~-X 100 In addition, the amount of each monomer constituting the styrene- (meth) acrylate-based copolymer in the continuous phase should satisfy the above conditions. Although not particularly limited, preferably, the styrene monomer unit is 10 to 70% by mass, the (meth) acrylate ester monomer unit is 30 to 90% by mass, and if necessary, It is from 0 to 10% by mass of a vinyl monomer unit copolymerizable with these monomers used. Particularly preferably, the styrene monomer unit is 20 to 60% by mass, the (meth) acrylate ester monomer unit is 40 to 80% by mass, and these monomers used as necessary. The copolymerizable vinylene monomer unit is 0 to 10% by mass.

Further, the amount of each monomer of the styrene- (meth) acrylic acid ester-based copolymer constituting the graft polymer of the dispersed phase is not particularly limited as long as the above-mentioned conditions are satisfied. Styrene monomer unit: 10 to 70% by mass, (meth) acrylate monomer unit: 30 to 90% by mass, and copolymerizable with these monomers used as necessary The content of the vinyl monomer unit is 0 to 10% by mass. Particularly preferably, the styrene-based monomer unit is 20 to 60% by mass, the (meth) acrylate ester-based monomer unit is 40 to 80% by mass, and these monomers used as necessary. The copolymerizable monomer unit is from 0 to 0% by mass. The method for producing the styrene- (meth) acrylate copolymer constituting the continuous phase of the thermoplastic resin composition of the present invention includes bulk polymerization, solution polymerization, suspension polymerization, and bulk suspension. Well-known techniques such as a synthesis method and an emulsion polymerization method can be exemplified. Either a batch polymerization method or a continuous polymerization method can be used.

 As a method for producing a graft polymer constituting the dispersed phase of the thermoplastic resin composition of the present invention, a polyolefin-based rubber-like elastic material is prepared by treating a carboxylic acid anhydride group, a carboxylic acid group, an epoxy group, a hydroxyl group and an amino group. After forming a modified polyolefin-based rubber-like elastic body modified with at least one monomer unit having a functional group selected from the above, a monomer having a functional group capable of reacting with the functional group of the monomer A method of obtaining a graft polymer by melt-mixing a styrene- (meth) acrylic acid ester-based copolymer obtained by copolymerizing the above with a modified polyolefin-based rubber-like elastic material and reacting them is performed. Further, when a copolymer having a carbon-carbon double bond of an olefin monomer and a non-conjugated diene monomer is used as the polyolefin rubber-like elastic material, in the presence of the polyolefin rubber-like elastic material, A styrene monomer, a (meth) acrylate monomer, and a vinyl monomer copolymerizable with these monomers, which are used as necessary, can be used in bulk polymerization, solution polymerization, and suspension polymerization. A method of performing a graft copolymerization by a known technique such as a suspension polymerization method, a bulk-suspension polymerization method, and an emulsion polymerization method is also included.

 In the present invention, the term "modified" means that a monomer unit used for the modification, for example, a maleic anhydride monomer unit, is present in the main chain or side chain of the polyolefin rubber-like elastic material. The denaturation method is not particularly limited. For example, JP-B-39-68010, JP-A-52-43667, JP-A-53-57176, JP-A-56-999 Modification can be carried out according to the methods disclosed in JP-A Nos. 25 and 58-445. It is preferable that the modification is performed as a graft rather than the introduction into the main chain from the viewpoint of low-temperature impact value and the like.

 The monomer used for the modification is not particularly limited as long as it can be modified with the monomer having the functional group, but is preferably a monomer having a carboxylic anhydride group or a hydroxyl group. Examples of the monomer having a carboxylic anhydride group include maleic anhydride, citraconic anhydride, 1,2-dimethylmaleic anhydride, ethyl maleic anhydride, phenylmaleic anhydride, and itaconic anhydride. Examples of the monomer include acrylic acid, methacrylic acid, monomethyl itaconate, monoethyl fumarate, cinnamic acid and fumaric acid, and are preferably maleic anhydride, acrylic acid and methacrylic acid, and particularly preferably. Maleic anhydride. These monomers may be used alone or in combination of two or more.

The monomer having a functional group capable of reacting with the monomer used for the modification includes a functional group capable of reacting with the functional group of the modified polyolefin rubber-like elastic material, and a styrene-based monomer. There is no particular limitation as long as it is a monomer copolymerizable with the monomer and the (meth) acrylate monomer, but the functional group of the modified polyolefin rubber-like elastic material is a carboxylic anhydride group or a carboxylic acid group. In the case, a monomer having an epoxy group, a hydroxyl group or an amino group, or a monomer having a carboxylic anhydride group, a hydroxyl group or an amino group when the functional group of the modified polyolefin rubber-like elastic material is an epoxy group or a hydroxyl group When the functional group of the rubber or modified polyolefin-based rubbery elastic body is an amino group, a monomer having a carboxylic anhydride group, a carboxyl group, an epoxy group or a hydroxyl group is preferred. Particularly preferred combinations include those in which the functional group of the modified polyolefin-based rubber-like elastic material has a carboxylic anhydride group or The monomer having a silyl group and a reactive functional group is a monomer having an epoxy group. Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl methyl methacrylate, vinyl daricidyl ether, aryl daricidyl ether, aryl glycidyl ether, and methallyl glycidyl ether. Glycidyl methacrylate. These monomers may be used alone or in combination of two or more.

 The amount of the monomer having a functional group in the modified polyolefin-based rubber-like elastic material is not particularly limited as long as the above-described conditions are satisfied, but is preferably 0.1 to 10% by mass. Yes, more preferably 0.5 to 5% by mass.

 Further, the amount of the monomer having a functional group in the styrene- (meth) acrylic acid ester-based copolymer used for the reaction with the modified polyolefin-based rubber-like elastic material is not particularly limited as long as the aforementioned conditions are satisfied. However, it is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass.

 A styrene- (meth) acrylic acid ester-based copolymer obtained by copolymerizing a modified polyolefin-based rubber-like elastic material and a monomer having a functional group capable of reacting with the functional group of the monomer used for the modification; Can be reacted by melt mixing using a usual melt kneading apparatus. Examples of the melt-kneading apparatus that can be suitably used include a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, a mixing roll, and the like, and particularly preferably a twin-screw extruder. The conditions of the melt mixing are not particularly limited as long as the thermoplastic resin composition under the above conditions is obtained, but preferably the resin temperature is 220 to 30 ° Τλ, and particularly preferably 240 It is desirable to optimize the screw configuration and cylinder temperature so that the temperature is up to 280 ° C. If the resin temperature is too low, the reaction will be insufficient and the desired graft ratio will not be obtained, and if the resin temperature is too high, the resin will be thermally decomposed and gelation due to excessive reaction will occur. Not good.

 Although the thermoplastic resin composition of the present invention has excellent weather resistance, an ultraviolet absorber, a light stabilizer, or an antioxidant may be used alone or in combination to further improve the weather resistance. Can be.

Examples of ultraviolet absorbers include 2- (5, -methyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-t-butyl-2'-hydroxyphenyl) benzotriazole, and 2- [2, -hydroxy 1 3 ', 5'-bis (α, 1-dimethylbenzyl) phenyl] benzotriazole, 2_ (3,, 5'-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 , — T_butyl-1, 5-methyl-2-hydroxyphenyl) 1 -5-chlorobenzotriazole, 2- (3,5'-di-t-butyl-2, hydroxyphenyl) 1 5—Black mouth benzotriazole, 2- (3,, 5, G-t-amyl-2, —hydroxyphenyl) benzotriazole, 2— [3,1 (3 ", 4", 5 ") , 6 "—tetrahydro 'phthalimidomethyl) 1, — Methyl-2, -hydroxyphenyl] benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -1-6- (2H-benzotriazole-1-yl) Benzotriazole-based ultraviolet absorbers such as [phenol], 2-ethoxy-12, -ethyl bisanilide, 2-ethoxy-5_t-butyl-2, monoethyl oxalate bisanilide and 2-ethoxy-4, 1-isodecylphenyl bisanilide oxalate, etc. Oxalanilide UV absorber, 2-hydroxy-41 n Octoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-14-methoxybenzophenone, 2-hydroxy-4-methoxy-15-sulfobenzophenone, 2,2, dihydroxy-14-methoxybenzo Benzophenone UV absorbers such as phenone, 2,2, dihydroxy-4,4,1-dimethoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, phenylsalicylate, p-t— Salicylic acid UV absorbers such as butylphenyl salicylate and p-octylphenyl salicylate, 2-ethylhexyl-2_cyano-3,3 'diphenylacrylic acid, ethyl-2-cyano3,3'- Cyanogen acrylate UV absorbers such as diphenyl chloride, rutile-type titanium oxide, and nana-type titanium oxide And titanium oxide-based ultraviolet stabilizers such as titanium oxide treated with a surface treating agent such as alumina, silica, silane coupling agent and titanium-based coupling agent.

 Light stabilizers include bis (2,2,6,6-tetramethyl-14-piperidyl) separate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, dimethyl succinate ' 11- (2-Hydroxyethyl) 4-Hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [[6, (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-Triazine-1,2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-1-piperidyl) imino]] and 1 — [2 -— [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] —4-1- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl -2, 2, 6, 6-tetramethylpiperidine and the like.

 Examples of antioxidants include triethylene glycol-bis [3_ (3_t_butyl-5-methyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -16_ (4-hydroxy- 3, 5—di-t-butylylanino) -1,

3,5-triazine, penyu erythrityltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionate, 2, 2-thiobis

Phenolic oxidation of (4_methyl-6_t-butylphenol) and 1,3,5-trimethyl_2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene Inhibitors, ditridecyl-3,3'-thiodipropionate, dilauryl-1,3'-thiodipropionate, ditetradecyl-3,3'-thiodipropionate, distearyl-1,3,3'-thiodipropionate, Dioctyl-3,3'-sulfur antioxidant such as thiodipropionate, trisnonylphenylphosphite, 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl-2-tridecyl) phosphite, (Tridecyl) Pentaerythri! ^ Bis (Oktadecyl) Pendiy Eri Sri! Ludi phosphite, bis (G-t-butylphenyl) ^ Ildiphosphite, bis (Gee t_butyl 4-methylphenyl) Rudiphosphite, dinonylphenyloctylphosphonite, tetrakis (2,4-di-t-butylphenyl) 1,4-phenylene-diphenylphosphonite, tetrakis (2,4-di_t-butylphenyl) )

Phosphorus antioxidants such as 4,4, -biphenylenedi-phosphonite, 10-decyloxy_9,10-dihydro-9-year-old 10-phosphaphenanthrene It is.

 Further, the thermoplastic resin composition of the present invention may contain additives such as a lubricant, a plasticizer, a coloring agent, an antistatic agent, a flame retardant, a mineral oil, a glass fiber, a carbon fiber, and an aramide fiber, depending on the application. Fillers such as fiber, talc, silica, myriki, and calcium carbonate may be blended within a range that does not impair the performance of the thermoplastic resin composition of the present invention.

 In the thermoplastic resin composition of the present invention, there is no particular limitation on the method of blending and melt-mixing the components, and a known method can be employed. For example, each raw material is uniformly mixed in advance with an evening tumbler or Henschel mixer, and then supplied to a single-screw extruder, twin-screw extruder, Banbury mixer, coneder, mixing roll, etc., and melt-mixed. There is a method of preparing as a sample. The thermoplastic resin composition of the present invention can be obtained by batch charging each component into a kneading apparatus.However, after obtaining a master batch pellet containing a high concentration of a graft polymer by melt mixing, The thermoplastic resin of the present invention is obtained by blending in a plurality of times, such as blending the styrene- (meth) acrylic acid ester-based copolymer and additives and the like as needed, and then blending them together. A resin composition can also be obtained.

 The thermoplastic resin composition of the present invention thus obtained can be processed into various molded articles by a method such as, for example, injection molding, compression molding, or extrusion molding, and then used.

 Example

 Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.

 First, the production of raw resin will be described.

(A) Manufacture of styrene- (meth) acrylate copolymer

 Reference Example 1: Styrene mono (meth) acrylate copolymer A_ 1

 100 kg of pure water, 0.5 g of sodium dodecylbenzenesulfonate, 0.5 g of calcium triphosphate, 250 g of styrene, 42 kg of styrene, and 58 kg of methyl methacrylate were put into an autoclave with a capacity of 250 liters, and polymerized. As an initiator, 150 g of t-butyl peroxyisobutyrate and 250 g of t-dodecylmer force were added, and the mixture was dispersed under stirring at a rotation speed of 150 rpm. This mixed solution was heated and polymerized at a temperature of 90 for 8 hours and at a temperature of 130 for 2.5 hours. After completion of the reaction, the resultant was washed, dehydrated and dried to obtain a styrene- (meth) acrylate copolymer A-1 in the form of beads. The polymerization rates of styrene and methyl methacrylate were both at least 99%.

 Reference Example 2: Styrene- (meth) acrylate copolymer A-2

 A styrene- (meth) acrylate-based copolymer A-1 was produced in the same manner as in Reference Example 1 except that t-dodecylmercaptan was changed to 50 g. An acrylate copolymer A-2 was obtained. The polymerization rates of styrene and methyl methyl acrylate were both 99% or more.

 Reference Example 3: Styrene- (meth) acrylate copolymer A-3

 A styrene- (meth) acrylate-based copolymer A-1 was produced in the same manner as in Reference Example 1 except that the amount of t-dodecylmercaptan was changed to 10 g. An acrylic ester copolymer A-3 was obtained. The polymerization rates of styrene and methyl methacrylate were both at least 99%.

Reference Example 4: Styrene mono (meth) acrylate copolymer A-4 100 kg of pure water, 0.5 g of sodium dodecylbenzenesulfonate, 250 g of tribasic calcium phosphate, 250 g of styrene, 25 kg of styrene, and 75 kg of methyl methacrylate were put into an autoclave with a capacity of 250 liters, and polymerized As an initiator, 150 g of t-butyl peroxyisobutyrate and 6.5 g of t-decyl mercaptan were added, and the mixture was dispersed with stirring at a rotation speed of 150 rpm. The mixture was polymerized by heating at 90 ° C. for 8 hours and at 130 ° C. for 2.5 hours. After completion of the reaction, the resultant was washed, dehydrated and dried to obtain a bead-like styrene- (meth) acrylate copolymer A-4. The polymerization rates of styrene and methyl methacrylate were both at least 99%.

 Reference Example 5: Styrene- (meth) acrylate copolymer A-5

 A styrene- (meth) acrylic bead was prepared in the same manner as in Reference Example 4 except that t-dodecylmercaptan was changed to 850 g. An acid ester copolymer A-5 was obtained. The polymerization rates of styrene and methyl methacrylate were both at least 99%.

 Reference Example 6: Styrene- (meth) acrylate copolymer A-6

 In Reference Example 4, except that the amount of t-dodecylmercaptan was changed to 100 g, a styrene- (meth) acrylate-based copolymer A-4 was produced in the same manner as the styrene- (meth) bead. An acrylate copolymer A-6 was obtained. The polymerization rates of styrene and methyl methacrylate were both at least 99%.

 Reference Example 7: Styrene- (meth) acrylic acid ester copolymer A- 7 copolymerized with a vinyl monomer having an epoxy group

 In an autoclave with a capacity of 250 liters, 100 kg of pure water, 0.5 g of sodium dodecylbenzenesulfonate, 250 g of tribasic calcium phosphate, 42 kg of styrene, 57 kg of methyl methacrylate, 57 kg of glycidyl methacrylate 1 Add 150 g of t-butylpropyloxybutyrate as a polymerization initiator and 400 g of t-dodecylmercaptan, and stir the mixture at 150 rpm. Dispersed. This mixed solution was heated and polymerized at a temperature of 90 for 8 hours and at a temperature of 120 for 1.5 hours. After completion of the reaction, washing, dehydration and drying were carried out to obtain a beaded styrene- (meth) acrylate copolymer A-7. The polymerization rates of styrene, methyl methacrylate and glycidyl methacrylate are all at least 99%, and the daricidyl methacrylate monomer unit in the styrene mono (meth) acrylate copolymer A-7 is 1.0. It is mass%.

 Reference Example 8: Styrene- (meth) acrylic acid ester-based copolymer obtained by copolymerizing a vinyl monomer having an epoxy group A-8

 In Reference Example 7, except that methyl methacrylate was changed to 57.6 kg and glycidyl methacrylate was changed to 0.4 kg, it was manufactured in the same manner as the styrene-mono (meth) acrylate ester copolymer A_7. A beaded styrene- (meth) acrylate ester copolymer A-8 was obtained. The polymerization rates of styrene, methyl methacrylate, and glycidyl methacrylate were all at least 99%, and dalicidyl methacrylate monomer in styrene mono (meth) acrylate copolymer A-8 The body unit is 0.4% by mass.

 Reference Example 9: Styrene mono (meth) acrylate ester copolymer obtained by copolymerizing a vinyl monomer having an epoxy group A-9

100 kg pure water, dodecylbenzenes in a 250 liter autoclave 0.5 g of sodium sulfonate, 250 g of tribasic calcium phosphate, 25 kg of styrene, 74 kg of methyl methacrylate, 1 kg of glycidyl methacrylate, 150 g of t_butylbutyloxyisobutyrate as a polymerization initiator, t 650 g of dodecyl mercaptan was added, and the mixture was dispersed with stirring at a rotation speed of 150 rpm. This mixed solution was heated and polymerized at a temperature of 90 ° C. for 8 hours and at a temperature of 120 ° C. for 1.5 hours. After completion of the reaction, the resultant was washed, dehydrated and dried to obtain a styrene- (meth) acrylate copolymer A-9 in the form of beads. The polymerization rates of styrene, methyl methacrylate, and glycidyl methacrylate are all 99% or more, and the glycidyl methacrylate monomer unit in the styrene- (meth) acrylate copolymer A_9 is 1.0. It is mass%.

 (B) Production of styrene-vinyl cyanide copolymer

 Reference Example 10: Styrene-vinyl cyanide copolymer B-1

 In a 250 liter autoclave, add 64 kg of pure water, 450 g of tribasic calcium phosphate, 55 kg of styrene, and 25 kg of acrylonitrile, and 150 g of t-butyl propyl acetate as a polymerization initiator and 380 g of t-dodecyl mercaptan. The mixture was added and dispersed under stirring at a rotation speed of 150 rpm. The mixture was heated to a temperature of 100 ° C. while stirring, and 30 k of pure water and 20 kg of styrene were separately added continuously over 6 hours. After the addition was completed, the temperature was raised to 120 ° C and left for 2 hours to complete the polymerization. After the completion of the reaction, the resultant was washed, dehydrated and dried to obtain a styrene-vinyl cyanide copolymer B-1 in the form of beads. The polymerization rates of styrene and acrylonitrile were both 99% or more.

 Reference Example 11: Styrene mono-cyanide copolymer obtained by copolymerizing a vinyl monomer having an epoxy group B-2

 A 250 liter autoclave is charged with 64 k of pure water, 450 g of tribasic calcium phosphate, 54 kg of styrene, 25 kg of acrylonitrile, 1 kg of glycidyl methacrylate, and 150 g of t-butyl peroxyacetate as a polymerization initiator. Then, 380 g of t-dodecylmer force was added, and the mixture was dispersed under stirring at a rotation speed of 150 rpm. The mixture was heated to a temperature of 100 ° C. while stirring, and 30 kg of pure water and 20 kg of styrene were separately added thereto continuously over 6 hours. After the addition was completed, the temperature was raised to 120 ° C and left for 2 hours to complete the polymerization. After completion of the reaction, the resultant was washed, dehydrated and dried to obtain a styrene-vinyl cyanide copolymer B-2 in the form of beads. The polymerization rates of styrene, acrylonitrile, and daricidyl methacrylate are all 99% or more, and the glycidyl methacrylate monomer unit in the styrene monocyanocyanide copolymer B-2 is 1.0% by mass. It is.

 (C) Manufacture of modified polyolefin rubber-like elastic material

 Reference Example 12: Modified polyolefin rubber-like elastic material C-1

20 kg of ethylene-propylene rubber with a glass transition temperature (Tg) of 55 ° C, 400 g of maleic anhydride in powder form, and 20 g of 2,5-dimethyl-2,5-bis (t-butyl peroxy) hexane Was charged into a 75-liter Henschel mixer through which nitrogen was passed, stirred for 5 minutes and uniformly blended. The mixture was resinized using a twin-screw extruder KTX-30 (Kobe Steel, L / D = 46.8). The conditions were adjusted so that the temperature was 250 to 260 ° C, and the mixture was melt-mixed to obtain a pellet-like modified polyolefin-based rubber-like polymer C-11. The maleic anhydride in the modified polyolefin-based rubber-like elastic material was used. The monomer unit was 1.8% by mass. For the measurement of maleic anhydride monomer units, sample pellets were vacuum dried at 150 ° C for 5 hours and subjected to FT-IR measurement (device name: “BIO- RAD FTS—575 C ”), and the amount of maleic anhydride monomer units was calculated using a previously prepared calibration curve.

 (D) Production of graft polymer-containing masterbatch pellets

 Reference Example 13: Master batch pellet containing graft polymer D-1

 The styrene- (meth) acrylic acid ester-based copolymer A-7 copolymerized with the epoxy group-containing Bier monomer of Reference Example 7 was 6.4 kg, and the modified polyolefin-based rubber-like elastic material of Reference Example 12 was used. After a 3.6 kg sample of C-1 was blended using a Henschel mixer, the cylinder temperature was adjusted to 250 t using a twin screw extruder KTX-30 (Kobe Steel, L / D = 46.8). : Melt mixing under the conditions of a screw rotation speed of 400 rpm and a discharge rate of 40 khr to obtain a graft polymer-containing mass batch pellet D_1.

 Reference Example 14: Master-batch pellet containing graft polymer D-2

 A master batch containing a graft polymer was prepared in the same manner as in Reference Example 13, except that the screw rotation speed was changed to 500 rpm and the discharge rate was changed to 30 kg / hr. Pellet D-2 is obtained.

 Reference Example 15: Master batch pellet D-3 containing graft polymer

 A master batch containing a graft polymer was prepared in the same manner as in Reference Example 13 except that the screw rotation speed was changed to 500 rpm and the discharge rate was changed to 2 O kg / hr. Pellet D-3 is obtained.

 Reference Example 16: Master batch pellet containing graft polymer D-4

 The styrene- (meth) acrylic acid ester-based copolymer A-8 copolymerized with an epoxy group-containing vinyl monomer of Reference Example 8 weighs 6.4 kg, and the modified polyolefin rubber-like elasticity of Reference Example 12 After blending 3.6 kg of the body C-1 using a Henschel mixer, the mixture was cooled with a twin-screw extruder KTX-30 (Kobe Steel, L / D = 46.8) to determine the cylinder temperature. The resulting mixture was melt-mixed under the conditions of 250 ° C, a screw rotation speed of 400 rpm, and a discharge rate of 40 kg / hr, to obtain a master polymer pellet D-4 containing a graft polymer.

 Reference Example 17: Master batch pellet containing a graft polymer D-5

 A master batch containing a graft polymer was manufactured in the same manner as in the graft polymer-containing master batch D-4, except that the screw rotation speed was changed to 500 rpm and the discharge rate was changed to 30 kg / hr in Reference Example 16. Pellet D-5 is obtained.

 Reference Example 18: One batch pellet containing graft polymer D-6

 The styrene- (meth) acrylic acid ester-based copolymer A-9 copolymerized with the vinyl monomer having an epoxy group of Reference Example 9 was 6.4 kg, and the modified polyolefin rubber-like elasticity of Reference Example 12 was used. After 3.6 kg of the body C-1 was blended using a Henschel mixer, the cylinder was cooled using a twin-screw extruder KTX-30 (Kobe Steel, L / D = 46.8) to determine the cylinder temperature. The mixture was melt-mixed under the conditions of 250 ° C, a screw rotation speed of 400 rpm, and a discharge rate of 40 kgZhr, to obtain a graft polymer-containing mass batch P-6.

Reference Example 19: Master-batch pellet containing graft polymer D-7 The styrene- (meth) acrylic acid ester copolymer A-7 copolymerized with an epoxy group-containing vinyl monomer of Reference Example 7 was 6.4 kg, and the modified polyolefin rubber elastomer of Reference Example 12 was used. After blending 3.6 kg of C-1 with a Henschel mixer, this was blended with a twin-screw extruder TEM-35B (manufactured by Toshiba Machine Co., Ltd., LZD = 36) at a cylinder temperature of 210 ° C. The mixture was melt-mixed under the conditions of a screw rotation speed of 200 rpm and a discharge rate of l S kgZhr to obtain a graft polymer-containing mass batch P-7. Reference Example 20: Master batch pellet containing graft polymer D-8

 Reference Example 11 Styrene mono-cyanide copolymer B_2 obtained by copolymerizing the vinyl monomer having an epoxy group of 1 was 6.4 kg, and modified polyolefin rubber-like elastic body C-11 of Reference Example 12 was 3 After blending 6 kg with a Henschel mixer, this was mixed with a twin screw extruder KTX-30 (Kobe Steel, LZD = 46.8) at a cylinder temperature of 250 and a screw rotation speed of 400 r. The mixture was melt-mixed under the conditions of pm and a discharge rate of 40 kgZhr to obtain a master batch pellet D-8 containing a graft polymer.

 (E) Production of thermoplastic resin

 Reference Example 21: Thermoplastic resin E-1

 A 100-liter autoclave was charged with 7.2 kg of ethylene-propylene-ethylidene norbornene rubber having a glass transition temperature (Tg) of 43 ° C, 13.8 kg of styrene, and 19.0 kg of methyl methacrylate. Stir at 60 ° C until the rubber is completely dissolved.Add 100 g of t_dodecylmer force and 160 g of t-butyl butoxybenzoate, polymerize at 90 ° C for 8 hours, and further polymerize at 120 ° C. The temperature was raised to C and left for 2 hours to complete the polymerization. The reaction liquid was supplied to a vented twin-screw extruder to perform devolatilization, and a pellet of thermoplastic resin E-1 was obtained. Examples 1 to 11 and Comparative Examples 1 to 8

 Contains a styrene- (meth) acrylate copolymer produced in Reference Examples 1 to 6, a styrene-pinyl cyanide copolymer produced in Reference Example 10, and a graft polymer produced in Reference Examples 13 to 20 After mixing the master batch pellets in the ratios shown in Tables 1 and 2 and mixing them with a Henschel mixer, the resin temperature was adjusted using a twin-screw extruder KTX-30 (manufactured by Kobe Steel, L / D = 46.8). The conditions were adjusted to 250 to 260 ° C, melt-mixed, and pelletized. Using the sample pellets obtained and the pellets obtained in Reference Example 21, each analysis value and each physical property value were measured according to the following measurement methods. Tables 1 and 2 show the measured values.

 (1) Measurement of mass ratio between continuous phase and dispersed phase

 The sample pellets (assuming mass A) whose mass has been measured in advance are stirred in methyl ethyl ketone (MEK) at a temperature of 23 X for 24 hours, and then the insoluble matter is separated from the MEK by a centrifuge. After the separation operation, the mixture was allowed to stand for 30 minutes. The operating conditions of the centrifuge are as follows.

Temperature: _ 9 ° C

Speed: 20000 r pm

Time: 60 minutes

Separate the supernatant and precipitate from the centrifuged solution, dry the precipitate with a vacuum dryer, measure the mass (assume mass B), and use the following Equations 4 and 5 to calculate the continuous phase. And the mass ratio of the dispersed phase were determined. Number 4

 A-B

 Continuous phase (% by mass) = X 100

A number 5

(2) Measurement of weight average molecular weight of continuous phase

 The supernatant liquid of the centrifuged solution was separated, and methanol was added to precipitate a styrene- (meth) acrylate-based copolymer (continuous phase). The precipitate was collected and measured under the following GPC measurement conditions.

Equipment name: SYSTEM—21 Shode X (Showa Denko KK)

Column: 3 PL gel MIXED-B in series

Temperature: 40 ° C

Detection: Differential refractive index

Solvent: tetrahydrofuran

Concentration: 2% by mass

Calibration curve: Prepared using standard polystyrene (PS) (manufactured by PL), and the weight average molecular weight was expressed in terms of PS.

 (3) Measurement of volume particle size distribution of dispersed phase

 Approximately lg of the sample pellet is stirred in 100 g of N, N-dimethylformamide (DMF) for 24 hours, diluted to an appropriate concentration with the addition of DMF, and analyzed by laser diffraction scattering method. (COULTER LS 230 type).

 (4) Graft ratio of dispersed phase

 Assuming that the mass ratio of the dispersed phase obtained by measuring the mass ratio of the continuous phase and the dispersed phase is X, and the mass ratio of the polyolefin rubber-like elastic material obtained from the compounding ratio is Y, The graft ratio was determined.

 Number 6

 ― Γ

 Graft rate (%) = —- "One X I 00

(5) Drop weight impact strength measurement

 Using an injection molding machine (SYCAP 165/75) manufactured by Sumitomo Heavy Industries, Ltd., a sample pellet was molded under the conditions of a cylinder temperature of 240 ° C and a mold temperature of 60 ° C. A plate test piece was prepared. Using a DuPont type falling weight impact tester, a weight of 500 g was dropped on the test piece, and the 50% crushing height was measured. (Unit: cm)

 (6) Appearance evaluation

Using an injection molding machine (IS-50EP) manufactured by Toshiba Machine Co., The test piece was molded under the conditions of a temperature of 240 ° C for the binder and a temperature of 60 ° C for the mold, and a square plate test piece measuring 55 x 90 x 2 mm was prepared. The test piece was measured for 60 ° specular glossiness in accordance with JISK-7105 (unit:%). In addition, the presence or absence of a flow mark was visually determined for this test piece.

〇: No flow mark

X: With flow mark

 (7) Weather resistance evaluation

 The test piece used for the gloss measurement was subjected to a weather resistance test under the following conditions, and the color difference AEab * before and after irradiation was measured according to JIS K-7105.

 Testing machine: Sunshine weather meter “WEL—SUN—HCH—EBJ (Suga Test Machine Co., Ltd.)

 Atmosphere: 63 ° C, with shower

Irradiation time: 1000 hours

table 1

 Example

 1 2 3 4 5 6 7 8 9 10 1 1

A-1 (Quality Wei) 75 65 50 25 15 50 50 Styrene- (meth) acrylate Este A-2 (MS¾P) 50

 Copolymer A—4 (fine 50

 A—5 (parts by mass) 50

 Distribution

 D-1 (fine 25 35 50 75 85 50

 Mouth

 Master D-2 containing Gerafto copolymer

 Let's Lettuce D-5 (Quality 50

 D—6 (parts by mass) 50 50

 Thermoplastic resin E-1) Mass ratio of 100th line Mass% 87. 4 82. 3 74. 7 62. 1 57. 1 74. 7 76. 5 76. 5 72. 5 77. 2 73. 4 M * Average molecular weight (MW) 119,000 116,000 114,000 105,000 102,000 177,000 85,000 72,000 115,000 113,000 110,000 min

 Distance to mass ratio Mass. / 0 12.6 17.7 25.3 37.9 42.9 25.3 23.5 23.5 27.5 22.8 26.6

 Volume average particle size 0.49 0.49 0.49 0.49 0.49 0.49 0.88 0.88 0.38 1.01 0.85 value

 Polyolefin-based comb-shaped bullet 1) Mass ratio of living body% 8.8 12.4 17.7 26.5 30.0 17.7 17.7 17.7 17.7 17.7 18.0 Graft 43 43 43 43 43 43 33 33 55 29 48 Drop Cai Jia (500g weight) cm 15 53 103> 150> 150 135 75 40 25 45 85

+ Object Photo-separation% 94 93 92 90 88 88 93 93 93 88 90 Property With or without flow mark 〇 〇 〇 〇 〇 〇 〇 〇 〇 候 耐 Weather resistance (color after illuminating fiber mlEab *) 4.1.4.4 4.5 5.4.8 5.0 4.4.3.4.2.4.4.5.0 11.5

Table 2 Comparative examples

 1 2 3 4 5 6 7 8

A-1 (parts by mass) 85 50 ₍ 50 50

 Styrene mono (meth) acrylate copolymer

 A—3 (parts by mass) 50

 Body

 A—6 (parts by mass) 50 Styrene-vinyl cyanide copolymer B-1 (parts by mass) 50 D—1 (parts by mass) 15 100 50

 D—3 (parts by mass) 50

 D—4 (parts by mass) 50

 To the master craft containing kraft copolymer. Let

 D-6 (parts by mass) 50

 D—7 (parts by mass) 50

 D—8 (parts by mass) 50 Weight ratio of continuous phase Mass% 92.4 49.5 70.3 78.4 79.1 74.7 76.5 75.6 min Weight average molecular weight of continuous phase (Mw) 120,000 92,000 116,000 112,000 112,000 217,000 59,000 126,000 % 7.6 50.5 29.7 21.6 20.9 25.3 23.5 24.4 Value Volume average particle diameter μm 0.49 0.49 0.29 1.72 1.40 0.49 0.88 0.64 e. Liolefin type: mass ratio of rubber-like elastic body mass% 5.3 35.3 17. ph 17.7 17.7 17.7 17.7 17.7

Graft ratio% 43 43 68 22 18 43 33 38 Drop weight impact strength (500 g weight) cm <10> 150 <10 20 <10 140 <10 130 Object Gloss% 94 85 93 83 88 80 94 80 Property With or without flow mark 〇 X 〇 X 〇 X 〇 候 Weather resistance (color difference before and after irradiation lEab *) 3.8 4.8 4.4 5.7 5.6 4.2 4.5 18.5

The examples relating to the thermoplastic resin composition of the present invention were all excellent in weather resistance, impact resistance, and appearance, but were compared in the thermoplastic resin composition not satisfying the conditions of the present invention. In the example, one of the physical properties out of weather resistance, impact resistance and appearance was inferior. Industrial applicability

 According to the present invention, a thermoplastic resin composition having weather resistance, impact resistance, and appearance can be provided.

Claims

The scope of the claims 1. Styrene containing (styrene) monomer, (meth) acrylate monomer, and, if necessary, vinyl monomer copolymerizable with these monomers. 50 to 90% by mass of a continuous phase of the acid ester copolymer;  A polyolefin-based rubber-like elastic material having a glass transition temperature (Tg) of less than or equal to 30 degrees Celsius is added to a styrene-based monomer, a (meth) acrylate-based monomer, 10 to 50% by mass of a polymer dispersed phase obtained by grafting a styrene- (meth) acrylate-based copolymer containing a vinyl monomer copolymerizable with a monomer  Wherein the weight average molecular weight of the continuous phase is 60, '000 to 200,000, and the volume average particle size of the dispersed phase is 0.3 to 1 A thermoplastic resin composition having a diameter of 5 m and a daraft ratio of 20% or more. 2. The thermoplastic resin composition according to claim 1, wherein the polyolefin rubber-like elastic body is a polymer or copolymer of an olefin monomer. ' 3. The dispersed phase is a monomer unit having at least one kind of monomer having a functional group selected from a carboxylic anhydride group, a propyloxyl group, an epoxy group, a hydroxyl group and an amino group. Styrene- (meth) acrylic material obtained by copolymerizing 0.1 to 10% by mass of a monomer unit having a functional group capable of reacting with the above functional group on a modified polyolefin rubber-like elastic material modified by 3. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a polymer obtained by grafting an acid ester copolymer by a reaction by melt mixing.  4. The modified polyolefin-based rubber-like elastic body in which the dispersed phase is modified with at least one or more monomer units 0.1 to 10% by mass of a monomer having a carboxylic anhydride group or a propyloxyl group, It is a polymer obtained by grafting a styrene- (meth) acrylate-based copolymer obtained by copolymerizing 0.1 to 10% by mass of a vinyl monomer unit having an epoxy group by a melt-mixing reaction. The thermoplastic resin composition according to claim 1, wherein:  5. The thermoplastic resin composition according to any one of claims 1 to 4, comprising a continuous phase of 60 to 85% by mass and a dispersed phase of 15 to 40% by mass.  6. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the continuous phase has a weight average molecular weight of 75,000 to 160,000.  7. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the dispersed phase has a volume average particle diameter of 0.4 to 1.0 m.  8. The thermoplastic resin composition according to any one of claims 1 to 7, wherein the graft ratio of the dispersed phase is 30% or more.