JP3476382B2 - Rubber-like polymer composition and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a rubber-like polymer composition having a specific structure, and an impact-resistant styrene-based resin composition using the rubber-like polymer composition. Specifically, the rubber-like polymer composition of the present invention is an impact-resistant styrene-based resin composition having a remarkably excellent balance of impact strength and gloss when used as a toughening agent for impact-resistant styrene-based resin compositions. I will provide a.

[0002]

2. Description of the Related Art Polystyrene has been used for various purposes because it has excellent rigidity, transparency, luster and the like and has good moldability. However, this polystyrene has a major drawback of being inferior in impact resistance, and various unvulcanized rubbers are used as a toughening agent in order to improve this drawback. Among them, impact-resistant styrene-based resin compositions obtained by radically polymerizing a styrene-based monomer in the presence of unvulcanized rubber and graft-polymerized on a rubber-like polymer are industrially widely produced.

As unvulcanized rubber used for this purpose, there are polybutadiene and styrene-butadiene copolymer, and polybutadiene is widely used for imparting excellent impact resistance. In recent years, as the applications of impact-resistant styrene resin compositions have spread to housings and other parts of household electric appliances, axle parts, office equipment parts, daily sundries and toys, etc. As a result, there is a strong demand for impact-resistant styrene-based resin compositions having an excellent balance of appearance characteristics and impact resistance.

The impact-resistant styrenic resin composition is obtained by dissolving polybutadiene rubber or styrene-butadiene copolymer rubber as a rubber-like polymer in a styrene monomer and subjecting it to bulk polymerization or bulk-suspension polymerization with stirring. It is generally manufactured in. Generally, the impact resistance can be improved by increasing the content of the rubber-like polymer, but the styrene resin having the increased rubber-like polymer has an improved impact strength but a reduced gloss. . On the other hand, the gloss can be improved by reducing the content of the rubber-like polymer or by refining the particles of the rubber-like polymer dispersed in the resin, but the impact resistance is significantly lowered.

Conventionally, as a method for improving impact-resistant styrenic resin compositions, the solution viscosity of a conjugated diene polymer is specified (Japanese Patent Publication No. 58-4934), the solution viscosity of a conjugated diene polymer and Mooney. Specification of relationship of viscosity (Japanese Patent Publication No. 53-44188), specification of relationship between solution viscosity of conjugated diene polymer and tensile elastic modulus and swelling degree in crosslinked organic peroxide (JP-A-60-25001). No. gazette) is proposed. However, in these methods, compared with the case of using conventional polybutadiene,
Although the balance between impact resistance and gloss is improved, it is not always satisfactory.

On the other hand, JP-A-61-143415,
JP-A-63-165413, JP-A-2-1321
No. 12, JP-A-2-208312, etc., propose a method of improving impact resistance and appearance characteristics by using a styrene-butadiene block copolymer having a specific structure. However, a detailed examination of these methods did not yield a practically satisfactory balance of impact resistance and appearance characteristics, and the copolymer was liable to be powdered and formed into a veil-like shape. Is difficult and
There is a problem in that it is difficult to handle the impact resistant styrene resin during manufacturing. In JP-A-4-209614, JP-A-5-148331 and JP-A-6-107744, a composition of a styrene-butadiene diblock copolymer and a butadiene polymer is used to obtain a powder. Rubber-like polymerization, which is difficult and easy to form into a veil, is described. In these methods, the balance between impact resistance and appearance characteristics is improved, but it is not always satisfactory. .

[0007]

As described above, when the conventional rubber-like polymer is used in the impact-resistant styrene resin, it is necessary to improve the conflicting balance between impact resistance and gloss to a satisfactory degree. Was difficult. The present invention is to solve the problems as described above, excellent in bale moldability, and when used as a toughening agent for impact-resistant resins,
The present invention provides a rubber-like polymer composition capable of remarkably improving the balance of physical properties of impact resistance and gloss, and an impact resistant styrene resin composition having remarkably improved balance of physical properties of impact resistance and gloss.

[0008]

In the present invention, impact resistance
Impact-resistant styrene-based resin with excellent balance of physical properties and gloss
As a result of a detailed study on obtaining a fat composition,
Has a specific structure that has not been studied as a toughening agent
A rubber-like polymer composition capable of achieving the above-mentioned object
The present invention has been completed and the present invention has been completed. That is, the present invention
Is: (1) The following general formula, Block copolymer (1): B1-S-B2 Polymer (2): B3 (However, the block B1 is composed of a conjugated diene monomer.
Polymer or conjugated diene-based monomer and aromatic vinyl monomer
Block B2 is a conjugated diene
Aromatic polymer or conjugated diene monomer
Block S is a copolymer composed of a vinyl group monomer
Is a polymer composed of an aromatic vinyl monomer,B3
Is a polymer composed of a conjugated diene-based monomer or a conjugated diene
It is a copolymer composed of a system monomer and an aromatic vinyl monomer.
Block copolymer (1) represented by
Rubber-like polymerization consisting of 90 parts by weight and 90 to 10 parts by weight of the polymer (2)
A body composition, (I) Gel permeation of block copolymer (1)
Peak part of the molecular weight distribution curve measured by chromatography
Polystyrene equivalent molecular weight (Mwp) of 100,000 to 600,000, (Ii) A wholly aromatic vinyl monomer in the block copolymer (1)
The content of the monomer (TS) is 10 to 60% by weight, (Iii) Block in block copolymer (1)
Gel Permeation Chromatography of Aromatic Vinyl Polymers
The peak portion of the molecular weight distribution curve measured by
Ristylene equivalent molecular weight (Mwps) is 10,000-1
50,000 and 2/3 or less of the peak molecular weight
The content ratio of the lower molecular weight part is 2 in the aromatic vinyl polymer.
0% by weight or less, (Iv) Gel permeation chromatography of polymer (2)
Of the peak part of the molecular weight distribution curve measured by the graph
Tilene equivalent molecular weight (Mwp2) is 100,000 to 500,000, (V) Peak molecular weight (Mw) of block copolymer (1)
p), block copolymer(1)Peak of block S in
Molecular weight (Mwps), peak of block copolymer (2)
The relationship of molecular weight (Mwp2) 0.2 × (Mwp−Mwps) ≦ Mwp2 ≦ 2.0 ×
(Mwp-Mwps) A rubbery polymer composition is provided. Also,

Block copolymer (1) and polymer (2)
However, it is also characterized in that an organolithium compound is obtained as an initiator in a hydrocarbon solvent. Further, a mixture of an aromatic vinyl monomer or a monomer mainly containing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer 75 to
An impact-resistant styrenic resin composition obtained by radical polymerization of 98 parts by weight and 2 to 25 parts by weight of a rubber-like polymer by a bulk polymerization method, a bulk suspension polymerization method, or a solution polymerization method, wherein Provided is an impact-resistant styrene resin composition, wherein the polymer is the rubber-like polymer composition described above or described.

The present invention will be described in detail below. (1) Rubber-like polymer composition (I) The rubber-like polymer composition of the present invention has the following general formula: Block copolymer (1): B1-S-B2 Polymer (2): B3 (However, the block B1 is composed of a conjugated diene monomer.
Polymer or conjugated diene-based monomer and aromatic vinyl monomer
Block B2 is a conjugated diene
Aromatic polymer or conjugated diene monomer
Block S is a copolymer composed of a vinyl group monomer
Is a polymer composed of an aromatic vinyl monomer,B3
Is a polymer composed of a conjugated diene-based monomer or a conjugated diene
It is a copolymer composed of a system monomer and an aromatic vinyl monomer.
Block copolymer (1) represented by
Rubber-like polymerization consisting of 90 parts by weight and 90 to 10 parts by weight of the polymer (2)
It is a body composition.

(Ii) Block Copolymer (1) The polystyrene reduced molecular weight (Mwp) at the peak of the molecular weight distribution curve of the block copolymer (1) of the present invention measured by gel permeation chromatography is 10 to 10.
The range is 600,000, preferably 100,000 to 450,000, and more preferably 150,000 to 400,000. Peak molecular weight (M
When wp) is less than 100,000, when used as a toughening agent for the impact resistant styrene resin composition, the resulting resin has poor impact strength. When the peak molecular weight exceeds 600,000, when used as a toughening agent for the impact-resistant styrene-based resin composition, the impact-resistant styrene-based resin composition is dissolved in an aromatic vinyl monomer and It takes a lot of time to transfer the solution, which is a big problem in the manufacturing process. further,
The rubber-like polymer composition is not preferable because it tends to be powdery and has poor moldability and is unlikely to be veiled.

The ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the block copolymer (1) is in the range of 1.1 to 3.0, preferably 1.1 to 2. The range is 0.0. The block B1 in the block copolymer (1) is
It is a polymer composed of a conjugated diene-based monomer or a copolymer composed of a conjugated diene-based monomer and an aromatic vinyl monomer. -The weight ratio of the conjugated diene monomer and the aromatic vinyl monomer is in the range of 100: 0 to 20:80, preferably 10
It is in the range of 0: 0 to 50:50. -The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of block B1 is in the range of 300 to 50,000, preferably 500 to
It is in the range of 3,000.

The total aromatic vinyl monomer content (TS) in the block copolymer (1) of the present invention is in the range of 10 to 60% by weight, preferably 20 to 50% by weight, more preferably 3%.
It is in the range of 0 to 50% by weight. If it is less than 10% by weight, the cold flow of the rubber-like polymer composition itself becomes remarkably large, problems occur in storage and transportation of the rubber, and handling as the rubber becomes difficult. Further, when it is used as a toughening agent for an impact resistant styrene resin composition, impact resistance is improved but gloss is slightly deteriorated, which is not preferable. When it exceeds 60% by weight, when it is used as a toughening agent for an impact-resistant styrene resin composition, the gloss of the resin composition is good, but the impact strength is poor, which is not preferable.

Next, the content of the aromatic vinyl monomer forming the block in the block copolymer (1) of the present invention is 50 to 100% by weight based on the total aromatic vinyl monomer content. The range is preferably 70 to 100% by weight. When the content of the aromatic vinyl monomer which is a block is less than 50% by weight, when it is used as a toughening agent for an impact-resistant styrene resin composition, the impact resistance of the resin composition is improved, but the gloss is improved. If it is desired to obtain an impact-resistant styrene-based resin composition that is slightly inferior and has excellent gloss, it is preferably 50% by weight or more.

The polystyrene reduced molecular weight (Mwps) at the peak of the molecular weight distribution curve measured by gel permeation chromatograph of the aromatic vinyl polymer forming the block in the block copolymer (1) is 10, 0
In the range of 0 to 150,000, preferably 30,000
To 100,000, more preferably 50,000 to 10
It is in the range of 000. When less than 10,000, when used as a toughening agent for an impact-resistant styrene resin composition, the impact resistance of the resin composition is improved, but the gloss is slightly inferior and the impact-resistant styrene resin composition is excellent in gloss. If it is desired to obtain a product, it is preferably 10,000 or more. Also,
When it exceeds 150,000, when it is used as a toughening agent for an impact resistant styrene resin composition, the gloss of the resin composition is good, but the impact strength is poor, which is not preferable. Further, the rubber-like polymer composition is not preferable because it tends to be powdery and has poor moldability and is unlikely to be veiled.

Further, the content ratio of the molecular weight part of 2/3 or less of the peak molecular weight of the block aromatic vinyl polymer in the block copolymer (1) is in the aromatic vinyl polymer. It is in the range of 20% by weight or less, preferably in the range of 15% or less. When it exceeds 20% by weight, the impact resistance of the resin composition is improved, but the gloss is slightly inferior, which is not preferable.

(Iii) Polymer (2) The polystyrene equivalent molecular weight (Mwp2) of the peak portion of the molecular weight distribution curve measured by gel permeation chromatography of the polymer (2) in the present invention is in the range of 100,000 to 500,000. , Preferably in the range of 150,000 to 400,000. When the peak molecular weight is less than 100,000, when used as a toughening agent for an impact resistant styrene resin composition, the resulting resin has poor impact strength. Further, when the peak molecular weight exceeds 500,000, a large problem in the manufacturing process such as spending a lot of time in dissolving in the aromatic vinyl monomer and transferring this solution at the time of manufacturing the impact resistant styrene resin composition. Becomes Further, the rubber-like polymer composition is not preferable because it easily becomes powdery and has poor moldability and is unlikely to be veiled.

The ratio Mw / Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (2) is in the range of 1.1 to 3.0, preferably 1.1 to 2. The range is 0.0. -The total aromatic vinyl monomer content in the polymer (2) of the present invention is in the range of 0 to 50% by weight, preferably 0.
Is in the range of up to 30% by weight. When it exceeds 50% by weight, when it is used as a toughening agent for an impact-resistant styrene resin composition, the gloss of the resin composition is good, but the impact strength is poor, which is not preferable.

(Iv) Block copolymer (1), polymer (2)
Next, the peak molecular weight (Mwp) of the block copolymer (1),
The relationship between the peak molecular weight (Mwps) of the block S in the block copolymer (1) and the peak molecular weight (Mwp2) of the polymer (2) is 0.2 × (Mwp-Mwps) ≤ Mwp2 ≤ 2.0x (Mwp- Mw
It is necessary to satisfy ps). The peak molecular weight (Mwp2) of the polymer (2) in the rubber-like polymer composition is 0.2 × (Mw
When it is smaller than the value of p-Mwps), when used as a toughening agent for an impact resistant styrene resin composition, the gloss of the resin composition is good but the impact strength is poor, which is not preferable. Also,
When Mwp2 exceeds the value of 2.0x (Mwp-Mwps), the impact resistance of the resin composition is improved but the gloss is inferior, which is not preferable.

(V) Constitution of rubber-like polymer composition The rubber-like polymer composition of the present invention comprises a block copolymer (1)
It is a composition comprising 10 to 90 parts by weight and 90 to 10 parts by weight of the polymer (2). Preferably, the block copolymer (1) 2
A composition comprising 0 to 80 parts by weight and the polymer (2) 80 to 20 parts by weight, more preferably 30 to 70 parts by weight of the block copolymer (1) and 70 to 30 parts by weight of the polymer (2). . When the proportion of the block copolymer (1) exceeds 90 parts by weight, when used as a toughening agent for an impact-resistant styrene resin composition, the resin composition has excellent gloss but poor impact resistance, which is not preferable. . Further, the rubber-like polymer composition is not preferable because it tends to be powdery and has poor moldability and is unlikely to be veiled. Block copolymer (1)
When the ratio of the rubber composition is less than 10% by weight, the cold flow of the rubber-like polymer composition itself becomes remarkably large and the rubber storage,
It causes problems in transportation and makes it difficult to handle as rubber. Further, when it is used as a toughening agent for an impact resistant styrene resin composition, impact resistance is improved but gloss is slightly deteriorated, which is not preferable.

(2) Production of rubber-like polymer composition (i) Any production method can be adopted as the production method of the rubber-like polymer composition of the present invention as long as the composition having the structure of the present invention can be obtained. can do. 1) As an example of the method for producing the rubber-like polymer composition of the present invention, the block copolymer (1) and the polymer (2) are separately produced, and the solutions of the respective components are mixed, and then the solvent is heated. It can be manufactured by the method of removing. 2) Mixing the solid components from which the solvent has been removed by using various mixing devices used for mixing ordinary polymer substances, for example, single-screw or multi-screw screw type extruders, mixing rolls, bumper mixers, kneaders, etc. It can also be produced by

3) A living polymer is produced by polymerizing a conjugated diene monomer in a hydrocarbon solvent using an organolithium compound as a catalyst, and the living polymer is added to a mixture of an aromatic vinyl monomer and a hydrocarbon solvent. And then polymerizing, and further adding a polymerization initiator of any one of the conjugated diene monomer and the living polymer or the organolithium compound, or 4) using an organolithium compound as a catalyst. , Producing a living polymer by polymerizing a conjugated diene-based monomer and an aromatic vinyl monomer, after adding the living polymer in a mixture of the aromatic vinyl monomer and a hydrocarbon solvent and polymerizing, Furthermore, a method for completing the polymerization by adding a polymerization initiator of any of the conjugated diene monomer and the living polymer or the organic lithium compound,

5) Using an organolithium compound as a catalyst, a conjugated diene monomer is polymerized to produce a living polymer, and the living polymer is added to a mixture of an aromatic vinyl monomer and a hydrocarbon solvent for polymerization. Then, a method of completing the polymerization by further adding a polymerization initiator of any one of the conjugated diene monomer, the aromatic vinyl monomer and the living polymer or the organolithium compound, or 6) the organolithium compound As a catalyst, a conjugated diene-based monomer and an aromatic vinyl monomer are polymerized to produce a living polymer, and the living polymer is added to a mixture of the aromatic vinyl monomer and a hydrocarbon solvent and polymerized. Further, a conjugated diene monomer, an aromatic vinyl monomer, and a polymerization initiator of either the living polymer or the organic lithium compound are added to complete the polymerization. It can be produced by law or the like.

(Ii) Production of Block Copolymer (1) As a production method of the block copolymer (1), for example,
1) After polymerizing a conjugated diene-based monomer in a hydrocarbon solvent using an organolithium catalyst, subsequently adding an aromatic vinyl monomer to form an aromatic vinyl monomer block, A method for producing a polymer by adding a conjugated diene-based monomer to complete the polymerization, or 2) polymerizing a conjugated diene-based monomer using an organolithium catalyst, and then adding an aromatic vinyl monomer to produce an aromatic compound. After forming a group vinyl monomer block, a conjugated diene monomer and an aromatic vinyl monomer are further added and random copolymerization is carried out, or 3) a conjugated diene monomer and an aromatic vinyl. After random copolymerization of a mixture of monomers using an organolithium catalyst, subsequently, an aromatic vinyl monomer is added to form an aromatic vinyl monomer block, and then a conjugated diene-based monomer is added. Add the body to complete the polymerization Method for production and 4) A mixture of a conjugated diene monomer and an aromatic vinyl monomer is randomly copolymerized using an organic lithium catalyst, and then an aromatic vinyl monomer is added to add aromatic vinyl. After the monomer block is formed, it can be produced by solution polymerization such as a method in which a conjugated diene monomer and an aromatic vinyl monomer are further added and random copolymerization is performed.

(Iii) Production of polymer (2) 1) The production method of the polymer (2) is, for example, produced by polymerizing a conjugated diene monomer and an organolithium catalyst in a hydrocarbon solvent. Or 2) a solution polymerization such as a method in which a mixture of a conjugated diene monomer and an aromatic vinyl monomer is copolymerized using an organolithium catalyst.

(Iv) Polymerization Components and Polymerization Conditions 1) Hydrocarbon Solvent Solution Examples of the hydrocarbon solvent used in the polymerization include butane,
Aliphatic hydrocarbons such as pentane and hexane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene are used. Preferred examples include hexane and cyclohexane. 2) Conjugated diene-based monomer Examples of the conjugated diene-based monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 3-methyl-1. , 3-pentadiene, 1,3-heptadiene, 1,3-hexadiene, and the like, and one kind or a combination of two or more kinds is used. Examples of preferable monomers include 1,3-butadiene and isoprene. 3) Aromatic vinyl-based monomer Further, examples of the aromatic vinyl-based monomer include styrene,
Examples thereof include p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenylethylene, and divinylbenzene, which may be used alone or in combination of two or more. Styrene is mentioned as a preferable monomer.

4) Organolithium Compound Catalyst The organolithium compound used for polymerizing the conjugated diene monomer and the aromatic vinyl monomer is a monoorganolithium compound or a polyfunctional organolithium compound, Alternatively, it may be a mixture of a monoorganolithium compound and a polyfunctional organolithium compound. Examples of the monoorganolithium compound include n-butyllithium and sec.
-Butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium, benzyllithium and the like can be mentioned, but n-butyllithium and sec-butyllithium are preferably used.

(V) Structural characteristics of rubber-like polymer composition, etc. When the rubber-like polymer composition of the present invention is used as a toughening agent for an impact-resistant styrene resin composition, it is obtained by its microstructure. The impact resistance of the obtained resin is slightly affected. For example, when butadiene is used as the conjugated diene monomer, the 1,2-vinyl content is 5-8.
0%, cis-1,4 content is preferably in the range of 10-85%, especially 1,2-vinyl content of 10-40
% Is preferable. When a rubber-like polymer composition having a 1,2-vinyl content outside this range is used, the resulting impact-resistant styrene resin composition has poor impact strength.

Adjustment of 1,2-vinyl content 1) There is no particular limitation on the method for adjusting the 1,2-vinyl content, and any conventional method can be used. For example, during anionic polymerization of a conjugated diene-based monomer, the polymerization system may include dimethyl ether, diethyl ether, tetrahydrofuran, 2,2-bis (oxolanyl) propane,
Ethers such as 1,1-bis (oxolanyl) ethane;
Amines such as dimethylamine; dimethyl sulfide,
It is achieved by adding thioethers such as diethyl sulfide and conducting the polymerization.

2) Further, a method of adding hexamethylphosphoramide (HMPA) by the polymerization method (Japanese Patent Publication No. 43-5).
904), tetramethylethylenediamine (TM)
EDA) (Japanese Patent Publication No. 42-17199) and diethylene glycol dimethyl ether. 3) The 1,2-vinyl bond may be polymerized so as to be uniform in the molecular chain, or may be polymerized so as to gradually change along the molecular chain (Japanese Patent Publication No. 47-47).
875), or may be polymerized so as to form a block-shaped bond (US Pat. No. 3,301,840). 4) In order to polymerize 1,2-vinyl bonds to be uniform in the molecular chain, the polymerization initiation temperature is usually 30 to 90 ° C.
The method of isothermal polymerization is adopted as much as possible. 5) Further, in order to polymerize the 1,2-vinyl bond so as to gradually change along the molecular chain, a method in which the polymerization is carried out at an elevated temperature, that is, a polymerization initiation temperature is usually 30 to 80 ° C. And a method in which the polymerization end temperature is 85 to 120 ° C. or 6) the 1,2-vinyl bond is polymerized so as to gradually change along the molecular chain. A method of gradually adding a regulator or the like is adopted.

(Vi) Post-treatment after polymerization 1) After the polymerization of the rubber-like polymer composition of the present invention is completed,
If necessary, it can be treated with water, an inorganic acid, an organic acid or the like. -Examples of inorganic acids include sulfuric acid, nitric acid, phosphoric acid, boric acid,
Examples include carbonic acid. The organic acid is an organic compound having an acidity in a broad sense, and examples thereof include compounds such as carboxylic acid, sulfonic acid, and sulfinic acid, but an organic compound having a carboxyl group is preferable. For example, propionic acid, benzoic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oxalic acid, glutaric acid, adipic acid, malonic acid, oleic acid, linoleic acid and the like or mixtures thereof can be mentioned. To be Of these, sulfuric acid, carbonic acid, boric acid, and stearic acid are particularly preferable.

2) The method of adding the compound is not particularly limited, but a method of adding the compound to the polymer solution in a batch system or a continuous system after completion of the polymerization reaction is generally used. 3) Recovery of the polymer from the polymer solution may be carried out, for example, by steam stripping or heat treatment after adding a stabilizer in order to prevent the polymer from undergoing oxidative degradation or thermal degradation when the solvent is removed. The rubbery polymer composition of the present invention can be obtained by a known polymer separation method such as roll, drum dryer drying, methanol precipitation drying, and vacuum drying. The stabilizer may be any known stabilizer that has been used conventionally, such as 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3-.
A phenolic compound such as (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate;
Organic phosphite compounds such as tris (2,4-ditert-butylphenyl) phosphite; 4,6
Various antioxidants such as sulfur-containing phenol compounds such as -bis [(octylthio) methyl] -0-cresol can be used alone or in combination of two or more.

(2) Impact-resistant styrene-based resin composition (i) Composition: The impact-resistant styrene-based resin composition of the present invention is a styrene-based resin composition containing 2 to 30% by weight of the above-mentioned rubber-like polymer composition. It is a resin composition. If the amount of rubber used is less than 2% by weight, the effect of improving the impact strength, which is the object of the present invention, is insufficient, and it is difficult to achieve the object of the present invention. On the other hand, 3
When the amount used exceeds 0% by weight, the impact strength is improved, but the properties inherent to the polystyrene resin, such as tensile strength, rigidity, and appearance properties such as gloss, are impaired, which is not preferable. Moreover, the viscosity of the graft polymerization solution becomes very high, which makes it difficult to produce the impact-resistant styrene resin composition of the present invention. Further, a mixture of the rubber-like polymer composition of the present invention with another rubber-like polymer can be used as a toughening agent. Other rubbery polymers include polybutadiene rubber,
Examples thereof include styrene-butadiene block copolymers and styrene-butadiene random copolymers. When the rubber-like polymer composition of the present invention is used by mixing with another rubber-like polymer, the use ratio thereof is 95: 5 by weight ratio of the rubber-like polymer composition and the other rubber-like polymer. The range is 20:80.

(Ii) Rubber particles-The rubber-like polymer composition rubber particles dispersed in the impact-resistant styrene resin composition obtained in the present invention have an average particle diameter of 0.05 to 4.0 µm. Preferably. The range is preferably 0.1 to 2.0 μm, and more preferably 0.2 to 1.5 μm. The average particle size is 0.
If it is less than 05 μm, the impact resistance of the resin composition is poor,
When it exceeds 4.0 μm, the gloss of the resin composition is inferior, which is not preferable. -To adjust the rubber particle size of the polymer, the rubber-like polymer composition is dissolved in an aromatic vinyl monomer, or a mixture of an aromatic vinyl monomer and a copolymerizable monomer, bulk polymerization, Bulk graft polymerization, when graft polymerization by solution polymerization, conditions under which shear stress is applied to the rubber solution, for example, the rubber particle diameter can be adjusted by changing the rotation speed of the stirrer.
By using the rubbery polymer composition of the present invention, smaller rubber particles can be obtained.

(Iii) Various structural characteristics 1) Gel content, etc. The gel content (toluene insoluble content) in the impact-resistant styrene resin composition obtained as described above is 5
The amount is preferably in the range of to 75% by weight, more preferably 10 to 50% by weight. If the gel content is too low, the impact resistance of the resin composition will be poor, and if it is too high, the fluidity of the resin composition will decrease, which is not preferable for processing. The swelling index of the gel in the resin composition in toluene (weight of toluene swollen material / dry weight after desolvation) is 5 to 15
Is preferable, and more preferably 7-12.
If the swelling index is too small, the impact resistance is inferior, and if it is too large, the impact resistance is lowered and the gloss is also deteriorated, which is not preferable. The control of the swelling index can be adjusted by the final reaction rate and the devolatilization temperature of the unreacted monomer when the vinyl monomer is graft polymerized by bulk polymerization, bulk suspension polymerization or solution polymerization. 2) Molecular weight of matrix resin part The molecular weight of the matrix resin part is preferably 70,000 to 500,000 in terms of polystyrene equivalent weight average molecular weight measured by gel permeation chromatography, and more preferably,
It is in the range of 100,000 to 300,000. If it is less than 70,000, the impact resistance is lowered, and if it exceeds 500,000, the fluidity is poor and it is not preferable in processing.

(Iv) Production Method 1) The method for obtaining the impact resistant styrene resin composition of the present invention is not particularly limited as long as it is considered so as to satisfy the constitutional requirements of the present invention, and is well known. The method of can be used. Usually, the rubber-like polymer composition of the present invention is dissolved in an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and a copolymerizable monomer so that the rubber solution is subjected to shear stress. Graft polymerization by bulk polymerization method, bulk suspension polymerization method, or solution polymerization method while stirring, and a copolymer of an aromatic vinyl monomer or a monomer copolymerizable with the aromatic vinyl monomer. Preferred is a method for obtaining an impact-resistant styrene-based resin composition in which the rubber-like polymer composition is dispersed in a matrix in the form of particles.

2) Aromatic Vinyl Monomer The aromatic vinyl monomer used in the present invention is α-alkyl such as styrene, vinylnaphthalene, α-methylstyrene, α-ethylstyrene, α-methyl-p-methylstyrene. Nuclear alkyl-substituted styrenes such as substituted styrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylvinylbenzene, p-tert-butylstyrene, monochlorostyrene, dichlorostyrene, tribromostyrene, tetra. Halogenated styrene such as bromostyrene, p-hydroxystyrene,
Examples thereof include o-methoxystyrene and the like, and they are used as one kind or as a mixture of two or more kinds. Of these, styrene,
α-methyl styrene and p-methyl styrene are preferred.

3) Other Copolymerizable Monomers Copolymerizable monomers other than aromatic vinyl monomers include unsaturated nitrile monomers, (meth) acrylic acid esters, and other copolymerizable monomers. It is selected from various monomers. -Acrylonitrile, methacrylonitrile, etc. are mentioned as an example of an unsaturated nitrile monomer, and they are used as 1 type or a mixture of 2 or more types. Acrylonitrile is particularly preferable. -Examples of (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, dodecyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate. , Amyl methacrylate,
Hexyl methacrylate, octyl methacrylate, dodecyl methacrylate, cyclohexyl methacrylate and the like can be mentioned, and they can be used alone or as a mixture of two or more. Especially, methyl methacrylate is preferable. -Other copolymerizable monomers include acrylic acid, methacrylic acid, vinyl acetate, maleic anhydride, N-methylmaleimide, N-phenylmaleimide and the like.

4) Inert Solvent Also, when the resin composition of the present invention is obtained, it is not compatible with the above-mentioned aromatic vinyl monomer or a mixed solution of the aromatic vinyl monomer and the copolymerizable monomer. Polymerization may be carried out by adding an active solvent. As the inert solvent, one or more polar solvents such as methyl ethyl ketone and cyclohexanone may be used in addition to ethylbenzene and toluene. The amount of these inert solvents is preferably 100 parts by weight or less, and more preferably 50 parts by weight or less with respect to 100 parts by weight of the vinyl monomer mixed solution in which the rubbery polymer composition is dissolved.

5) Catalyst In the present invention, the radical polymerization of the aromatic vinyl monomer having the rubbery polymer composition dissolved therein or the mixed solution of the aromatic vinyl monomer and the copolymerizable monomer is carried out. It is also possible to carry out the polymerization in the presence of an organic peroxide or an azo compound. As the organic peroxide, peroxyketals such as 1,1-bis (t-butylperoxy) cyclohexane and 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane; Dialkyl peroxides such as -t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and dicumyl peroxide; benzoyl peroxide, m-
Diacyl peroxides such as toluoyl peroxide and lauroyl peroxide; peroxydicarbonates such as dimyristyl peroxydicarbonate and diisopropyl peroxydicarbonate;

Peroxyesters such as t-butylperoxyisopropyl carbonate, t-butylperoxyacetate, di-t-butyldiperoxyisophthalate and t-butylperoxybenzoate; cyclohexanone peroxide, methyl ethyl ketone peroxide, etc. Ketone peroxides; p-mentor hydroperoxide, t-butyl hydroperoxide,
Hydroperoxides such as cumene hydroperoxide are used. -As the azo compound, azobisisobutyronitrile, azobiscyclohexanecarbonitrile or the like is used. These are used alone or in combination of two or more. The amount of the organic peroxide or azo compound used is preferably in the range of 10 to 1,000 ppm in the vinyl monomer mixture.

6) Chain Transfer Agent In the present invention, a known chain transfer agent may be used. Examples of the chain transfer agent include n-dodecyl mercaptan, tert-dodecyl mercaptan, α-methylstyrene dimer, 1-phenylbutene-2-fluorene,
Mercentanes such as dipentene and chloroform, terpenes, halogen compounds and the like can be used.

(V) Various additives 1) In the resin composition of the present invention, known antioxidants,
A stabilizer such as an ultraviolet stabilizer may be added. -As an antioxidant, for example, octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, 2,6-di-tert-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,4
6-dimethylphenol, 2,2'-methylenebis (4
-Ethyl-6-t-butylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol),
2,4-bis [(octylthio) methyl] -o-cresol, triethylene glycol-bis [3- (3-t-
Butyl-5-methyl-4-hydroxyphenyl) propionate], tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, and the like. The amount of antioxidant added is 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the resin composition.

As the UV stabilizer, for example, 2-
Triazoles such as (5-methyl-2-hydroxyphenyl) benzotriazole, 21- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-). 4-piperidyl) sebacate and other hindered amines, as well as pt-butylphenyl salicylate and 2,2′-dihydroxy-4-methoxybenzophenone. Particularly preferred are triazole-based and hindered amine-based singly or in combination. -The addition amount of these ultraviolet stabilizers is 100
It is preferably 0.01 to 5 parts by weight, and more preferably 0.05 to 2 parts by weight, per part by weight.

2) Internal Lubricant It is also possible to add a commonly used internal lubricant such as liquid paraffin, mineral oil, or organic polysiloxane, if necessary. For example, polydimethylsiloxane, which is an organic polysiloxane, may be added in an amount of 0.005 to 10 parts by weight based on 100 parts by weight of the resin composition.

3) Flame Retardant and Flame Retardant Auxiliary Agent Further, when processing the resin composition obtained in the present invention, a flame retardant and a flame retardant auxiliary agent may be blended, if necessary, to give a flame retardant formulation. Is. -There are various types of flame retardants, but all conventionally known flame retardants are included, and halogen-based flame retardants, phosphorus-based flame retardants and the like are effective. For example, decabromodiphenyl oxide, tetrabromobisphenol A, an oligomer of tetrabromobisphenol A, tris- (2,3-dibromopropyl-1) isocyanurate, ammonium phosphate, red phosphorus, tricresyl phosphate and the like can be mentioned. . Examples of the flame retardant aid include antimony trioxide, antimony pentoxide, sodium antimonate, antimony trichloride,
Antimony pentachloride, zinc borate, barium metaborate,
Examples thereof include zirconium oxide. Flame retardant is resin 1
5 to 40 parts by weight are preferably used per 00 parts by weight. The flame retardant aid is preferably 2 to 100 parts by weight of the resin.
20 parts by weight are used. 4) Other additives In addition, various additives such as a lubricant, a release agent, a filler, an antistatic agent, and a coloring agent can be blended, if necessary.

(V) Blending of other thermoplastic resin Still another thermoplastic resin such as general-purpose polystyrene, A
S resin, ABS resin, AES resin, MBS resin, polyphenylene ether, polycarbonate, styrene-butadiene copolymer, methyl methacrylate / styrene copolymer resin, maleic anhydride / styrene copolymer resin, polyamide resin, polyester resin, etc. You may mix. By adding these resins, heat resistance, rigidity, impact resistance, appearance, paintability, etc. are imparted, and they are blended and used depending on their use.

(Vi) The impact resistant styrene resin composition of the present invention is molded by a processing method such as injection molding or extrusion molding,
A wide variety of practically useful products can be obtained.
It is used in a wide variety of applications such as electric appliances, cabinets for OA equipment, housings, interior / exterior parts for automobiles, parts for housing / furniture, antenna parts for broadcasting / communication, and others.

[0049]

EXAMPLES Some examples will be shown below to show concrete embodiments of the present invention, but these are for explaining the technical contents of the present invention more specifically, and limit the present invention. Not a thing. <Measurement Method> Various measurements were made by the following methods. [Peak Molecular Weight of Rubbery Polymer] This is a polystyrene-equivalent molecular weight measured and calculated by GPC (gel permeation chromatography). (GPC measurement conditions) Measurement model LC Module1 solvent manufactured by Waters, THF (tetrahydrofuran) column PL gel manufactured by Polymer Laboratories × 3 columns Column temperature 35 ° C Liquid flow rate 0.7 ml / min Sample concentration 0.1 wt% Sample injection amount 40 μl Detector Showa Denko Shodex RI SE-61

(GPC measurement conditions for rubber samples BS-1 to BS-8) Measurement model LC Module1 solvent THF (tetrahydrofuran) column manufactured by Waters Co., Ltd. Dupont Zorbax 1000S × 4 column temperature 35 ° C. Delivery flow rate 0.4 ml / min Sample Concentration 0.1% by weight Sample injection amount 40 μl Detector Showa Denko Shodex RI SE-61 [microstructure] Infrared spectrophotometer (Perkin Elmer FT-IR16
50) using the Hampton method [Analytical Chemistr
y, 21,923 (1949)]. [Bound Styrene Content] It was measured by an ordinary method using an ultraviolet spectrophotometer (Hitachi UV200).

[Block Styrene Content] The rubbery polymer composition was treated with osmium tetroxide as a catalyst.
-Method of oxidative decomposition with butyl hydroperoxide [IM Kolthoff, et.al., J. Poym. Sci. 1, 4 29 (194
6)], the amount of polystyrene component obtained by decomposition was measured using an ultraviolet spectrophotometer (Hitachi UV200) and expressed as% by weight relative to the rubber-like polymer before decomposition. [Measurement of peak molecular weight and constituents of block styrene part] Oxidative decomposition of a rubber-like polymer with t-butyl hydroperoxide using osmium tetroxide as a catalyst [I.
M.Kolthoff, et.al., J.Poym.Sci.1,429 (1946)] is a polystyrene-equivalent molecular weight of polystyrene obtained by GPC (gel permeation chromatography).

[0052]     (GPC measurement conditions) Measurement model Waters company LC Module1 Solvent THF (tetrahydrofuran) Column Polymer Laboratories PL gel x 3 Column temperature 35 ℃ Liquid flow rate 0.7 ml / min Sample concentration 0.1% by weight Sample injection volume 0.1 ml Detector Showa Denko Shodex RI SE-61

Ratio of Constituents The ratio of constituents is a value measured and calculated by the following method. Standard polystyrene (1.55 million, 410,000, 1
10,000, 35,000, 0.850,000, 0.180 million) GPC was measured, the retention time at each peak position was determined, and a correlation curve between the molecular weight and the retention time was prepared. The area of the molecular weight part of 2/3 or less of the peak molecular weight was obtained from the correlation curve and calculated as the ratio of the total area of the GPC molecular weight distribution curve of the block styrene part. [Izod impact strength] The obtained composition was compression-molded to prepare a test piece having a thickness of 3.2 mm, which was measured according to JIS-K-7110. [Glossiness] The glossiness (incident angle 60 °) of the gate portion and the end portion was measured and averaged according to ASTM D-638.

[Rubber Particle Diameter] The obtained resin was dissolved in dimethylformamide (DMF) while applying ultrasonic vibration, and then measured with a laser diffraction particle size distribution analyzer (LA-920: manufactured by Horiba Ltd.). , 50% median diameter. (10) [Evaluation of Moldability of Rubbery Polymer] The moldability of the rubbery polymer composition was evaluated under the following conditions. Mold shape for compression molding 10 cm × 10 cm × 2 cm Compression pressure 150 kg / cm ² Compression time 30 seconds Compression temperature 25 ° C. Sample amount used 250 g After pressure molding under the above conditions, the sample protruding from the mold is removed and the molded product is removed. The appearance was visually and visually checked and evaluated according to the following criteria.

(1) Production of Living Polymer (B1) An autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed and dried, and after purging with nitrogen, dried 1,3-butadiene under the conditions shown in Table 1. Styrene, cyclohexane, tetrahydrofuran or N, N, N ', N'
-Tetramethylethylenediamine was added, then n-butyllithium was added, and the mixture was reacted at 45 ° C for about 2 hours to prepare. An autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed and dried, and after purging with nitrogen, dried 1,3-butadiene, cyclohexane, under the conditions shown in Table 1.
Divinylbenzene and tetrahydrofuran were added, and then n-butyllithium was added and reacted at 45 ° C. for about 2 hours for adjustment. The living anionic polymer prepared under these conditions was soluble in cyclohexane and had no gel at all. The divinylbenzene used to prepare the catalyst was 56% by weight of the isomer mixture (m-divinylbenzene = 40% by weight,
p-divinylbenzene = 16% by weight) and the balance was ethylvinylbenzene = 44% by weight, which was commercially available divinylbenzene.

(2) Production of Styrene-Butadiene Block Copolymer (1) An autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed and dried, and after purging with nitrogen, prepurified and dried under the conditions shown in Table 2. Styrene, cyclohexane,
Tetrahydrofuran was added, and then the living polymer shown in Table 1 was added to initiate polymerization. After the completion of the polymerization, butadiene was further added to continue the polymerization.
After the completion of the polymerization, methanol was added next to completely deactivate the living polymer. 2,6-Di-tert-butyl-4-methylphenol was added as a stabilizer to the polymer solution thus obtained in an amount of 0.1% by weight per 100 parts by weight of the polymer.
The solvent was removed by adding 5 parts by weight and steam stripping, and after dehydration, the hot roll (110
(° C) to obtain block copolymers shown in Table 2 (Rubber samples No. BSB-1 to BSB-7).

An autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed and dried, and after purging with nitrogen, prepurified and dried styrene and cyclohexane were added under the conditions shown in Table 2 to prepare a living room shown in Table 1. Polymer was added to initiate polymerization. After completion of the polymerization, butadiene and styrene were subsequently added, and the polymerization was further continued. After the completion of the polymerization, methanol was added next to completely deactivate the living polymer. To the polymer solution thus obtained, as a stabilizer, 0.5 part by weight of 2,6-di-tert-butyl-4-methylphenol was added per 100 parts by weight of the polymer, and the solvent was removed by steam stripping. After dehydration, Subsequently, it was dried with a hot roll (110 ° C.) to obtain a styrene-butadiene block copolymer shown in Table 2 (Rubber sample No. BSB-8).

[0058]

[Table 1]

[0059]

[Table 2]

An autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed and dried, and after purging with nitrogen, butadiene, cyclohexane, and tetrahydrofuran which had been previously purified and dried were added under the conditions shown in Table 3, and then,
Polymerization was initiated by adding n-butyllithium. After completion of the polymerization, styrene was subsequently added, and the polymerization was further continued. Further, butadiene was added to continue the polymerization. After the completion of the polymerization, methanol was added next to completely deactivate the living polymer. To the polymer solution thus obtained, as a stabilizer, 0.5 part by weight of 2,6-di-tert-butyl-4-methylphenol was added per 100 parts by weight of the polymer, and the solvent was removed by steam stripping. After dehydration, Subsequently, it was dried with a hot roll (110 ° C.) to obtain a block copolymer shown in Table 3 (Rubber samples No. BSB-9 and BSB-10).

An autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed and dried, and after purging with nitrogen, styrene, cyclohexane, and tetrahydrofuran, which had been previously purified and dried, were added under the conditions shown in Table 3, and then n
-Butyllithium was added to initiate polymerization. After completion of the polymerization, butadiene was subsequently added, and the polymerization was further continued. After the completion of the polymerization, methanol was added next to completely deactivate the living polymer. 2,6-Di-tert-butyl-4-methylphenol was added as a stabilizer to the polymer solution thus obtained, per 100 parts by weight of the polymer.
Add 0.5 parts by weight and remove the solvent by steam stripping. After dehydration, continue to hot roll (11
The block copolymer shown in Table 3 was obtained (rubber sample No. BSB-11).

[0062]

[Table 3]

(3) Production of butadiene-based polymer (1) An autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed and dried, and after purging with nitrogen, it was previously purified and dried under the conditions shown in Table 4. 3-butadiene (B-6,
For B-7, 1,3-butadiene and styrene), cyclohexane and tetrahydrofuran were added, and then n-butyllithium was added to initiate polymerization. After the completion of the polymerization, methanol was added next to completely deactivate the living polymer. To the polymer solution thus obtained, as a stabilizer, 0.5 part by weight of 2,6-di-tert-butyl-4-methylphenol was added per 100 parts by weight of the polymer, and the solvent was removed by steam stripping. After dehydration, Subsequently, it was dried with a hot roll (110 ° C.), and the butadiene polymers (B-1 to B-9) shown in Table 4 were obtained.
Got

[0064]

[Table 4]

(Examples 1 to 9) The obtained block copolymer (1) and butadiene polymer (2) were blended under the conditions shown in Table 5 to give a rubbery polymer composition shown in Table 5. I got a thing.

[0066]

[Table 5] (Comparative Examples 1 to 6) The obtained block copolymer (1) and butadiene-based polymer (2) were blended under the conditions shown in Table 6 to obtain a rubber-like polymer composition shown in Table 6. It was

[0067]

[Table 6]

(Examples 10 to 16) <Production of Styrene-Butadiene Copolymer and Butadiene Polymer Composition> An autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed and dried, and after purging with nitrogen, Table 7
Under the conditions shown in (1), styrene, cyclohexane, and tetrahydrofuran that had been purified and dried in advance were charged, and the living polymer shown in Table 1 was added to start polymerization. After completion of the polymerization, the monomer and the living polymer or n-butyllithium were subsequently added under the conditions shown in Table 7, and the polymerization was further continued. After the completion of the polymerization, methanol was added next to completely deactivate the living polymer. To the polymer solution thus obtained, as a stabilizer, 0.5 part by weight of 2,6-di-tert-butyl-4-methylphenol was added per 100 parts by weight of the polymer, and the solvent was removed by steam stripping. After dehydration, Subsequently, it was dried with a hot roll (110 ° C.) to obtain a rubber-like polymer composition shown in Table 7 (Rubber sample No. SB-1 to SB-).
7). The composition ratio of the styrene-butadiene copolymer and the butadiene-based polymer was determined from the area ratio of each separated by GPC. The styrene content of the styrene-butadiene copolymer is a value calculated from the styrene content in the rubber-like polymer composition and the composition ratio of the styrene-butadiene copolymer and the butadiene-based polymer.

Example 17 An autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed and dried, and after purging with nitrogen, butadiene (70 g) which had been purified and dried in advance under the conditions shown in Table 7 and cyclohexane and tetrahydrofuran were used. It was charged and n-butyllithium was added to initiate polymerization. After completion of the polymerization, styrene (140 g) was subsequently added, and the polymerization was further continued. After completion of the polymerization, butadiene (490 g) and n-butyllithium were subsequently added under the conditions shown in Table 7, and the polymerization was further continued. After the completion of the polymerization, methanol was added next to completely deactivate the living polymer. To the polymer solution thus obtained, as a stabilizer, 0.5 part by weight of 2,6-di-tert-butyl-4-methylphenol was added per 100 parts by weight of the polymer, and the solvent was removed by steam stripping. After dehydration, Subsequently, it was dried with a hot roll (110 ° C.) to obtain a rubber-like polymer composition shown in Table 7 (Rubber sample No. SB-8).

Comparative Example 7 <Production of Styrene-Butadiene Copolymer and Butadiene Polymer Composition> An autoclave equipped with a stirrer and a jacket having an internal volume of 10 L was washed and dried, and after nitrogen substitution, Table 7
Under the conditions shown in (1), styrene, cyclohexane, and tetrahydrofuran that had been purified and dried in advance were added, and n-butyllithium was added to start polymerization. After completion of the polymerization, 1,3-butadiene and n-butyllithium were subsequently added under the conditions shown in Table 7, and the polymerization was further continued. After the completion of the polymerization, methanol was added next to completely deactivate the living polymer. To the polymer solution thus obtained, as a stabilizer, 0.5 part by weight of 2,6-di-tert-butyl-4-methylphenol was added per 100 parts by weight of the polymer, and the solvent was removed by steam stripping. After dehydration, Subsequently, it was dried with a hot roll (110 ° C.) to obtain a rubber-like polymer composition shown in Table 7 (Rubber sample No. SB-9).

[0071]

[Table 7]

(Examples 18 to 35) <Production of Impact-Resistant Styrene Resin Composition> Using various rubber-like polymer compositions shown in Tables 8 and 9, impact-resistant styrene was prepared by the bulk polymerization method described below. A resin composition was obtained. To a reactor equipped with a stirrer and a jacket, ethylbenzene and styrene were added in the types and proportions shown in Tables 8 and 9, and then n-octadecyl-3- (3 ', 5'-di-tert-butyl- was added as a polymer composition and a stabilizer. 0.3 parts by weight of 4'-hydroxyphenyl) propionate and 0.05 parts by weight of t-dodecyl mercaptan were added and dissolved by stirring. To this, 1 × 10 −4 mol of di-tert-butyl peroxide was added to 1 mol of the monomer, and 1
Polymerization was carried out at 10 ° C. for 3 hours, 140 ° C. for 5 hours, and 180 ° C. for 2 hours. Further, after heating at 230 ° C. for 30 minutes, the unreacted product was removed under reduced pressure, and the obtained polymer was pulverized,
Pelletized with an extruder. The physical properties of the resulting impact resistant styrene resin composition are shown in Tables 8 and 9. As is clear from the results of the examples, it is understood that the impact resistant styrene resin composition produced by using the rubbery polymer composition of the present invention has an excellent balance between gloss and impact strength.

(Example 36) <Production of ABS resin> The same reactor as in Example 1 was used,
Ethylbenzene, styrene and acrylonitrile were added in the types and proportions shown in Table 9, and then n-octadecyl-3- (3 ′, 5) was added as a polymer composition and a stabilizer.
0.3 parts by weight of'-tert-butyl-4'-hydroxyphenyl) propionate and 0.05 parts by weight of t-dodecyl mercaptan were added and dissolved by stirring. Ditert-butyl peroxide was added thereto in an amount of 1 × 10 −4 mol based on 1 mol of the monomer, and polymerization was performed at 110 ° C. for 3 hours, 140 ° C. for 5 hours, and 180 ° C. for 2 hours. Further, after heating at 230 ° C. for 30 minutes, the unreacted product was removed under reduced pressure, and the obtained polymer was crushed and pelletized with an extruder to obtain an ABS resin. Table 9 shows the physical properties of the obtained ABS resin composition. The ABS resin produced using the styrene-butadiene block copolymer of the present invention is
It can be seen that the rubber particle size is reduced and the balance between gloss and impact strength is excellent.

Example 37 <Production of MBS Resin> The same reactor as in Example 1 was used,
Ethylbenzene, styrene, and methylmethacrylate were added in the types and proportions shown in Table 9, and then n-octadecyl-3- (3 ', 3', as a polymer composition and a stabilizer.
0.3 parts by weight of 5'-tert-butyl-4'-hydroxyphenyl) propionate and 0.05 parts by weight of t-dodecyl mercaptan were added and dissolved by stirring. Ditert-butyl peroxide was added thereto in an amount of 1 × 10 −4 mol based on 1 mol of the monomer, and polymerization was performed at 110 ° C. for 3 hours, 140 ° C. for 5 hours, and 180 ° C. for 2 hours. Furthermore, after heating at 230 ° C. for 30 minutes, the unreacted product was removed under reduced pressure, and the obtained polymer was pulverized and pelletized with an extruder to obtain an MBS resin.

[0075]

[Table 8]

[0076]

[Table 9]

Comparative Examples 8 to 14 <Production of Impact-Resistant Styrene Resin Composition> Using various rubber-like polymer compositions shown in Table 10, the impact-resistant styrene was prepared in the same manner as in Example 17. A resin composition was obtained.
Table 10 shows the physical properties of the obtained impact resistant styrene resin composition.
Shown in. When a rubber-like polymer composition outside the scope of the present invention was used, impact strength or gloss was inferior, and an impact-resistant styrene resin composition excellent in both was not obtained.

[0078]

[Table 10]

[0079]

The rubber-like polymer composition having a specific structure of the present invention has a structure that has not been hitherto known, and particularly when it is used as a toughening agent for an impact-resistant styrene resin composition, Compared with the conventional impact-resistant styrene resin composition, a product having a remarkably excellent balance of physical properties of impact resistance and gloss can be obtained, and electronic appliances such as TVs and VTRs, home electric appliances such as air conditioners and refrigerators, It has an industrially excellent effect that it can be used in a wide variety of applications such as general equipment such as OA office equipment, stationery, toys, leisure sports goods, household goods, building materials / household parts, and food containers.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 62-280211 (JP, A) JP 63-301210 (JP, A) JP 64-79251 (JP, A) JP 10- 265537 (JP, A) Special Table 10-510567 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 53/02 C08L 9/00 C08F 297/04

Claims (3)

(57) [Claims] 1. The following general formula, block copolymer (1): B1-S-B2 polymer (2): B3 (wherein block B1 is a polymer composed of a conjugated diene-based monomer or a conjugated diene-based monomer). A block B2 is a copolymer composed of a monomer and an aromatic vinyl monomer, and the block B2 is a polymer composed of a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer. Block S is a polymer composed of an aromatic vinyl monomer, B3 is a polymer composed of a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer A rubber-like polymer composition comprising 10 to 90 parts by weight of a block copolymer (1) represented by the formula (1) and 90 to 10 parts by weight of a polymer (2): ) Gel permeation chromatograph of block copolymer (1) The polystyrene reduced molecular weight (Mwp) of the peak portion of the measured molecular weight distribution curve is 100,000 to 600,000, and (ii) the total aromatic vinyl monomer content (TS) in the block copolymer (1) is 10 to 60 weight. %, (Iii) the polystyrene reduced molecular weight (Mwps) of the peak part of the molecular weight distribution curve measured by gel permeation chromatography of the aromatic vinyl polymer which is a block in the block copolymer (1) is 10, 000-1
50,000 and the content ratio of the molecular weight part of 2/3 or less of the peak molecular weight is
20% by weight or less of the aromatic vinyl polymer, and (iv) the polystyrene reduced molecular weight (Mwp2) of the peak portion of the molecular weight distribution curve of the polymer (2) measured by gel permeation chromatography is 10 to 50. (V) Peak molecular weight (Mw) of block copolymer (1)
p), peak molecular weight of block S in block copolymer (1) (Mwps), peak molecular weight of polymer (2) (M)
The relationship of wp2) is 0.2 × (Mwp−Mwps) ≦ Mwp2 ≦ 2.0 ×
(Mwp-Mwps), The rubber-like polymer composition characterized by the above-mentioned. 2. A block copolymer (1) andPolymer
(2) initiates an organolithium compound in a hydrocarbon solvent
It is obtained as an agent, The go of claim 1, characterized in that
Mume-shaped polymer composition. 3. 75 to 98 parts by weight of a mixture of an aromatic vinyl monomer or a monomer mainly composed of a monomer copolymerizable with an aromatic vinyl monomer and 2 to 25 parts by weight of a rubber-like polymer. And a rubber-like polymer according to claim 1 or 2, wherein the rubbery polymer is an impact-resistant styrene-based resin composition obtained by radical polymerization by bulk polymerization, bulk suspension polymerization or solution polymerization. A high-impact styrene-based resin composition, which is a polymer composition.