JP2003313255A - Styrenic resin composition and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a styrenic resin composition enhanced in the balance between impact resistance, rigidity and gloss. <P>SOLUTION: The styrenic resin composition is obtained by the radical polymerization of a mixture comprising 70-98 pts.wt. of a monomer component comprising a mixture of an aromatic vinyl monomer and a monomer copolymerizable therewith, 2-30 pts.wt. of a component (1) being a modified polymer obtained by the addition reaction of a functional group-containing modifier with a specific polymer or the hydrogenated matter thereof and 0.5-300 pts.wt. per 100 pts.wt. of the component (1) of a component (2) being a reinforcing filter. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a styrenic resin composition which uses a modified polymer having a specific structure and a reinforcing filler and has an excellent balance of impact strength, rigidity and gloss.

[0002]

2. Description of the Related Art Polystyrene is 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, styrene-based resin compositions obtained by radically polymerizing a styrene-based monomer in the presence of unvulcanized rubber and graft-polymerizing the rubber-like polymer have been widely produced industrially. As an unvulcanized rubber used for this purpose, there are polybutadiene and styrene-butadiene copolymer, and in particular polybutadiene is widely used for imparting excellent impact resistance.

In recent years, applications of styrene-based resin compositions include housing and other parts of household electric appliances, axle parts,
As it spreads to office equipment parts, daily sundries, toys, etc., various superior properties are required, and styrene resin compositions with excellent balance of appearance properties, rigidity and impact resistance are becoming stronger. Is requested. The styrene-based resin composition, as a rubber-like polymer, polybutadiene rubber, styrene-butadiene copolymer rubber is dissolved in a styrene monomer, while stirring, bulk polymerization or bulk-suspension polymerization method It is common.

Generally, the impact resistance can be improved by increasing the content of the rubber-like polymer, but the styrene resin containing the rubber-like polymer increases the impact strength, but the rigidity. And the gloss decreases. On the other hand, the improvement in gloss is
This can be achieved by reducing the content of the rubber-like polymer or by making the particles of the rubber-like polymer dispersed in the resin finer, but the impact resistance is remarkably lowered.

Conventionally, as a method for improving a styrene resin composition, the solution viscosity of a conjugated diene polymer has been specified (Japanese Patent Publication No. 58-4934), and the relationship between the solution viscosity of a conjugated diene polymer and the Mooney viscosity. Specialization (Japanese Patent Publication Sho 53-4
4188), specification of the relationship between the solution viscosity of the conjugated diene polymer and the tensile elastic modulus and swelling degree of the crosslinked organic peroxide (Japanese Patent Laid-Open No. 60-25001). However, in these methods,
The impact resistance and gloss balance are improved as compared with the case of using conventional polybutadiene, but they are 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 has not yielded a practically satisfactory balance between impact resistance and appearance characteristics.

[0007]

As described above, when the conventional rubber-like polymer is used for the styrene resin, it is difficult to improve the impact resistance, rigidity and gloss to a satisfactory degree. there were. The present invention is to solve the above problems, using a modified polymer having a specific structure and a reinforcing filler, impact resistance, a styrene resin composition having improved physical balance of rigidity and gloss It is provided.

[0008]

The present invention is directed to a conjugated diene polymer having a specific functional group, a modified polymer composed of a conjugated diene and a vinyl aromatic compound, or a modified polymer obtained by adding hydrogen to the modified polymer. It was found that a styrene resin composition having a significantly improved balance of physical properties such as impact resistance, rigidity and gloss can be obtained by using a hydrogenated polymer and a reinforcing filler, and completed the present invention.

That is, the present invention is as follows. 1. Monomer component 70, which is an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and a copolymerizable monomer
98 parts by weight, 2 to 30 parts by weight of a component (1) which is a modified polymer obtained by addition reaction of a functional group-containing modifier with at least one polymer selected from the following a and b, or a hydrogenated product thereof, a ． Conjugated diene polymer b. A polymer composed of a conjugated diene and a vinyl aromatic hydrocarbon and a component (2) which is a reinforcing filler are added to the component (1) 1
A styrene resin composition obtained by radical polymerization of a mixture of 0.5 to 300 parts by weight per 100 parts by weight.

2. 70-98 parts by weight of a monomer component which is an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and a copolymerizable monomer, and at least one polymer selected from the following a and b Component (1) which is a modified polymer obtained by addition reaction of a functional group-containing modifier with
30 parts by weight, a. Conjugated diene polymer b. 0.5 to 300 parts by weight of component (2), which is a polymer-reinforcing filler composed of a conjugated diene and vinyl aromatic hydrocarbon, per 100 parts by weight of component (1), and a crosslinking agent component (3) are added as component (1). ) 0.01 to 20 per 100 parts by weight
A styrene resin composition obtained by radical polymerization of a mixture of parts by weight.

The present invention will be specifically described below.
The component (1) used in the present invention is a modified polymer obtained by adding a functional group-containing modifier to at least one polymer selected from the following a and b obtained by using an organolithium compound as a polymerization catalyst, or The hydrogenated product. a. Conjugated diene polymer b. Polymer consisting of conjugated diene and vinyl aromatic hydrocarbon The vinyl aromatic hydrocarbon content of the modified polymer consisting of the conjugated diene and vinyl aromatic hydrocarbon used in the present invention or its hydrogenated product is generally 5 to 95% by weight. %, More preferably 1
It is 0 to 90% by weight, more preferably 15 to 85% by weight. In the present invention, the vinyl aromatic hydrocarbon content is 5
When it is less than wt%, it is considered to be substantially a conjugated diene polymer. The vinyl aromatic hydrocarbon in the modified polymer comprising the conjugated diene and the vinyl aromatic hydrocarbon or the hydrogenated product thereof may be distributed uniformly or in a taper shape.

Further, in the polymer, a plurality of portions in which the vinyl aromatic hydrocarbon is uniformly distributed and / or a plurality of portions in which the vinyl aromatic hydrocarbon is distributed may coexist.
In order to obtain a styrenic resin composition having particularly good impact resistance, it is recommended that the vinyl aromatic hydrocarbon content of the modified polymer or its hydrogenated product is 60% by weight or less, preferably 50% by weight or less. It In the modified polymer composed of a conjugated diene and a vinyl aromatic hydrocarbon used in the present invention or a hydrogenated product thereof, the ratio of the vinyl aromatic hydrocarbon polymer block to the total vinyl aromatic hydrocarbon content in the polymer. (Hereinafter, the ratio of the vinyl aromatic hydrocarbon polymer block content to the total vinyl aromatic hydrocarbon content in the polymer is referred to as the vinyl aromatic hydrocarbon block ratio) can be set arbitrarily and is 80% by weight or less. , Preferably 50% by weight
Below 80% by weight, more preferably below 20% by weight, a styrene resin composition having a better impact resistance can be obtained.
When it is more than 85% by weight, preferably 85% by weight or more, a styrene resin composition having a better gloss can be obtained.

The content of the vinyl aromatic hydrocarbon polymer block is measured by, for example, a method of oxidatively decomposing the copolymer before hydrogenation with tert-butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLT).
HOFF, et al. J. Polym. Sci. 1,
429 (1946)), using the weight of the vinyl aromatic hydrocarbon polymer block component (provided that the vinyl aromatic hydrocarbon polymer component having an average degree of polymerization of about 30 or less is excluded). Then, it can be obtained from the following equation. Content of vinyl aromatic hydrocarbon polymer block (% by weight) = (weight of vinyl aromatic hydrocarbon polymer block in polymer before hydrogenation / weight of polymer before hydrogenation) ×
100

In the present invention, the modified polymer before the hydrogenation reaction is obtained by the addition reaction of a modifying agent described below to the living end of the polymer obtained by a known method using an organic lithium compound as a polymerization catalyst, For example, it has a structure represented by the following general formula. (B) _n -X (AB) _n -X, A- (BA) _n -X, B- (AB) _n -X, X- (AB) _n , X- (A -B) _n- X, X-A- (BA) _n- X, X-B- (AB) _n- X, [(B-A) _n ] _m- X, [(A-B ) _N ] _m -X, [(BA) _n -B] _m -X, [(AB) _n -A] _m -X (In the above formula, A is a vinyl aromatic hydrocarbon polymer or vinyl. An aromatic hydrocarbon polymer segment, B is a conjugated diene polymer or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon, or a conjugated diene polymer segment or a copolymer of a conjugated diene and a vinyl aromatic hydrocarbon. It is a united segment, n is an integer of 1 or more, preferably 1
Is an integer of ~ 5. m is an integer of 2 or more, preferably 2
It is an integer of 11. X represents a modifier residue to which an atomic group having a functional group described later is bonded. When X is added by a metallation reaction described below, A and / or B
Is attached to the side chain of. Further, the structures of the polymer chains bonded to X in plural may be the same or different. The polymer used in the present invention may be any mixture of the polymers represented by the above general formula.

In the present invention, the microstructure (cis, trans, vinyl ratio) of the conjugated diene moiety in the polymer is
It can be optionally changed by using a polar compound described below, and when 1,3-butadiene is used as the conjugated diene, the 1,2-vinyl bond amount is preferably 5 to 90.
%, More preferably 10 to 80%, when isoprene is used as the conjugated diene or when 1,3-butadiene and isoprene are used in combination, 1,2-vinyl bond and 3,
The total amount of 4-vinyl bonds is preferably 3 to 80%, more preferably 5 to 70%. However, when the hydrogenated product is used as the polymer, the microstructure is such that when 1,3-butadiene is used as the conjugated diene, the 1,2-vinyl bond content is preferably 10 to 80%, more preferably 1
5 to 75%, particularly preferably 20 to 50%. When isoprene is used as a conjugated diene or when 1,3-butadiene and isoprene are used in combination, 1,2-vinyl bond and 3,4-vinyl bond are used. The total amount of binding is preferably 5
It is recommended to be 70%, more preferably 10-50%.

In the present invention, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, if 1,3-butadiene is used as the conjugated diene,
-Vinyl bond content) is hereinafter referred to as vinyl bond content. In the present invention, a conjugated diene polymer or a copolymer comprising a conjugated diene and a vinyl aromatic hydrocarbon, or a conjugated diene polymer segment or a copolymer segment comprising a conjugated diene and a vinyl aromatic hydrocarbon has a vinyl bond content of There may be at least one different portion. For example, the vinyl bond content is 25% or less, preferably 10 to 23% and the vinyl bond content is more than 25%, preferably 28.
At least one 80% to 80% portion may be present. Further, in a polymer having two or more segments B, the vinyl bond content of each segment B may be the same or different.

In the present invention, the conjugated diene is a diolefin having a pair of conjugated double bonds, for example, 1,3
-Butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene,
1,3-pentadiene, 1,3-hexadiene and the like, but particularly common ones are 1,3-butadiene,
Examples include isoprene. These may be used not only in one kind but also in two or more kinds in the production of one polymer.
Examples of vinyl aromatic hydrocarbons include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene and vinylanthracene. However, styrene is particularly common. These may be used not only in one kind but also in two or more kinds in the production of one polymer.

In the present invention, when isoprene and 1,3-butadiene are used in combination as the conjugated diene, the mass ratio of isoprene and 1,3-butadiene is preferably 95/5 to 5/5.
It is 5/95, more preferably 90/10 to 10/90, and further preferably 85/15 to 15/85. In particular, when a composition having good low temperature characteristics is obtained, the mass ratio of isoprene and 1,3-butadiene is preferably 49/51 to
It is recommended to be 5/95, more preferably 45/55 to 10/90, and further preferably 40/60 to 15/85. When isoprene and 1,3-butadiene are used in combination, a composition having a good balance of appearance properties and mechanical properties can be obtained even in molding at high temperature.

In the present invention, as the solvent used for producing the polymer, butane, pentane, hexane, isopentane, heptane, octane, isooctane and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, Alicyclic hydrocarbons such as ethylcyclohexane, or hydrocarbon solvents such as aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene can be used. These may be used alone or as a mixture of two or more.

The organolithium compound used for producing the polymer is a compound having one or more lithium atoms bonded in the molecule, such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, Examples include sec-butyllithium, tert-butyllithium, hexamethylenedilithium, butadienyldilithium, and isoprenyldilithium. These may be used alone or as a mixture of two or more.
In addition, the organolithium compound may be dividedly added once or more during the polymerization in the production of the polymer.

In the present invention, the polymerization rate during the production of the polymer is adjusted, the microstructure of the polymerized conjugated diene moiety is changed,
A polar compound or a randomizing agent can be used for the purpose of adjusting the reactivity ratio between the conjugated diene and the vinyl aromatic hydrocarbon. Examples of the polar compound and the randomizing agent include ethers, amines, thioethers, phosphoramide, potassium salt or sodium salt of alkylbenzene sulfonic acid, potassium or sodium alkoxide, and the like.

Examples of suitable ethers are dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether,
It is diethylene glycol dibutyl ether. As amines, tertiary amine, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines can be used. Examples of the phosphine and phosphoramide include triphenylphosphine and hexamethylphosphoramide.

In the present invention, the polymerization temperature for producing the polymer is preferably -10 to 150 ° C, more preferably 30 to 120 ° C. The time required for the polymerization varies depending on the conditions, but it is preferably within 48 hours, particularly preferably 0.5 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within the range of the above-mentioned polymerization temperature and is a pressure sufficient to maintain the monomer and the solvent in the liquid phase. Further, it is preferable that impurities such as water, oxygen, carbon dioxide gas, etc. which inactivate the catalyst and the living polymer are not mixed in the polymerization system.

Component (1), which is the modified polymer or hydrogenated product thereof in the present invention, is obtained by addition-reacting a functional group-containing modifier with the polymer to form a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid. Halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group,
Thioaldehyde group, carboxylic acid ester group, amide group,
Sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silanol Group, an alkoxysilane, a silicon halide group, a tin halide group, an alkoxytin group, a modified polymer having at least one atomic group having at least one functional group selected from a phenyltin group bonded thereto, or a hydrogenated product thereof. Is.

A method for obtaining a modified polymer having an atomic group having such a functional group bonded thereto or a hydrogenated product thereof is selected from the above functional groups in the polymer by an addition reaction with the living end of the polymer. A modified polymer having a functional group forming at least one atomic group having at least one functional group bonded thereto or a hydrogenated product thereof, or an atomic group having the functional group protected by a known method is bonded. It can be obtained by a method in which the modifying agent used is subjected to an addition reaction.

As another method, a method in which an organic alkali metal compound such as an organic lithium compound is reacted with the polymer (metalation reaction), and the above modifier is added to the organic alkali metal-added polymer is added. To be In the latter case, the hydrogenation product of the polymer may be obtained and then the metalation reaction may be carried out to react the above-mentioned modifier. Depending on the type of modifier, the hydroxyl group, amino group, etc. may generally be an organic metal salt at the stage of reaction with the modifier, in which case it should be treated with a compound having active hydrogen such as water or alcohol. Thus, a hydroxyl group or an amino group can be obtained.

In the present invention, when the modifier is reacted with the polymer, a partially unmodified polymer may be mixed with the modified polymer of the component (1). It is recommended that the proportion of the unmodified polymer mixed in the modified polymer of the component (1) is preferably 70% by weight or less, more preferably 60% by weight or less, further preferably 50% by weight or less.
Since the modified polymer of the present invention has at least one functional group described above in the atomic group bonded to the modified polymer or its hydrogenated product, it is a component (2) which is a reinforcing filler, particularly a silica-based inorganic material. High affinity with fillers, metal oxides, and metal hydroxides, and interaction due to physical affinity such as chemical bond between functional groups of reinforcing filler and hydrogen bond between mutual functional groups. Is effectively exhibited, and a chemical bond or a physical affinity is generated with the cross-linking agent specified in the present invention to obtain a resin composition having the excellent properties intended by the present invention. You can

Particularly preferred as the modified polymer of the component (1) used in the present invention or its hydrogenated product is at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group. It is a modified polymer having at least one atomic group bonded thereto or a hydrogenated product thereof.

In the present invention, an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group is preferably an atomic group represented by the following formulas (1) to (14). An atomic group selected from those represented by such general formulas is given.

[0030]

[Chemical 3]

(In the above formula, R ^{1 to} R ⁴ are hydrogen or a carbon number of 1
A hydrocarbon group having 1 to 24 carbon atoms or a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group. R ⁵ has 1 to 1 carbon atoms
A hydrocarbon chain having 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group. Elements such as oxygen, nitrogen, and silicon are bound to the hydrocarbon groups of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ in a bonding mode other than hydroxyl group, epoxy group, silanol group, and alkoxysilane group. It may be. R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms. )

In the present invention, at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group is used.
Examples of the modifier used for obtaining the individually bonded modified polymer or the hydrogenated product thereof include the following.

For example, tetraglycidyl metaxylene diamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyl diaminodiphenylmethane,
Diglycidyl aniline and diglycidyl orthotoluidine. Further, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldisilane Propoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldiethylethoxysilane, γ-glycidoxyp Pyrdimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropylmethyldiisopropeneoxysilane, bis (γ-glycidoxypropyl) dimethoxysilane, It is bis (γ-glycidoxypropyl) diethoxysilane.

Further, bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) dibutoxysilane, bis (γ-glycidoxypropyl) diphenoxysilane, bis (γ-glycid) Xypropyl) methylmethoxysilane, bis (γ-glycidoxypropyl) methylethoxysilane, bis (γ-glycidoxypropyl) methylpropoxysilane, bis (γ-
Glycidoxypropyl) methylbutoxysilane, bis (γ-glycidoxypropyl) methylphenoxysilane, tris (γ-glycidoxypropyl) methoxysilane, γ-methacryloxypropyltrimethoxysilane,
γ-methacryloxypropyltriethoxysilane, γ-
Methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, bis (γ-methacryloxypropyl) dimethoxysilane and tris (γ-methacryloxypropyl) methoxysilane.

Further, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyl-triethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-
Tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β- (3,4
-Epoxycyclohexyl) ethyl-triphenoxysilane, β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyl-ethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldiethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyl-methyldiethoxysilane.

In addition, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane, β- (3,3
4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane, β- (3,3 4-epoxycyclohexyl) ethyl-
Diethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β-
(3,4-Epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylbutoxysilane, β- (3,4
-Epoxycyclohexyl) ethyl-dimethylphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane. Further, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea, N-methylpyrrolidone and the like can be mentioned.

A modified polymer in which at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group is bonded by reacting the above-mentioned modifier. Is obtained. When a functional group-containing modifier is added to the living end of the polymer having segment A and segment B,
The living end of the polymer is segment A or segment B
Any of

The amount of the above-mentioned modifier used is more than 0.5 equivalents and not more than 10 equivalents, preferably more than 0.7 equivalents and not more than 5 equivalents, more preferably 1 equivalent to the living end of the polymer. It is recommended to use more than 1 equivalent and 4 equivalents or less. In the present invention, the amount of the living terminal of the polymer may be calculated from the amount of the organolithium compound used for the polymerization and the number of lithium atoms bonded to the organolithium compound, or the obtained weight. It may be calculated from the number average molecular weight of the coalescence.

In the present invention, the hydrogenated product of the modified polymer is
It is obtained by hydrogenating the modified polymer obtained above. The hydrogenation catalyst is not particularly limited and is a conventionally known (1) supported heterogeneous hydrogenation in which a metal such as Ni, Pt, Pd or Ru is supported on carbon, silica, alumina, diatomaceous earth or the like. Catalyst, (2) Ni, Co, Fe, C
A so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as r or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum, (3) Ti, Ru, Rh, Zr
A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound is used. As a specific hydrogenation catalyst,
Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841 and Japanese Patent Publication No. 1-379.
70, Japanese Patent Publication 1-53851, Japanese Patent Publication 2-
The hydrogenation catalyst described in Japanese Patent No. 9041 can be used. Preferred hydrogenation catalysts include a mixture of a titanocene compound and a reducing organometallic compound.

As the titanocene compound, Japanese Patent Application Laid-Open No. 8-1
The compounds described in Japanese Patent Publication No. 09219 can be used,
Specific examples include at least one or more ligands having a (substituted) cyclopentadienyl skeleton, indenyl skeleton, or fluorenyl skeleton such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Compounds.
Further, as the reducing organic metal compound, an organic alkali metal compound such as organic lithium, an organic magnesium compound,
Examples thereof include organic aluminum compounds, organic boron compounds and organic zinc compounds.

The hydrogenation reaction is preferably carried out in the temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used in the hydrogenation reaction is preferably 0.1 to
15 MPa, more preferably 0.2 to 10 MPa, further preferably 0.3 to 5 MPa is recommended. The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction is a batch process,
Either a continuous process or a combination thereof can be used.

In the hydrogenated product of the modified polymer used in the present invention, the total hydrogenation rate of unsaturated double bonds based on the conjugated diene compound can be arbitrarily selected according to the purpose and is not particularly limited. More than 70%, preferably 75% or more, more preferably 85% or more, particularly preferably 90% of the unsaturated double bond based on the conjugated diene compound in the polymer.
The above may be hydrogenated, or only a part thereof may be hydrogenated. When hydrogenating only a part, the hydrogenation rate is 1
0 to 70%, or 15 to 65%, particularly preferably 20 to
It is preferably 60%.

Further, in the present invention, in the hydrogenated polymer, the hydrogenation rate of vinyl bond based on the conjugated diene before hydrogenation is preferably 85% or more, more preferably 9%.
It is recommended to be 0% or more, more preferably 95% or more in order to obtain a composition having excellent thermal stability. here,
The hydrogenation rate of vinyl bonds means the proportion of hydrogenated vinyl bonds in the vinyl bonds based on the conjugated diene before hydrogenation incorporated in the polymer. The hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the polymer is not particularly limited, but preferably 50%.
Or less, more preferably 30% or less, still more preferably 20% or less.
% Or less is recommended. The hydrogenation addition rate can be known by a nuclear magnetic resonance apparatus (NMR).

The weight average molecular weight of the modified polymer or its hydrogenated product used in the present invention is 50,000 or more from the viewpoint of the mechanical strength of the resin composition and the solubility in aromatic vinyl monomers and the like. To 1.5 million or less, more preferably 100,000 to 1,000,000, still more preferably 150 to 600,000. The molecular weight distribution is 1.05 to 6, preferably 1.
1 to 6, more preferably 1.55 to 5.0, and particularly preferably 1.6 to 4. Setting the molecular weight distribution within such a range is recommended in terms of the miscibility between the component (1) and the component (2).

In the present invention, the amount of vinyl bond based on the conjugated diene compound in the polymer is determined by the nuclear magnetic resonance apparatus (NM
R) can be used to find out. The hydrogenation rate can also be known using the same device. The weight average molecular weight of the polymer or its hydrogenated product is measured by gel permeation chromatography (GPC), and the molecular weight of the peak of the chromatogram is determined by measuring a commercially available standard polystyrene. The peak molecular weight is used for the calculation). The molecular weight distribution of the polymer can be similarly determined from the measurement by GPC.

The modified polymer or the hydrogenated solution thereof obtained as described above is subjected to removal of the catalyst residue, if necessary,
The modified polymer or its hydrogenated product can be separated from the solution. As a method for separating the solvent, for example, a method in which a polar solvent that is a poor solvent for the polymer such as acetone or alcohol is added to the solution after polymerization or hydrogenation to precipitate and recover the polymer, a modified polymer or the Examples thereof include a method in which the hydrogenated solution is poured into hot water with stirring, and the solvent is removed by steam stripping to recover the solvent, or a method in which the polymer solution is directly heated to distill off the solvent. still,
The modified polymer or its hydrogenated product used in the present invention includes various phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers,
Stabilizers such as amine stabilizers can be added.

Next, the component (2) used in the present invention is a known reinforcing filler such as light calcium carbonate, heavy calcium carbonate, various surface-treated calcium carbonate, magnesium carbonate, aluminum silicate or silicic acid. Synthetic silicates such as magnesium and calcium silicate, silica, talc, mica, clay, magnesium hydroxide, aluminum hydroxide, barium sulfate, magnesium sulfate, calcium sulfate, natural silicic acid, synthetic silicic acid, titanium oxide, magnesium oxide , Alumina, carbon and the like. Preferred reinforcing fillers include silica-based inorganic fillers, metal oxides, metal hydroxides, and carbon. The reinforcing filler is not limited to one type
One or more species can be used in combination.

The silica-based inorganic filler used in the present invention refers to solid particles having a chemical unit of SiO ₂ or Si ₃ Al as a main component, and examples thereof include silica, clay, talc, mica, diatomaceous earth, and wollast. Inorganic fibrous substances such as knight, montmorillonite, zeolite and glass fiber can be used. Further, a silica-based inorganic filler having a hydrophobic surface, or a mixture of a silica-based inorganic filler and a non-silica-based inorganic filler can also be used. Silica and glass fibers are preferred in the present invention. Examples of silica that can be used include dry method white carbon, wet method white carbon, synthetic silicate white carbon, and so-called colloidal silica. These have a particle size of 0.01 to 15
It is preferably 0 μm. In addition, in the composition of the present invention, in order to disperse silica in the composition and sufficiently exert the effect of adding silica, the average dispersed particle diameter is 0.05 to 1 μm.
m is preferred, and more preferably 0.05-0. 5 μm
Is.

The metal oxide used in the present invention has the chemical formula M
_x O _y (M is a metal atom, x and y are each an integer of 1 to 6) refers to solid particles having a constituent unit as a main component, for example, alumina, titanium oxide, magnesium oxide, zinc oxide, etc. are used. You can Also, a mixture of a metal oxide and an inorganic filler other than the metal oxide can be used. The metal hydroxide used in the present invention is aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, calcium hydroxide, barium hydroxide, oxidized. Hydrate inorganic fillers such as hydrates of tin and hydrates of inorganic metal compounds such as borax, of which magnesium hydroxide and aluminum hydroxide are preferred.

The carbon black used in the present invention includes FT, SRF, FEF, HAF, ISAF, SAF.
, Etc., carbon black of each class can be used, nitrogen adsorption specific surface area is 50 mg / g or more, DBP oil absorption is 80 ml
/ 100 g carbon black is preferred.

In the present invention, the amount of the reinforcing filler as the component (2) is 0.5 to 300 parts by weight, preferably 1 part by weight per 100 parts by weight of the modified polymer or the hydrogenated product of the component (1). To 200 parts by weight, more preferably 5 to 100 parts by weight. When the compounding amount of the component (2) is less than 0.5 part by weight, the effect of adding the reinforcing filler is not exhibited, while when it exceeds 300 parts by weight, the processability and mechanical strength of the obtained resin are poor, which is preferable. Absent.

In the present invention, the crosslinking agent of component (3) is
A modified polymer or a hydrogenated product thereof is a cross-linking agent having a functional group reactive with the terminal functional group of the component (1), and a particularly preferred cross-linking agent is a modified polymer or a hydrogenated product thereof (1). And a functional group having reactivity with the functional group of the reinforcing filler used as the component (2). Preferred as the crosslinking agent of the component (3) are a carboxyl group, an acid anhydride group, an isocyanate group,
It is a crosslinking agent having a functional group selected from an epoxy group, a silanol group, and an alkoxysilane group. The compounding amount of the cross-linking agent is 100 (100) of the modified polymer or its hydrogenated product.
0.01 from the viewpoint of the mechanical strength of the composition per part by weight.
It is more than 20 parts by weight and is 20 from the viewpoint of the intended action and effect.
It is less than or equal to parts by weight. Preferably 0.02 to 10 parts by weight,
It is more preferably 0.05 to 7 parts by weight.

Specific examples of the cross-linking agent of the component (3) include, as the cross-linking agent having a carboxyl group, maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid,
Aliphatic carboxylic acids such as sebacic acid, dodecanedicarboxylic acid, carballylic acid, cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, pyro Examples thereof include aromatic carboxylic acids such as meritic acid.

As the cross-linking agent having an acid anhydride group, maleic anhydride, itaconic anhydride, pyromellitic dianhydride, cis-4-cyclohexane-1,2-dicarboxylic acid anhydride, 1,2,4,5- Benzenetetracarboxylic dianhydride, 5- (2,5-dioxytetrahydroxyfuryl)
-3-Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride and the like. Examples of the crosslinking agent having an isocyanate group include toluylene diisocyanate, diphenylmethane diisocyanate, and polyfunctional aromatic isocyanate. The cross-linking agent having an alkoxysilane is bis- (3-triethoxysilylpropyl) -tetrasulfane, an ethoxysiloxane oligomer.

Examples of the cross-linking agent having an epoxy group are tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-m-xylenediamine, diglycidylaniline, ethylene glycol diglycidyl, propylene glycol diglycidyl, and diglycidyl terephthalate. For example, ester acrylate. Particularly preferred cross-linking agents are carboxylic acids having two or more carboxyl groups or acid anhydrides thereof, or cross-linking agents having two or more acid anhydride groups, isocyanate groups, epoxy groups, silanol groups, and alkoxysilane groups. maleic anhydride,
Examples are pyromellitic dianhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, toluylene diisocyanate, and tetraglycidyl-1,3-bisaminomethylcyclohexane.

In the present invention, a secondary modified polymer (in the present invention, defined as component (1-1)) obtained by reacting the above component (1) with the component (3) in advance can be used. When the component (1) is reacted with the component (3) in advance, the component (1)
The amount of the component (3) is 0.3 to 10 mol, preferably 0.4 to 5 mol, and more preferably 0.5 to 4 mol, per equivalent of the functional group bonded to. Examples of the method of reacting the component (1) with the component (3) in advance include a melt-kneading method described later and a method of dissolving or dispersing and mixing each component in a solvent and reacting the components. In the case of the melt kneading method, the kneading temperature is generally in the range of 50 to 250 ° C, preferably 80 to 230 ° C.

Further, in the method of dissolving or dispersing and mixing each component in a solvent or the like and reacting, the solvent is not particularly limited as long as it dissolves or disperses each component, and aliphatic hydrocarbon, alicyclic carbon In addition to hydrocarbon solvents such as hydrogen and aromatic hydrocarbons, halogen-containing solvents, ester solvents, ether solvents and the like can be used. In such a method, a particularly preferable method is a method in which the component (3) is added to the solution in which the component (1) is produced and reacted to obtain the component (1-1). The reaction temperature is generally -10 to 15
The temperature is 0 ° C, preferably 30 to 120 ° C. Although the time required for the reaction varies depending on the conditions, it is generally within 3 hours, preferably from several seconds to 1 hour.

When the component (1-1) thus obtained is blended with the component (2) to give a styrene resin composition, the component (1-1) is further added to 100 parts by weight of the component (1-1). 0.01 to 20 parts by weight can be blended.
In the present invention, in order to make the interaction between the component (1) or the component (1-1) and the component (2) close, the component (1) or the component (1-1) and the component (2) are respectively added. A silane coupling agent having an affinity or a binding group can be used.

Specific examples of the silane coupling agent include bis- [3- (triethoxysilyl) -propyl].
-Tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis- [2- (triethoxysilyl) -ethyl] -tetrasulfide, 3-
Mercaptopropyl-trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropylbenzothiazoletetrasulfide, vinyltrimethoxysilane, vinyltri Ethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-
Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyl and methyldimethoxysilane.

Further, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3. -Aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl)
3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3
-Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and the like.

A preferred silane coupling agent is one having a silanol group or an alkoxysilane and at the same time a mercapto group or / and a polysulfide bond in which two or more sulfurs are linked, and an example thereof is bis- [3-
(Triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl]
-Disulfide, bis- [2- (triethoxysilyl)
-Ethyl] -tetrasulfide, 3-mercaptopropyl-trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropylbenzothiazoletetra Examples include sulfide.

The content of the silane coupling agent is 0.1 to 30% by weight based on the reinforcing filler of the component (2).
Preferably 0.5 to 20% by weight, more preferably 1 to 1
It is 5% by weight. The compounding amount of the silane coupling agent is 0.
If it is less than 1% by weight, there is no compounding effect, and if it exceeds 30% by weight, there is no further improvement effect. The method for obtaining the styrene-based resin composition of the present invention is not particularly limited as long as it is considered so as to satisfy the constituent requirements of the present invention, and a known method can be used.

In the present invention, the modified polymer of component (1) or its hydrogenated product and the reinforcing filler of component (2) can be copolymerized with an aromatic vinyl monomer or an aromatic vinyl monomer. Graft polymerization by bulk polymerization method, bulk suspension polymerization method or solution polymerization method while stirring and mixing so as to apply shear stress to the mixture as a mixture of monomer components which is a mixture with various monomers. The modified polymer or a hydrogenated product of the aromatic vinyl-based monomer or the copolymer of the aromatic vinyl monomer and the copolymerizable monomer is added to the matrix. A styrene resin composition in which a graft polymer in which a monomer component, which is a mixture of a vinyl monomer or an aromatic vinyl monomer and a copolymerizable monomer, is grafted, is dispersed in a particulate form. The method of obtaining is preferred. In the present invention, the styrene resin composition is not grafted with a monomer component which is an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and a copolymerizable monomer. A modified polymer or a hydrogenated product thereof may be included.

As a method for dissolving and dispersing the modified polymer or its hydrogenated product and the reinforcing filler in the above-mentioned monomer components to obtain a mixture, the modified polymer or its hydrogenated product (component 1) and the reinforcing property can be used. Method of dissolving / dispersing filler (component 2) in each monomer component, modified polymer (component 1), reinforcing filler (component 2) and crosslinking agent (component 3) are each dissolved in monomer component. -Dispersion method, modified polymer or its hydrogenated product (component 1) and reinforcing filler (component 2) are mixed in advance in a solvent, Banbury mixer, roll, kneader, single screw. Extruder, twin-screw extruder,
A method of dissolving and dispersing the modified polymer composition kneaded using a general mixer such as a multi-screw extruder in a monomer component, or a modified polymer or a hydrogenated product thereof (component 1), Reinforcing filler (component 2) and cross-linking agent (component 3) are mixed in advance in a solvent, Banbury mixer, roll, kneader, single screw extruder, twin screw extruder, multi screw screw. -A method of dissolving / dispersing the modified polymer composition kneaded using a general kneader such as an extruder in a monomer component.

The aromatic vinyl monomer used in the present invention includes styrene, vinylnaphthalene, α-methylstyrene, α-ethylstyrene, α-alkyl-substituted styrene such as α-methyl-p-methylstyrene, m-methylstyrene, and the like. Nuclear alkyl-substituted styrenes such as p-methylstyrene, 2,4-dimethylstyrene, ethylvinylbenzene, p-tert-butylstyrene, halogenated styrenes such as monochlorostyrene, dichlorostyrene, tribromostyrene, tetrabromostyrene, etc. Examples of p-hydroxystyrene, o-methoxystyrene, etc.
It is used as a kind or a mixture of two or more kinds. Of these, styrene, α-methylstyrene and p-methylstyrene are preferable.

The copolymerizable monomer other than the aromatic vinyl monomer is selected from unsaturated nitrile monomers, (meth) acrylic acid esters, other copolymerizable monomers and the like. is there. Examples of unsaturated nitrile monomers include acrylonitrile, methacrylonitrile and the like,
Used as one kind or as a mixture of two or more kinds. Acrylonitrile is particularly preferable.

Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate,
Dodecyl acrylate, cyclohexyl acrylate,
Methylmethacrylate, ethylmethacrylate, propylmethacrylate, butylmethacrylate, amylmethacrylate, hexylmethacrylate, octylmethacrylate, dodecylmethacrylate, cyclohexylmethacrylate, etc. are mentioned, and they are used singly or as a mixture of two or more kinds. Especially, methyl methacrylate is preferable. Other copolymerizable monomers include acrylic acid, methacrylic acid, vinyl acetate, maleic anhydride, N-
Examples include methylmaleimide and N-phenylmaleimide.

Further, in obtaining the styrene resin composition of the present invention, a monomer component which is the above-mentioned aromatic vinyl monomer or a mixture of the aromatic vinyl monomer and a copolymerizable monomer. Alternatively, an inert solvent may be added to carry out the polymerization. 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, more preferably 50 parts by weight or less, based on 100 parts by weight of the monomer component.

In the present invention, a monomer component which is an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer, a modified polymer or a hydrogenated product thereof and a reinforcing property. When radically polymerizing a mixture of fillers, the polymerization can be carried out in the presence of an organic peroxide or an azo compound.

As the organic peroxide, 1,1-bis (t
-Butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane and the like peroxyketals; di-t-butylperoxide, 2,5-dimethyl-2, 5-di (t-
Butyl peroxy) hexane, dicumyl peroxide and other dialkyl peroxides; benzoyl peroxide, m-toluoyl peroxide, lauroyl peroxide and other diacyl peroxides; dimyristyl peroxydicarbonate, diisopropyl peroxydiene Peroxydicarbonates such as carbonates;
t-butyl peroxyisopropyl carbonate, t-
Peroxyesters such as butylperoxyacetate, di-t-butyldiperoxyisophthalate and t-butylperoxybenzoate; ketone peroxides such as cyclohexanone peroxide and methyl ethyl ketone peroxide; p-mentor hydroperoxide, Hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide are used. As the azo compound, azobisisobutyronitrile, azobiscyclohexanecarbonitrile, etc. are used. These are used alone or in combination of two or more.

The amount of organic peroxide or azo compound used is
The range of 10 to 1000 ppm in the monomer component is preferable. Further, in the present invention, a known chain transfer agent is used. As the chain transfer agent, for example, n-dodecyl mercaptan, tert-dodecyl mercaptan, α-methylstyrene dimer, 1-phenylbutene-2-fluorene, mercaptans such as dipentene and chloroform, terpenes, halogen compounds and the like can be used.

In the styrene resin composition of the present invention,
A known stabilizer such as an antioxidant or an ultraviolet stabilizer may be added. Examples of the antioxidant include octadecyl-3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -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 can be mentioned, and the addition amount thereof is 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the styrene resin composition.

Examples of the UV stabilizer include 2- (5
-Methyl-2-hydroxyphenyl) benzotriazole, triazoles such as 21- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-) Piperidyl)
Hindered amines such as sebacate, pt
-Butylphenyl salicylate, 2,2'-dihydroxy-4-methoxybenzophenone and the like. Particularly preferred are triazole-based and hindered amine-based singly or in combination. The amount of these ultraviolet stabilizers added is preferably 0.1 per 100 parts by weight of the styrene resin composition.
The amount is 01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight. In addition, it is possible to add an internal lubricant such as liquid paraffin, mineral oil, or organic polysiloxane, which is usually used, if necessary. For example, 0.005 to 10 parts by weight of polydimethylsiloxane which is an organic polysiloxane may be added to 100 parts by weight of the styrene resin composition.

Gel content in the styrene resin composition obtained as described above (content of toluene insoluble content)
Is preferably 5 to 75% by weight, more preferably 10 to 50% by weight. If the gel content is too low, the impact resistance of the styrene resin composition will be poor, and if it is too high, the fluidity of the styrene resin composition will decrease, which is not preferable for processing. The swelling index of the gel in the styrene resin composition in toluene (weight of toluene swollen material / dry weight after desolvation) is preferably in the range of 5 to 15,
More preferably, it is 7-12. If the swelling index is too small, the impact resistance will be poor, and if it is too large, the impact resistance will decrease.
It is not preferable because it also deteriorates the gloss. The control of the swelling index can be adjusted by the final reaction rate and the devolatilization temperature of the unreacted monomer when the monomer component is graft polymerized by bulk polymerization, bulk suspension polymerization or solution polymerization.

The molecular weight of the matrix resin portion is preferably 70,000 to 500,000, and more preferably 100,000 to 300,000 in terms of polystyrene equivalent weight average molecular weight measured by gel permeation chromatography. 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. In the present invention, a particularly preferable styrene resin composition is a matrix of a polymer of an aromatic vinyl monomer or a copolymer of an aromatic vinyl monomer and a copolymerizable monomer. Component (1) or component (1-) which is a polymer or its hydrogenated product.
A graft polymer obtained by grafting a monomer component, which is an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and a copolymerizable monomer, to 1) is dispersed in the form of particles, and A styrene-based polymer having a form in which the modified polymer or the hydrogenated portion thereof present in the particulate dispersion layer, or in the vicinity thereof, the whole amount or a part of the component (2) which is a reinforcing filler is present. It is a resin composition.

Further, in processing the styrene resin composition obtained in the present invention, it is possible to add a flame retardant and a flame retardant auxiliary, if necessary, to give a flame retardant formulation. There are various types of flame retardants, but all conventionally known flame retardants are included, and halogen-based flame retardants, phosphorus-based flame retardants, hydroxide-based flame retardants, silicon-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, magnesium hydroxide. , Aluminum hydroxide and the like. Examples of the flame retardant aid include antimony trioxide, antimony pentaoxide, sodium antimonate, antimony trichloride, antimony pentachloride, zinc borate, barium metaborate, zirconium oxide and the like.

If desired, various additives such as a lubricant, a release agent, a filler, an antistatic agent and a coloring agent can be added. Still other thermoplastic resins such as general-purpose polystyrene, AS resin, ABS resin, AES resin, MBS resin, polyphenylene ether, polycarbonate, styrene-butadiene copolymer resin, methylmethacrylate / styrene copolymer resin, maleic anhydride / styrene. It may be mixed with a copolymer resin, a polyamide resin, a polyester resin or the like. By adding these resins, heat resistance, rigidity, impact resistance, appearance, paintability, etc. are given,
It is used as a blend depending on its application.

The styrene resin composition of the present invention can be molded into a wide variety of practically useful products by molding by processing methods such as injection molding and extrusion molding. 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.

[0079]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples. 1. Characteristics of polymer (1) Styrene content It was measured using an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450). (2) Polystyrene block content Using a polymer before hydrogenation, I. M. Kolthoff, et.al. ，
J. Polym. Sci. It was measured by the method described in 1,429 (1946). (3) Vinyl bond amount and hydrogenation rate Nuclear magnetic resonance apparatus (BRUXER, DPX-400)
Was measured using. (4) Molecular weight and molecular weight distribution Measured by GPC [apparatus: Shimadzu LC10], tetrahydrofuran was used as a solvent, and the measurement condition was temperature 3
Performed at 5 ° C. The molecular weight is a calibration curve obtained by measuring the molecular weight of the peak in the chromatogram from the measurement of commercially available standard polystyrene (created using the peak molecular weight of standard polystyrene).
Is the weight average molecular weight determined by using. The molecular weight distribution is the ratio of the obtained weight average molecular weight and number average molecular weight.

(5) Ratio of unmodified polymer The sample solution containing the modified polymer and the low molecular weight internal standard polystyrene was applied by applying the property that the modified component is adsorbed on the GPC column having silica gel as the packing material. (4)
The ratio of the modified polymer to the standard polystyrene in the chromatogram measured by the method is compared with the ratio of the modified polymer to the standard polystyrene in the chromatogram measured by the silica-based column GPC [the device is Zorbax manufactured by DuPont]. The amount of adsorption to the silica column was measured from the difference of The ratio of the unmodified polymer is the ratio of those not adsorbed on the silica column.

2. Physical Properties of Styrenic Resin Composition (1) Notched Izod Impact Strength Measured according to JIS-K-7110. (2) Flexural modulus Measured according to ASTM-D790. (3) Rubber particle size 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.), It is a value calculated as a% median diameter.

3. Preparation of hydrogenation catalyst 1 liter of dried and purified cyclohexane was charged into a reaction vessel purged with nitrogen, 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride was added, and n containing 200 mmol of trimethylaluminum with sufficient stirring. -Hexane solution was added and reacted at room temperature for about 3 days.

4. Preparation of modified polymer a. Polymer 1 With an internal volume of 10 liters, an autoclave equipped with a stirrer and a jacket and capable of temperature control is used as a reactor, and 800 g of butadiene from which impurities have been removed, 5500 g of cyclohexane, and 1.37 g of tetrahydrofuran as a polar substance are charged into the reactor. Then, the temperature inside the reactor was maintained at 40 ° C. N-butyllithium 0.76 as a polymerization initiator
A cyclohexane solution containing g was fed to the reactor. After the reaction was started, the temperature inside the reactor gradually increased due to the heat generated by the polymerization. The final reactor internal temperature reached 75 ° C.

After the completion of the polymerization reaction, the reactor was used as a modifier.
Tetraglycidyl-1,3-bisaminomethylcyclohexane (hereinafter referred to as modifier M1) was added in an amount of 1.5 equivalents to n-butyllithium used for the polymerization, and the mixture was maintained at 75 ° C for 5 minutes to carry out the modification reaction. Carried out. Thereafter, methanol was added, and then octadecyl-3- (3,3 as a stabilizer.
After adding 0.3 parts by mass of 5-di-t-butyl-4-hydroxyphenyl) propionate to 100 parts by mass of the polymer, the solvent was removed. When the obtained modified polymer (Polymer 1) was analyzed, the vinyl bond content was 18%.

B. Polymer 2 With an internal volume of 10 liters, an autoclave equipped with a stirrer and a jacket and capable of controlling temperature is used as a reactor, 600 g of butadiene from which impurities have been removed, 200 g of styrene, 5500 g of cyclohexane, and 1.37 g of tetrahydrofuran as a polar substance. Was charged into the reactor, and the temperature inside the reactor was maintained at 40 ° C. A cyclohexane solution containing 0.85 g of n-butyllithium as a polymerization initiator was supplied to the reactor. After the reaction was started, the temperature inside the reactor gradually increased due to the heat generated by the polymerization.

After the completion of the polymerization reaction, 2 equivalents of the modifier M1 as a modifier was added to the reactor with respect to the n-butyllithium used for the polymerization, and the mixture was kept at 75 ° C. for 5 minutes to carry out the modification reaction. After that, methanol was added, and then 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the polymer, and the solvent was added. Was removed. Analysis of the resulting modified polymer (Polymer 2) revealed that the styrene content was 25% by weight, the vinyl bond content in the butadiene portion was 15%, and the block styrene content was 11% by weight.

C. Polymer 3 With an internal volume of 10 liters, an autoclave equipped with a stirrer and a jacket and capable of controlling temperature is used as a reactor, and 600 g of butadiene with impurities removed, 200 g of styrene, 5500 g of cyclohexane, and 1.37 g of tetrahydrofuran as a polar substance. Was charged into the reactor, and the temperature inside the reactor was maintained at 40 ° C. A cyclohexane solution containing 0.85 g of n-butyllithium as a polymerization initiator was supplied to the reactor. After the reaction was started, the temperature inside the reactor gradually increased due to the heat generated by the polymerization. The final reactor internal temperature reached 75 ° C.

After the completion of the polymerization reaction, the reactor was used as a modifier.
1,3-Dimethyl-2-imidazolidinone (hereinafter referred to as modifier M2) was added in an amount of 1 equivalent to n-butyllithium used for the polymerization, and the modification reaction was carried out at 75 ° C. for 5 minutes. . Methanol was then added, and then octadecyl-3- (3,5-di-t-butyl-4) as a stabilizer.
-Hydroxyphenyl) propionate polymer 100
The solvent was removed after adding 0.3 parts by weight to parts by weight. Analysis of the obtained modified polymer (Polymer 3) revealed that the styrene content was 25% by weight, the vinyl bond content in the butadiene portion was 15%, and the block styrene content was 11% by weight.

D. Polymer 4 A n-hexane solution containing 16% by weight of a monomer having a butadiene / styrene weight ratio of 82/18 at a concentration of 16% was fed to a stirrer having an internal volume of 10 L and a jacketed tank reactor at a feed rate of 157 g / min. Then, the cyclohexane solution of n-butyllithium was fed at a rate of 0.15 g of n-butyllithium to 100 g of the monomer, and N, N, N ′, N′-tetramethylethylenediamine (TMEDA) was added as a polar substance. The cyclohexane solution of was fed at a feed rate such that TMEDA was 0.11 g per 100 g of the monomer, and continuous polymerization was carried out at 86 ° C.

Next, the living polymer obtained by continuous polymerization was reacted with 0.5 mol of the modifier M1 as a modifier with respect to 1 mol of n-butyllithium used for the polymerization. The obtained polymer was analyzed and found to have a styrene content of 1
8% by weight, vinyl bond content of butadiene part is 30% by weight
Met. From the analysis value of the amount of block styrene, the block of styrene was not present. Next, a hydrogenation catalyst was added to the polymer obtained by continuous polymerization in an amount of 100 ppm as Ti per 100 parts by weight of the polymer, and the hydrogen pressure was 0.7 MPa.
a, Hydrogenation reaction was performed at a temperature of 65 ° C. Thereafter, methanol was added, and then octadecyl-3- (3,3 as a stabilizer.
0.3 parts by weight of 5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by weight of the polymer. The resulting modified hydrogenated copolymer (Polymer 4) is
The styrene content was 18% by weight, the vinyl bond content in the butadiene portion before hydrogenation was 30% by weight, and the hydrogenation rate was 45%.

E. Polymer 5 In a tank-type reactor with an agitator and a jacket having an internal volume of 10 L, a feed rate of 157 g / min of an n-hexane solution containing a monomer having a butadiene / styrene weight ratio of 82/18 at a concentration of 16% by weight. Then, the cyclohexane solution of n-butyllithium was supplied at a feeding rate such that 0.09 g of n-butyllithium was added to 100 g of the monomer, and N, N, N ′, N′-tetramethylethylenediamine (TMEDA) was used as a polar substance. The cyclohexane solution of was fed at a feed rate such that TMEDA was 0.08 g per 100 g of the monomer, and continuous polymerization was performed at 86 ° C.

Next, the living polymer obtained by continuous polymerization was reacted equimolarly with the n-butyllithium used in the polymerization as a modifier M2 as a modifier. When the obtained polymer was analyzed, the styrene content was 18% by weight,
The vinyl bond content of the butadiene part was 30% by weight.
From the analysis value of the amount of block styrene, the block of styrene was not present. Next, 100 ppm of Ti was added to the polymer obtained by continuous polymerization as Ti per 100 parts by weight of the polymer, and the hydrogen pressure was 0.7 MPa and the temperature was 6 MPa.
The hydrogenation reaction was carried out at 5 ° C. Then add methanol,
Next, as a stabilizer, octadecyl-3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate was added in an amount of 0.3 part by weight based on 100 parts by weight of the polymer. The obtained modified hydrogenated copolymer (Polymer 5) had a styrene content of 18% by weight, a vinyl bond content of 30% by weight in the butadiene portion before hydrogenation, and a hydrogenation rate of 50%.

F. Polymer 6 Polymer 1 contains 1 mol of maleic anhydride per equivalent of functional group bonded to the polymer (hereinafter, referred to as cross-linking agent D1).
Was blended using a closed kneading machine equipped with a temperature control device (internal volume 1.7 liters) and kneading at a filling rate of 65% and a rotor rotation speed of 66/77 rpm. A polymer (polymer 6) was obtained.

G. Polymer 7 To the solution of Polymer 3, 1 mol of the cross-linking agent D1 was added per 1 equivalent of the functional group bonded to the polymer and reacted to obtain a secondary modified polymer of Polymer 3 (Polymer 7).

[0095]

Example 1 Using various modified polymers of polymers 1 to 7, a styrene resin composition is obtained by the bulk polymerization method described below. 92 parts by weight of styrene, 8 parts by weight of modified polymer, and silica were added to a stirrer and a jacketed reactor,
Then, as a stabilizer, n-octadecyl-3- (3 ',
0.3 parts by weight of 5'-tert-butyl-4'-hydroxyphenyl) propionate, t as a chain transfer agent
Add 0.05 parts by weight of dodecyl mercaptan and stir to dissolve. To this, 60 ppm of 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane was added to the styrene monomer.
Hours, 120 ° C for 2 hours, 150 ° C for 2 hours, 170 ° C
Polymerization for 2 hours. Furthermore, after heating at 230 ° C. for 30 minutes, unreacted products are removed under reduced pressure, and the obtained styrene resin composition is crushed and pelletized by an extruder. The resulting styrene resin composition exhibits excellent impact resistance.

[0096]

Example 2 A styrene resin composition was prepared in the same manner as in Example 1 except that the same reactor as in Example 1 was used and 69 parts by weight of styrene and 23 parts by weight of acrylonitrile were used. Called resin).
The ABS resin obtained exhibits excellent impact resistance.

[0097]

INDUSTRIAL APPLICABILITY When the modified polymer having a specific structure of the present invention or a hydrogenated product thereof and a reinforcing filler are used as a toughening agent for a styrenic resin composition, they are compared with conventional styrenic resin compositions. Thus, a product having a remarkably excellent balance of physical properties such as rigidity, impact resistance and luster can be obtained. Electronic devices such as TVs and VTRs, home electric appliances such as air conditioners and refrigerators, general equipment such as OA office equipment, stationery, It has an industrially excellent effect that it can be used in a wide variety of applications such as toys, leisure sports goods, household goods, building materials / household parts, and food containers.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J011 PA03 PA07 PA13 PA16 PA79                       PB22 PB40 PC02 PC08                 4J026 AA16 AA17 AA67 AA68 AA69                       AC11 AC16 AC17 AC18 AC21                       AC23 AC24 AC26 AC31 AC32                       BA05 BA06 BA20 BA24 BA27                       BA31 BA35 BA38 DA02 DA17                       DA18 DB02 DB15 FA02 GA06                       GA09

Claims (16)

[Claims] 1. 70 to 98 parts by weight of a monomer component which is an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and a copolymerizable monomer, and at least one selected from the following a and b. Component (1) 2-3 which is a modified polymer obtained by addition reaction of a functional group-containing modifier with one polymer or a hydrogenated product thereof.
0 parts by weight, a. Conjugated diene polymer b. A polymer composed of a conjugated diene and a vinyl aromatic hydrocarbon and a component (2) which is a reinforcing filler are added to the component (1) 1
A styrene resin composition obtained by radical polymerization of a mixture of 0.5 to 300 parts by weight per 100 parts by weight. 2. 70 to 98 parts by weight of a monomer component which is an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and a copolymerizable monomer, and at least one selected from the following a and b. Component (1) 2-3 which is a modified polymer obtained by addition reaction of a functional group-containing modifier with one polymer or a hydrogenated product thereof.
0 parts by weight, a. Conjugated diene polymer b. 0.5 to 300 parts by weight of component (2), which is a polymer-reinforcing filler composed of a conjugated diene and vinyl aromatic hydrocarbon, per 100 parts by weight of component (1), and a crosslinking agent component (3) are added as component (1). ) 0.01 to 20 per 100 parts by weight
A styrene-based resin composition obtained by radically polymerizing a mixture containing 1 part by weight. 3. 70 to 98 parts by weight of a monomer component which is an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and a copolymerizable monomer, and at least one selected from the following a and b. Functionality in which a cross-linking agent component (3) is bonded to the component (1) in the component (1), which is a modified polymer obtained by addition-reacting a functional group-containing modifier to one polymer or a hydrogenated product thereof. Group 1
2 to 30 parts by weight of secondary modified polymer (1-1) reacted in an amount of 0.3 to 10 mol per equivalent, a. Conjugated diene polymer b. A polymer composed of a conjugated diene and a vinyl aromatic hydrocarbon and a component (2) which is a reinforcing filler are added to the component (1) 1
A styrene resin composition obtained by radical polymerization of a mixture of 0.5 to 300 parts by weight per 100 parts by weight. 4. The component (2) is at least one component selected from the group consisting of silica-based inorganic fillers, metal oxides, metal hydroxides, and carbon. The styrene-based resin composition according to any one of 3 above. 5. The styrene resin composition according to claim 2 or 3, wherein the component (3) is a crosslinking agent having reactivity with the functional group of the component (1). 6. A rubber composition obtained by mixing the components (1) and (2) is an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and a copolymerizable monomer. The method for producing a styrenic resin composition according to claim 1, wherein the radical polymerization is carried out after being dissolved and dispersed in the monomer component. 7. A rubber composition obtained by mixing the component (1), the component (2) and the component (3) with an aromatic vinyl monomer,
The styrene-based resin composition according to claim 2, wherein the radical-polymerization is carried out after dissolving and dispersing in a monomer component which is a mixture of an aromatic vinyl monomer and a copolymerizable monomer. Manufacturing method. 8. A unit amount which is an aromatic vinyl monomer or a mixture of an aromatic vinyl monomer and a copolymerizable monomer after mixing the components (1-1) and (2). The method for producing a styrenic resin composition according to claim 3, wherein the radical polymerization is carried out after being dissolved and dispersed in the body component. 9. The component (1) has at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group.
The styrene resin composition according to any one of claims 1 to 5, wherein the styrene resin compositions are individually bonded. 10. The component (1) is a hydroxyl group, an epoxy group,
9. A styrene resin composition according to claim 6, wherein at least one atomic group having at least one functional group selected from an amino group, a silanol group and an alkoxysilane group is bonded. Manufacturing method. 11. The functional group-containing modifier has an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group in the polymer through an addition reaction with the polymer. The styrenic resin composition according to any one of claims 1 to 5 or 9, which is a modifying agent having a functional group that forms at least one modified polymer or a hydrogenated product thereof. . 12. The functional group-containing modifier has an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group in the polymer by an addition reaction with the polymer. The styrenic resin composition according to any one of claims 6 to 8 or 10, which is a modifying agent having a functional group that forms at least one modified polymer or a hydrogenated product thereof. Manufacturing method. 13. The crosslinking agent component (3) is a crosslinking agent having a functional group selected from a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, an alkoxysilane group, a hydroxyl group and an amino group. Items 2-5,
The styrene-based resin composition according to any one of 9 and 11. 14. The crosslinking agent component (3) is a crosslinking agent having a functional group selected from a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, an alkoxysilane group, a hydroxyl group and an amino group. The method for producing a styrene resin composition according to claim 7, 8, 10, or 12. 15. The component (1) is represented by the following formula (1) to formula (1)
At least one atomic group having at least one functional group selected from 4) is bonded, and the styrene resin composition according to any one of claims 1 to 5, 9, 11, or 13. . [Chemical 1] (In the above formula, R ^{1 to} R ⁴ are each a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, or a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group; A hydrocarbon group of 24. R ⁵ has 1 to 4 carbon atoms
A hydrocarbon chain of 8 or a hydrocarbon chain of 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group. R ¹ ~
Elements such as oxygen, nitrogen and silicon may be bound to the hydrocarbon group of R ^{4 and} the hydrocarbon chain of R ⁵ by a binding mode other than hydroxyl group, epoxy group, silanol group and alkoxysilane group. . R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms. ) 16. The component (1) is represented by the following formula (1) to formula (1)
At least one atomic group having at least one functional group selected from 4) is bonded, and the styrenic resin composition according to any one of claims 6 to 8, 10, 12, or 14. Manufacturing method. [Chemical 2] (In the above formula, R ^{1 to} R ⁴ are each a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, or a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group; A hydrocarbon group of 24. R ⁵ has 1 to 4 carbon atoms
A hydrocarbon chain of 8 or a hydrocarbon chain of 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group. R ¹ ~
Elements such as oxygen, nitrogen and silicon may be bound to the hydrocarbon group of R ^{4 and} the hydrocarbon chain of R ⁵ by a binding mode other than hydroxyl group, epoxy group, silanol group and alkoxysilane group. . R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms. )