JP6068962B2 - Rubber composition for reinforcing styrene resin - Google Patents

Description

  The present invention relates to a rubber composition for reinforcing a styrene-based resin and a rubber-reinforced styrene-based resin composition using the same.

  Conventionally, various studies have been made on rubber compositions for providing rubber-reinforced styrene-based resin compositions having a balance between gloss and impact properties.

  For example, in Patent Document 1, a star-shaped branched diene rubber comprising a star-shaped branched diene rubber having a cis 1,4-structure content of less than 75% and a linear diene rubber having a cis 1,4-structure content of less than 50%, and It is disclosed that a vinyl aromatic polymer having good gloss and high impact can be obtained by using a rubber characterized in that the viscosity of the polymer is lower than that of linear diene rubber.

Patent Document 2 proposes a technique characterized by a combination of styrene-butadiene copolymer rubber and polybutadiene.
In Patent Document 3, a polybutadiene rubber having a coupling degree of 50% or more and a polybutadiene having a star shape in which at least 50% by weight of five polymer chains are combined is characterized by being used in combination. Proposals have been made on impact-resistant styrenic resins.
By the way, the branched diene rubbers described in Examples of Patent Documents 1 to 3 are conjugated dienes having active ends obtained by polymerizing conjugated diene monomers in the presence of an organic lithium catalyst in an organic solvent. This is a conjugated diene rubber whose molecular weight is increased by reacting a halogen-based coupling agent with a rubber-based rubber, but if halogen such as chlorine ion is contained, a reactor or the like can be used in the production of a styrene-based resin composition. There are problems such as corrosion problems and difficulty in controlling the rubber particle size by affecting the grafting properties during production (reaction).
Therefore, as a method for producing a branched diene rubber by using a non-halogen coupling agent, for example, in Patent Document 4, a method using an epoxy coupling agent is used, and in Patent Document 5, an alkoxysilane compound is used as a cup. Proposals have been made for methods of use as ring agents.

Special table 2002-536515 gazette JP 63-301210 A JP-A 61-266448 Japanese Patent No. 2538629 Japanese Patent No. 3842485

However, Patent Document 1 does not describe the optimum range of viscosity composed of star-branched diene rubber and linear diene rubber, and there is room for further improvement in order to obtain a more desirable balance between gloss and impact strength. . In addition, there is room for further improvement from the viewpoint of graft properties and rubber particle diameter control during production of the rubber-reinforced styrene resin composition.
Patent Documents 2 and 3 do not describe a combination of a branched diene rubber and a linear diene rubber, and there is room for improvement in order to obtain a desirable balance between gloss and impact strength.
Further, Patent Documents 4 and 5 do not describe a combination of a non-halogen diene rubber and a linear diene rubber, and there is room for further improvement in order to obtain a desirable balance between gloss and impact strength. In addition, there is room for further improvement in the gel amount and gel particle size.
As described above, the conventional styrene resin reinforcing rubber has room for improvement from the viewpoints of corrosion of the reaction apparatus, the control of the rubber particle diameter, and the balance between gloss and impact resistance during the production of the styrene resin composition. There is.
The present invention has been made in view of the above circumstances, reduces the problem of corrosion of the reaction apparatus, etc. during the production of the rubber-reinforced styrene resin composition, facilitates control of the rubber particle diameter, gloss and impact resistance An object of the present invention is to provide a rubber composition for reinforcing a styrene resin that can provide a rubber-reinforced styrene resin composition having an excellent balance of properties, and a rubber-reinforced styrene resin composition using the same.

As a result of intensive studies, the present inventors have mixed the above-mentioned problem by mixing two kinds of conjugated dienes having a specific Mooney viscosity (ML _{1 + 4} 100 ° C.) and a 5 mass% styrene solution viscosity (SV) ratio. As a result, the present invention has been completed.
That is, the present invention is as follows.
[1] As the component (a), the ratio of Mooney viscosity (ML _{1 + 4} 100 ° C.) to 5% by mass styrene solution viscosity (SV) (ML _{1 + 4} 100 ° C./SV) is 0.8 to 1.8. As a component (b), a ratio of Mooney viscosity (ML _{1 + 4} 100 ° C.) to 5 mass% styrene solution viscosity (SV) (ML _{1 + 4} 100 ° C./SV) is 0.3 to A rubber composition containing a conjugated diene rubber that is 0.6,
10 to 55 parts by mass of the component (a), 90 to 45 parts by mass of the component (b), and 10 halogens to 100 parts by mass of the total content of the component (a) and the component (b). A rubber composition for reinforcing a styrene-based resin, which is × 10 ⁻⁴ parts by mass or less.
[2] The styrene-based resin reinforcement according to [1], wherein the 5 mass% styrene solution viscosity (SV) of the component (a) is smaller than the 5 mass% styrene solution viscosity (SV) of the component (b). Rubber composition.
[3] The styrene-based resin reinforcement according to [1] or [2], wherein the mixture of the component (a) and the component (b) has a 5 mass% styrene solution viscosity (SV) of 40 to 70 mPa · s. Rubber composition.
[4] The component (a) according to any one of [1] to [3], wherein the component (a) is a conjugated diene rubber polymerized with an alkyllithium initiator and coupled using an alkoxysilyl compound. A rubber composition for reinforcing styrene resin.
[5] The rubber composition for reinforcing a styrene-based resin according to any one of [1] to [4], wherein the viscosity (SV) of 5% by mass of the component (a) is 20 to 55 mPa · s. object.
[6] The rubber composition for reinforcing a styrene-based resin according to any one of [1] to [5], wherein the viscosity of the 5% by weight styrene solution (SV) of the component (b) is 70 to 150 mPa · s. object.
[7] A rubber-reinforced styrene resin composition using the rubber composition according to any one of [1] to [5].
[8] Ratio of Mooney viscosity (ML _{1 + 4} 100 ° C.) and 5 mass% styrene solution viscosity (SV) (ML ₁ ) dispersed in the matrix as the component (a) as a matrix made of styrene-based polymer Conjugated diene rubber having ₊₄ 100 ° C / SV) of 0.8 to 1.8, and Mooney viscosity (ML _{1 + 4} 100 ° C) and 5 mass% dispersed in the matrix as component (b) A conjugated diene rubber having a styrene solution viscosity (SV) ratio (ML _{1 + 4} 100 ° C./SV) of 0.3 to 0.6, and the sum of the component (a) and the component (b) The rubber reinforcement which contains 10-55 mass parts of said (a) component, 90-45 mass parts of said (b) component with respect to 100 mass parts of content, and halogen is 10x10 < ^-4 > mass part or less. Styrenic resin composition.

  According to the present invention, the rubber-reinforced styrene is reduced in the corrosion problem of the reaction apparatus during the production of the rubber-reinforced styrene resin composition, the rubber particle diameter is easily controlled, and the balance between gloss and impact resistance is excellent. A rubber composition for reinforcing a styrene-based resin that can provide a resin-based resin composition can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.
[Styrene-based resin reinforcing rubber composition]
In this embodiment, as the component (a), the ratio of Mooney viscosity (ML _{1 + 4} 100 ° C.) to 5 mass% styrene solution viscosity (SV) (ML _{1 + 4} 100 ° C./SV) is 0.8 to 1. The ratio of the Mooney viscosity (ML _{1 + 4} 100 ° C.) to the 5% by mass styrene solution viscosity (SV) (ML _{1 + 4} 100 ° C./SV) is 0 as the component (b). A rubber composition containing a conjugated diene rubber that is 3 to 0.6, wherein the component (a) is added to 10 parts with respect to 100 parts by mass of the total content of the component (a) and the component (b). It is a rubber composition for reinforcing a styrene-based resin, containing ~ 55 parts by mass, 90 to 45 parts by mass of the component (b), and halogen is 10 × 10 ^-4 parts by mass or less.
In this embodiment, when calculating the ratio of the Mooney viscosity (ML _{1 + 4} 100 ° C.) to the 5% by mass styrene solution viscosity (SV) (ML _{1 + 4} 100 ° C./SV), the 5% by mass styrene solution viscosity ( The unit of (SV) is mPa · s.

In the rubber composition of the present embodiment, the ratio of Mooney viscosity (ML _{1 + 4} 100 ° C.) to 5 mass% styrene solution viscosity (SV) (ML _{1 + 4} 100 ° C./SV) is 0.8 to 1.8. A ratio (ML _{1 + 4} 100 ° C./SV) of a conjugated diene rubber (component (a)), Mooney viscosity (ML _{1 + 4} 100 ° C.) to 5% by mass styrene solution viscosity (SV) is 0.3 to 0 .6 containing a specific amount of the conjugated diene rubber (component (b)) can provide a rubber-reinforced styrene resin composition having high impact characteristics and excellent gloss, It becomes easy to control the rubber particle diameter during production of the composition.

In this embodiment, the Mooney viscosity (ML _{1 + 4} 100 ° C.) is measured using a Mooney viscometer (manufactured by Shimadzu Corporation, “SMV-202”) in accordance with JIS K6300 (ISO 289-1). First, the sample is preheated for 1 minute, the rotor is rotated at 2 rpm, the torque after 4 minutes is measured, and the value is taken as the Mooney viscosity.

  In the present embodiment, the 5 mass% styrene solution viscosity (SV) is a solution viscosity (SV) measured at 25 ° C. at a rubber concentration of 5 mass% in styrene, and specifically, 2.385 g of conjugated diene rubber. Is dissolved in 50 mL of styrene and measured at 25 ° C. using a Cannon Fenceke viscometer. In this embodiment, the unit of mPa · s is used for the 5 mass% styrene solution viscosity (SV).

<Conjugated diene rubber>
Both the component (a) and the component (b) are conjugated diene rubbers. Here, the conjugated diene rubber refers to a polymer containing repeating units derived from a conjugated diene monomer.
The conjugated diene monomer is not particularly limited. For example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, Examples include conjugated dienes such as 1,3-heptadiene and 1,3-hexadiene, and 1,3-butadiene is particularly preferred.

For example, when butadiene is used as the conjugated diene monomer, the microstructure of the conjugated diene rubber used in this embodiment is the content of 1,2-vinyl bond (hereinafter referred to as “1,2-vinyl content”). Is preferably 10 to 80%, and the cis-1,4 bond content is preferably in the range of 10 to 85%, and in particular, the 1,2-vinyl content is preferably 12 to 40%. .
The method for adjusting the 1,2-vinyl content is not particularly limited, and a conventionally known method can be used. For example, during polymerization of a conjugated diene monomer, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF), etc .; amines such as dimethylamine; and thioethers such as dimethyl sulfide and diethyl sulfide are added to the polymerization system. By doing so, the 1,2-vinyl content in the conjugated diene rubber can be adjusted to a desired range.
The 1,2-vinyl bond may be present uniformly in the molecular chain, or may be present so as to gradually decrease along the molecular chain (Japanese Patent Publication No. 47-875), or even a block. May be present (US Pat. No. 3,318,840). The method for making the 1,2-vinyl bond uniform in the molecular chain is not particularly limited. For example, a method in which the polymerization initiation temperature is set to 30 to 90 ° C., and the polymerization is performed at a constant temperature as much as possible, and 1 The method for gradually changing the 2-vinyl bond along the molecular chain is not particularly limited. For example, a method in which the polymerization is carried out at an elevated temperature, that is, the polymerization initiation temperature is usually 30 to 80 ° C. And a method of setting the polymerization end temperature to 85 to 120 ° C. or a method of gradually adding the 1,2-vinyl content adjusting agent during the polymerization.

The production method of the conjugated diene rubber used in the present embodiment is not particularly limited, and examples thereof include a method of polymerizing a conjugated diene monomer by coordination polymerization, anionic polymerization, cationic polymerization, or the like. Among the polymerization methods, anionic polymerization is preferable from the viewpoint of easy control of the structure.
The conjugated diene monomer is not particularly limited, and examples thereof include the conjugated dienes, and 1,3-butadiene is particularly preferable.
The anionic polymerization is not particularly limited, and a known method can be applied, and examples thereof include anionic living polymerization using an initiator such as an organic lithium compound in a hydrocarbon solvent.

  The hydrocarbon solvent is not particularly limited, and examples thereof include aliphatic hydrocarbons such as butane, pentane and hexane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. Preferred examples include hexane and cyclohexane.

  The organolithium compound is a monoorganolithium compound or a polyfunctional organolithium compound, or may be a mixture of a monoorganolithium compound and a polyfunctional organolithium compound. Examples of the monoorganolithium compound include n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium, benzyllithium, etc., preferably n-butyllithium, sec-Butyllithium is used. Examples of the polyfunctional organolithium compound include dilithiomethane, 1,4-dilithiobutane, 1,6-dilithiohexane, 1,4-dilithiocyclohexene, 1,4-dilithio-2-ethylcyclohexane, 1,3-dilithio-4-phenylbutane, 1,2-dilithio-1,2-diphenyl-ethane, 1,10-dilithiodecane, 1,20-dilithioeicosane, 1,1-dilithiodiphenylene, 1,4-dilithiobenzene, 1,5-dilithionaphthalene , Dilithiopolybutadiene, dilithioisoprene, dilithiodiisoprene, dilithiopolyisoprene, 2,2'-2 "-trilithio-p-terphenyl, 1,3,5-trilithiobenzene, 1,3,5-trilithio-2,4 6-triethylbenzene, n-butyllithium and 1,3-buta Reactants ene and divinylbenzene, reaction products of n- butyl lithium and polyacetylene compound.

  In the polymerization, from the viewpoint of improving the effect of suppressing gel formation, allenes such as propadiene and 1,2-butadiene may be added to the polymerization system together with the monomer and the inert solvent.

<(A) component>
The rubber composition of this embodiment has a ratio of Mooney viscosity (ML _{1 + 4} 100 ° C.) to 5 mass% styrene solution viscosity (SV) (ML _{1 + 4} 100 ° C./SV) of 0.8 to 1.8. It contains the component (a) which is a conjugated diene rubber.
Since the ML _{1 + 4} 100 ° C./SV of the component (a) is 0.8 or more, the change rate of the cold flow of the conjugated diene rubber of the component (a) is reduced, and the rubber composition of this embodiment is obtained. When used, the handleability is good and the adhesion and retention during pulverization is reduced, and is preferably 1.0 or more, more preferably 1.1 or more. On the other hand, when ML _{1 + 4} 100 ° C./SV of the component (a) is 1.8 or less, generation of particles having a large gel particle size when the rubber composition of this embodiment is used for a styrene resin. Can be suppressed, and the gloss becomes good, preferably 1.7 or less, more preferably 1.6 or less.

The method of setting ML _{1 + 4} 100 ° C./SV of component (a) to 0.8 to 1.8 is not particularly limited. For example, a conjugated diene monomer is conjugated using an organolithium compound in a hydrocarbon solvent. There is a method of polymerizing a diene to obtain a conjugated diene rubber having an active lithium terminal, and then adjusting the resulting conjugated diene rubber by further coupling reaction. Various means for controlling the branching and molecular weight of the conjugated diene rubber can be used to achieve the desired solution viscosity and Mooney viscosity. For example, when the coupling rate is increased, ML _{1 + 4} 100 ° C./SV tends to increase, and when the coupling rate is adjusted low, ML _{1 + 4} 100 ° C./SV tends to decrease.

Although the coupling agent used by the said coupling reaction is not specifically limited, From the point of coupling rate adjustment (reactivity), the alkoxysilane compound represented by following General formula (1) can be used conveniently.
R _X -Si- (OR) _4-X (1)
(In the formula, R represents the same or different alkyl group having 1 to 10 carbon atoms and aryl group. X is an integer of 0 or 1.)

  Examples of the alkoxysilane compound represented by the general formula (1) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, tetrabutoxysilane, tetraphenoxysilane, and the like. Species or two or more can be used in any combination. Preferred coupling agents include tetramethoxysilane and tetraethoxysilane.

The amount of the coupling agent used is not particularly limited, but is preferably 0.05 mol times with respect to 1 mol of the organolithium compound catalyst used in producing the conjugated diene rubber having an active lithium terminal. It is above, More preferably, it is the range of 0.1-0.4 times mole. The reaction time between the conjugated diene rubber having an active lithium terminal and the compound can be adjusted over a wide range, but the reaction time is usually 1 minute to 60 minutes, preferably 1 minute to 30 minutes. These compounds may be used as they are, or may be used after being dissolved in a solvent. When a solvent is used, a hydrocarbon solvent which is inactive with respect to active lithium is used.
The said hydrocarbon solvent is not specifically limited, For example, benzene, toluene, a cyclohexane, n-hexane etc. can be mentioned.

In the coupling reaction, the method for adding the coupling agent is not particularly limited, but a batch or continuous addition method is generally used. In the case of a batch system, a conjugated diene rubber having a molecular weight distribution Mw / Mn of 1.1 to 1.4 is obtained. In the case of a continuous system, a conjugated diene rubber having a molecular weight distribution Mw / Mn of 1.5 to 2.5 is obtained. It is done. Here, Mw is a weight average molecular weight in terms of polystyrene obtained by gel permeation chromatography (GPC) measurement, and Mn is a number average molecular weight.
When the molecular weight distribution Mw / Mn is 1.1 to 1.9, the cold flow is improved, and when used for a styrene resin, the gel particle size adjustment is excellent.

The reaction temperature of the conjugated diene rubber having an active lithium terminal and the coupling agent is preferably in the range of 50 to 130 ° C. More preferably, it is 80 degreeC-110 degreeC. When the reaction temperature is 130 ° C. or lower, the coupling efficiency is improved, and the Mooney viscosity (ML _{1 + 4} 100 ° C.) of the present embodiment and the solution viscosity (SV) measured at 25 ° C. with a rubber concentration of 5 mass% in styrene. ) Conjugated diene rubber having a ratio (ML / SV) of 0.8 to 1.8 can be obtained efficiently. In the case of 50 degreeC or more, it is preferable in industrial implementation from the viewpoint that the reactivity of the conjugated diene rubber having the active lithium terminal and the coupling agent is improved, and a special operation for cooling the reaction vessel is not required.

In the coupling reaction, if necessary, a deactivator, a neutralizing agent, and the like may be added to the resulting conjugated diene rubber solution after the coupling reaction.
The quenching agent is not particularly limited, and examples thereof include water; alcohols such as methanol, ethanol, and isopropanol.
The neutralizing agent is not particularly limited, and examples thereof include carboxylic acids such as stearic acid, oleic acid, and versatic acid (a mixture of carboxylic acids having 9 to 11 carbon atoms, mainly 10 and having many branches); inorganic Examples include an acid aqueous solution and carbon dioxide gas.
Furthermore, it is preferable to add a rubber stabilizer from the viewpoint of preventing gel formation and improving the stability during processing. The addition of the rubber stabilizer is preferably carried out after adding a deactivator or a neutralizing agent in order to suppress coloring of the rubber stabilizer.

From the viewpoint of adjusting the gel particles in the rubber-reinforced styrene resin to an average particle size suitable for high gloss, the 5 mass% styrene solution viscosity (SV) of the component (a) is 20 to 55 mPa · s. More preferably, it is 20-50 mPa * s, More preferably, it is 25-45 mPa * s. When the 5 mass% styrene solution viscosity (SV) of the component (a) is 20 mPa · s or more, the cold flow of the rubber is improved, and when it is 50 mPa · s or less, the gel particles in the rubber-reinforced styrene resin The average particle size suitable for high gloss can be easily adjusted.
In order to effectively balance the impact resistance and gloss when obtaining a rubber-reinforced styrene resin, it is important to adjust the form and particle size of the gel particles of the styrene resin. However, it is preferable that it is smaller than SV of (b) component from the point which makes such adjustment easy.

<(B) component>
In the rubber composition of this embodiment, the ratio of Mooney viscosity (ML _{1 + 4} 100 ° C.) to 5 mass% styrene solution viscosity (SV) (ML _{1 + 4} 100 ° C./SV) is 0.3 to 0.6. The component (b) which is a certain conjugated diene rubber is contained. (B) ML _{1 + 4} 100 ° C./SV of the component is 0.3 or more, so that the change rate of cold flow of the conjugated diene rubber is reduced, and handling property when the rubber composition of the present embodiment is obtained, The adhesion and retention during pulverization is reduced, etc., and is preferably 0.35 or more, more preferably 0.45 or more. On the other hand, when ML _{1 + 4} 100 ° C./SV of the component (b) is 0.6 or less, solubility and thermal stability (gel formation) can be improved, and the rubber composition of this embodiment can be used as a styrene resin. When used in the above, the effect of combining the component (a) and the component (b), that is, compatibility when dissolved in the vinyl aromatic monomer, the gel particle size can be easily adjusted. 55 or less, more preferably 0.5 or less. (B) As a method for adjusting ML _{1 + 4} 100 ° C./SV of component to 0.3 to 0.6, a conjugated diene is polymerized using a conjugated diene monomer in a hydrocarbon solvent using an organolithium compound, Various means for controlling the molecular weight can be used without conducting the coupling reaction or by performing a small amount of coupling reaction. Here, the coupling reaction is not particularly limited, and for example, the method as described above can be used. For example, if the heat residence time in the reaction vessel after the conjugated diene polymerization is reduced or slightly coupled, ML _{1 + 4} 100 ° C / SV tends to increase, and the reaction vessel stays after the conjugated diene polymerization. When the time is shortened or the reaction temperature is lowered, ML _{1 + 4} 100 ° C./SV tends to decrease.

  From the viewpoint of adjusting the form of the gel particles in the rubber-reinforced styrene-based resin (whether the rubber component is dense or sparse) and the amount of the gel, the 5 mass% styrene solution viscosity (SV) of the component (b) is: 70 to 150 mPa · s, more preferably 70 to 130 mPa · s, still more preferably 75 to 120 mPa · s, and particularly preferably 80 to 110 mPa · s. When the 5 mass% styrene solution viscosity (SV) of the component (b) is 70 mPa · s or more, the form of the gel particles in the rubber-reinforced styrene resin is salami particles with a loose rubber component, and is 150 mPa · s or less. In this case, there are few large particles in the rubber-reinforced styrene resin, and it becomes easy to adjust the average particle size of the gel particles suitable for high gloss.

<Composition>
The rubber composition of the present embodiment is composed of 10 to 55 parts by mass of the component (a) and 90 to 90 parts of the component (b) with respect to 100 parts by mass of the total content of the component (a) and the component (b). Contains 45 parts by mass.
When the component (a) is 10 parts by mass or more and the component (b) is 90 parts by mass or less, when the rubber-reinforced styrene resin composition is used, the gloss is excellent and the gel particle size is also reduced. When the component (a) is 55 parts by mass or less and the component (b) is 45 parts by mass or more, when a rubber-reinforced styrene resin composition is obtained, the impact resistance is good and the gel amount is large. It is preferable to contain 20-50 mass parts of said (a) component, 80-50 mass parts of said (b) component, 30-45 mass parts of said (a) component, and 70-55 said (b) component. It is more preferable to contain a part by mass.

  When the rubber composition of the present embodiment is used to obtain a rubber-reinforced styrene-based resin, the 5 mass% styrene solution viscosity (SV) of a mixture of the component (a) and the component (b) from the viewpoint of balance between impact resistance and gloss. Is preferably 30 to 80 mPa · s, more preferably 35 to 75 mPa · s, and still more preferably 40 to 70 mPa · s.

  The combination of the conjugated diene rubber present in the rubber composition of the present embodiment is a component (a) having a 5% by mass styrene solution viscosity (SV) of 20 to 55 mPa · s and a 5% by mass styrene solution viscosity (SV). (B) component whose is 70-150 mPa * s is preferable.

<Halogen content>
The rubber composition of this embodiment has a halogen content of 100 parts by mass with respect to the total content of the component (a) and the component (b). When the halogen content is 10 × 10 ⁻⁴ parts by mass or less, corrosion of the reaction apparatus or the like during the production of the styrene resin composition is prevented, and the graft properties during the production (during the reaction) are affected, so that the rubber particles The diameter can be controlled. The amount is preferably 7 × 10 ⁻⁴ parts by mass or less, more preferably 5 × 10 ⁻⁴ parts by mass or less.
The rubber composition of the present embodiment can contain 10 × 10 ⁻⁴ parts by mass or less of halogen by substantially not containing halogen in the rubber production stage or the like. “Substantially free of halogen” means that no halogen is used as a raw material in the polymerization of conjugated diene rubbers, including monomers, solvents, catalysts, coupling agents, and other additives.

<Other ingredients>
The rubber composition of the present embodiment preferably contains a rubber stabilizer from the viewpoint of preventing gel formation and improving the stability during processing.
The stabilizer for rubber is not particularly limited, and known ones can be used. For example, 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5 ′ Phenol compounds such as -di-tert-butyl-4'-hydroxyphenyl) propionate; organic phosphite compounds such as tris- (2,4-di-tert-butylphenyl) phosphite; 2,4-bis [ (Octylthio) methyl] -O-cresol and other sulfur-containing phenol compounds; or n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate and tris- (2 , 4-di-tert-butylphenyl) phosphite and other known stability such as a combination of phenolic and organic phosphite It can be used.
Further, rubber components other than the component (a) and the component (b) may be included. Examples of the rubber other than the component (a) and the component (b) include, for example, a conjugated diene rubber other than the component (a) and the component (b), a random butadiene-styrene copolymer, a block butadiene-styrene copolymer, natural Rubber and the like.

[Rubber-reinforced styrene resin composition]
The rubber-reinforced styrene resin composition of the present embodiment is a rubber-reinforced styrene resin composition using the above rubber composition. Since the rubber composition of this embodiment is used, the balance between glossiness and impact resistance is excellent.
The rubber-reinforced styrene-based resin composition of the present embodiment includes a matrix composed of a styrene-based polymer, Mooney viscosity (ML _{1 + 4} 100 ° C.) and 5% by mass styrene dispersed in the matrix as component (a). A conjugated diene rubber having a solution viscosity (SV) ratio (ML _{1 + 4} 100 ° C./SV) of 0.8 to 1.8, and a Mooney viscosity (ML) dispersed in the matrix as component (b) _{1 + 4} 100 ° C.) and a 5 mass% styrene solution viscosity (SV) ratio (ML _{1 + 4} 100 ° C./SV) of 0.3 to 0.6, and a conjugated diene rubber, 10 to 55 parts by mass of the component (a), 90 to 45 parts by mass of the component (b), and 10 × 10 6 halogens per 100 parts by mass of the total content of the component a) and the component (b). ^-4 parts by mass or less of a rubber-reinforced styrene resin composition Include.

<Method for Producing Rubber Reinforced Styrene Resin Composition>
The production method of the rubber-reinforced styrene resin composition is not particularly limited, and examples thereof include continuous bulk polymerization and solution polymerization. The polymerization is carried out in the presence of thermal polymerization or an initiator.
In general, first, the conjugated diene rubber of this embodiment is dissolved in a vinyl aromatic monomer, and if necessary, a solvent such as toluene and ethylben, an internal lubricant such as liquid paraffin, mineral oil, and organic polysiloxane, an oxidation In the case of non-catalytic thermal polymerization, an inhibitor, mercaptans, α-methylstyrene dimer, etc. are added, and heat polymerization is usually performed at a temperature of 95 to 200 ° C. In addition, in initiator polymerization in the presence of a radical initiator, The styrene polymerization operation is continued at a temperature lower than usual, for example, 60 to 180 ° C.

  Examples of typical vinyl aromatic monomers used in the production of the styrene-based resin composition include all isomers of styrene, alphamethylstyrene, vinyltoluene, and the like, and styrene is particularly preferable. Vinyl aromatic monomers can also be combined with other copolymerizable monomers. Examples of these copolymerizable monomers include acrylic monomers such as acrylonitrile, methacrylonitrile, methacrylic acid, methyl methacrylate, acrylic acid and methyl acrylate, maleimide, phenylmaleimide and maleic anhydride. The polymerization of the vinyl aromatic monomer is carried out in the presence of a pre-dissolved diene, resulting in an impact modified or graft rubber containing product. Examples of these are described in U.S. Pat. Nos. 3,123,655, 3,346,520, 3,639,522 and 4,409,369.

  The amount of rubber initially dissolved in the vinyl aromatic monomer is not particularly limited and depends on the desired concentration of rubber in the intended rubber-reinforced styrenic resin composition, the conversion during polymerization, and the viscosity of the solution. Typically, the amount of rubber initially dissolved in the vinyl aromatic monomer is 6% by weight or more, preferably 6.5% by weight or more, more preferably 7% by weight or more, based on the total weight of the composition. Preferably it is 8.0 mass% or more and 15 mass% or less, Preferably it is 14 mass% or less, More preferably, it is 13 mass% or less, Most preferably, it is 12 mass% or less.

  When an initiator is used, there are suitable initiators that can impart the desired graft of polymer to the rubber particles under conditions of polymerization of the vinyl aromatic monomer and polymerization promotion. Typical initiators include tertiary butyl peroxybenzoate and tertiary butyl peroxyacetate, tertiary butyl peroxyoctoate, dibenzoyl peroxide, dilauroyl peroxide, 1,1-bis tertiary butyl peroxy There are peroxide initiators such as cyclohexane, 1,3-bis tert-butylperoxy-3,3,5-trimethylcyclohexane and dicumyl peroxide. Photochemical initiation techniques can be used if desired. Preferred initiators include tertiary butyl peroctoate, tertiary butyl isopropyl percarbonate, dibenzoyl peroxide, tertiary butyl peroxybenzoate, 1,3-bis tertiary butyl peroxycyclohexane and tertiary butyl peroxyacetate. is there.

  The amount of the initiator is not particularly limited, and may be used in a concentration range depending on various factors including the initiator used, the polymer graft ratio, and the conditions for performing bulk polymerization. The initiator is usually used in an amount of 0 to 2000 ppm, preferably 100 to 1500 ppm, based on the weight of the vinyl aromatic monomer.

  The solvent used in the production of the rubber-reinforced styrene resin is not particularly limited, and representative solvents include aromatic or substituted aromatic hydrocarbons such as benzene, ethylbenzene, toluene, and xylene; heptane, hexane, and octane. Substituted or unsubstituted, straight or branched chain saturated aliphatic hydrocarbons having 5 or more carbon atoms, such as cyclohexane and the like, and alicyclic or substituted alicyclic hydrocarbons having 5 or 6 carbon atoms such as cyclohexane . Preferred solvents include substituted aromatic hydrocarbons, with ethylbenzene and xylene being particularly preferred. In general, the solvent is used in an amount sufficient to improve processability and heat transfer during polymerization. These amounts will vary depending on the rubber, monomer and solvent used, the equipment and the desired degree of polymerization. When used, the solvent is usually used in an amount of not more than about 35% by weight, preferably 2 to 25% by weight, based on the total weight of the solution.

  Polymerization of plasticizers such as mineral oil, glidants, lubricants, antioxidants, catalysts, mold release agents, or chain transfer agents containing alkyl mercaptans such as n-dodecyl mercaptan during the production of rubber reinforced styrenic resins Auxiliaries and other substances may be added. When used, the chain transfer agent may be present at 0.001 to 0.5% by weight, based on the total weight of the polymerization mixture to which it is added.

  After polymerization of the rubber-reinforced styrenic resin, crosslinking of the rubber in the product, removal of unreacted monomers and solvents and other volatiles when used are carried out using known means. For example, the polymerization mixture may be put into a deaerator and heated, for example, 200 to 300 ° C., and the monomer and other volatile components may be flashed off under vacuum.

  The produced polymer is washed, dried, and used as pellets or powder as necessary. In addition to the above, a rubber-reinforced styrene resin composition can be obtained by a conventionally known method obtained by improving or improving these methods.

  The rubber-reinforced styrene resin composition obtained by using the rubber composition for styrene resin of the present embodiment does not contain halogen as compared with the conventional impact-resistant styrene resin, and is a styrene resin composition. It improves the problem of corrosion of reactors in production and the problem of difficulty in controlling the rubber particle size by affecting the grafting properties during production (reaction), and has a good balance between gloss and impact resistance. Electronic devices such as TVs and VTRs, home appliances such as air conditioners and refrigerators, general equipment such as OA office equipment, stationery, toys, leisure sports goods, household goods, building materials / housing parts, food containers, etc. It has an industrially excellent effect that it can be used.

Hereinafter, specific embodiments of the present embodiment will be described by way of examples. However, this is for more specifically explaining the gist of the present invention, and does not limit the present invention.
The analysis of the conjugated diene rubber and the rubber composition was performed by the following method.
(1) Molecular weight distribution (Mw / Mn)
Using a GPC measuring apparatus (“HLC-8320” manufactured by Tosoh Corporation) connected with three columns each having a polystyrene gel as a packing material, chromatograms were measured, and standard polystyrene (Shodex STANDARD KIT “SM-105”). The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined based on a calibration curve using, and the molecular weight distribution (Mw / Mn) was calculated.
The column used was one composed of a guard column: TSKguardcolumn SuperMP (HZ) -H manufactured by Tosoh Corporation and a column: TSKgel G6000H, G5000H, G4000H manufactured by Tosoh Corporation.
The RI detector attached to HLC-8320GPC was used under the conditions of an oven temperature of 35 ° C. and a THF flow rate of 1.0 mL / min.
As a measurement solution, 5 mg of a measurement sample was dissolved in 5 mL of THF, and 50 μL of the measurement solution was injected into a GPC measurement device.
(2) 1,2-vinyl content After completely dissolving 0.1 g of a sample for measurement with 10 mL of carbon disulfide, an infrared spectrophotometer ("Spectram 100" manufactured by Perkin Elmer Co., Ltd.) was used using a 0.5 mm cell. )) Was used to measure the spectrum.
Subsequently, vinyl content was calculated | required by the Morero method (LA Chimica Industries 41,758 (1959)) for the acquired spectrum.
(3) 5 mass% styrene solution viscosity (5 wt% SV)
2.385 g of conjugated diene rubber was dissolved in 50 mL of styrene and measured at 25 ° C. using a Cannon Fenceke viscometer.
(4) Mooney Viscosity Mooney viscosity was measured using a Mooney viscometer (manufactured by Shimadzu Corporation, “SMV-202”) in accordance with JIS K6300 (ISO 289-1). The measurement temperature was 100 ° C.
First, after preheating the sample for 1 minute, the rotor was rotated at 2 rpm and the torque after 4 minutes was measured to obtain the Mooney viscosity (ML _{1 + 4} 100).
(5) cold flow cold flow measurements, 40 mm × 40 mm × thickness (H ₀₎ to 50mm sample, from the thickness after standing over a 1kg load at 25 ° C. 60 minutes (H _100), the change rate of the thickness (%) Was measured. The rate of change in thickness was evaluated by the following formula. It was judged that the larger this value, the easier the conjugated diene rubber was deformed.
Thickness change rate (%) = (H ₀ −H ₁₀₀ ) × 100 / H ₀
(6) Halogen content Sample gas is burned by a pretreatment device for ion chromatography (Mitsubishi Analitech's automatic combustion device, "AQF-100 type"). Dissolve and absorb. The peak of this dissolved solution is measured using an ion chromatograph (“ICS-1500”, manufactured by Dionex), and the halogen concentration is calculated from a calibration curve.

Analysis and evaluation of the rubber-reinforced styrene resin composition were carried out by the methods shown below.
(7) Gel amount, Swelling Index
After the rubber-reinforced styrene resin composition (sample) was dissolved in toluene, it was separated into a dissolved portion and an undissolved portion (gel) with a centrifuge, and the amount of the undissolved portion was measured by removing the dissolved solution ( WetGel). Furthermore, the toluene dissolved in the undissolved portion was removed by vacuum drying, and the undissolved portion after vacuum drying was measured (DryGel).
The gel amount and the Welling Index were calculated from the measured undissolved amount (WetGel, DryGel) according to the following formula.
Gel amount (%) = (DryGel / sample amount) × 100
Swelling Index = (WetGel / DryGel)
(8) Gel particle diameter After dissolving the rubber-reinforced styrene-based resin composition in dimethylformamide (DMF), the sample bottle containing the solution was dispersed for 2 hours with an ultrasonic cleaner, and then the gel particles were dispersed. Using a laser type particle size distribution analyzer (manufactured by HORIBA, “LA-920”), a solution in which gel particles are dispersed in a batch cell containing DMF was dropped and measured to obtain an average particle size.
(9) Melt flow rate (MFR)
According to the test method of JIS-K-7210, measurement was performed at a test temperature of 200 ° C. and a load of 5 kg.
(10) Izod impact strength (Izod)
It measured according to JIS-K-7110 using the injection-molded test piece (with a notch) of 3.2 mm in thickness.
(11) Gloss Using the injection-molded test piece, the glossiness (incident angle 60 °) of the gate part and the end gate part was measured and averaged according to ASTM D-523.

Hereinafter, specific examples of polymerization of conjugated diene rubber, examples and comparative examples will be described specifically, but the present invention is not limited thereto.
Unless otherwise specified, the amount is expressed in mass parts or mass%.

[Production Example 1] (Conjugated Diene Rubber (Polymer A))
The autoclave with a volume of 10 L and a jacketed autoclave was washed and dried, and after purging with nitrogen, 700 g of 1,3-butadiene purified and 5000 g of cyclohexane were added in advance, and then tetrahydrofuran was added to cyclohexane as a regulator of 1,2-vinyl content. Further, 0.12 parts by mass of an n-butyllithium / n-hexane solution per 100 parts by mass of 1,3-butadiene was added as an organic lithium compound initiator, and polymerization was started at 65 ° C. 1,3-Butadiene is completely polymerized to obtain a conjugated diene rubber having an active lithium terminal, and then 0.15 mol of tetraethylene is added to this conjugated diene rubber having an active lithium terminal with respect to 1 mol of an organolithium compound. After ethoxysilane is added and allowed to undergo a coupling reaction for 30 minutes, 10 parts by weight of water per 100 parts by weight of conjugated diene rubber (polymer) is added to the resulting conjugated diene rubber solution, and carbon dioxide is further added. did. Carbon dioxide was added in an amount of 1 mol with respect to 1 mol of the organic lithium compound under a pressure of 0.3 MPa (gauge pressure), and carbon dioxide, water, and a polymer solution were mixed and contacted.
As a stabilizer in the conjugated diene rubber solution thus obtained, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 2,4-bis [(octylthio) Methyl] -O-cresol was added in an amount of 0.3 parts by weight and 0.1 parts by weight per 100 parts by weight of the polymer, respectively, and the solvent was removed by steam stripping, followed by dehydration and subsequent drying with a hot roll (110 ° C.). 5% styrene solution viscosity (SV) shown in Table 1 is 44 mPa · s, Mooney viscosity (ML _{1 + 4} 100 ° C.) is 37, ML _{1 + 4} 100 ° C./SV is 0.84. A polymer A was obtained.

[Production Example 2] (Conjugated Diene Rubber (Polymer B))
The autoclave with a volume of 10 L and a jacketed autoclave was washed and dried, and after purging with nitrogen, 700 g of 1,3-butadiene purified and 5000 g of cyclohexane were added in advance, and then tetrahydrofuran was added to cyclohexane as a regulator of 1,2-vinyl content. Further, 0.16 parts by mass of n-butyllithium / n-hexane solution per 100 parts by mass of 1,3-butadiene was added as an organolithium compound initiator, and polymerization was started at 65 ° C. 1,3-Butadiene is completely polymerized to obtain a conjugated diene rubber having an active lithium end, and then 0.32 mol of tetraethylene is added to 1 mol of the organic lithium compound. Methoxysilane was added and allowed to undergo a coupling reaction for 10 minutes. Further, 10 parts by mass of water per 100 parts by mass of the conjugated diene rubber (polymer) was added to the conjugated diene rubber solution, and carbon dioxide was further added. Carbon dioxide was added in an amount of 1 mol with respect to 1 mol of the organic lithium compound under a pressure of 0.3 MPa (gauge pressure), and carbon dioxide, water, and a conjugated diene rubber solution were mixed and contacted.
As a stabilizer in the conjugated diene rubber solution thus obtained, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 2,4-bis [(octylthio) Methyl] -O-cresol was added in an amount of 0.3 parts by weight and 0.1 parts by weight per 100 parts by weight of the polymer, respectively, and the solvent was removed by steam stripping, followed by dehydration and subsequent drying with a hot roll (110 ° C.). 5% styrene solution viscosity (SV) shown in Table 1 is 28 mPa · s, Mooney viscosity (ML viscosity _{1 + 4} 100 ° C.) is 42, ML _{1 + 4} 100 ° C./SV is 1.50 conjugated diene rubber A polymer A was obtained.

[Production Example 3] (Conjugated Diene Rubber (Polymer C))
An autoclave (a tank with a stirrer) having an internal volume of 11 L, an internal height-to-diameter ratio (L / D) of 4, an inlet at the bottom, an outlet at the top, a stirrer and a temperature control jacket Two reactors were connected in series, and the first reactor was a polymerization reactor and the second reactor was a coupling reactor.
In advance, impurities such as moisture were removed, 1,3-butadiene was mixed at 42.2 g / min, 1,2-butadiene at 0.008 g / min, and n-hexane at 198.8 g / min. Was continuously fed to the bottom of the first reactor while adjusting the temperature to 15 ° C. Further, n-butyllithium as an organolithium compound initiator is supplied to the bottom of the first reactor at a rate of 1.2 mmol / min, and the polymerization reaction is continued so that the internal temperature of the reactor outlet becomes 100 ° C. I let you.
The temperature of the second reactor was kept at 100 ° C., and the conjugated diene rubber solution flowing out from the top of the first reactor was continuously supplied from the bottom, and tetramethoxysilane was further added as a coupling agent at 0.32 mmol / min. The coupling reaction was carried out at the rate added from the bottom of the second reactor. To the conjugated diene rubber solution flowing out from the top of the second reactor, 10.0 parts by weight of water per 100 parts by weight of the conjugated diene rubber is added, and then carbon dioxide is added in moles to the added n-butyllithium. The mixture was continuously added at a ratio of 1: 1.5, and stearic acid, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 2, 4-bis [(octylthio) methyl] -O-cresol was continuously added so as to be 0.035 g, 0.1 g, and 0.1 g, respectively, per 100 parts by mass of the conjugated diene rubber to complete the coupling reaction. I let you. The obtained conjugated diene rubber solution was subjected to steam stripping to remove the solvent, and after dehydration, it was subsequently dried by a hot roll (110 ° C.), and the 5% styrene solution viscosity (SV) shown in Table 1 was 33 mPa · s. A polymer C which is a conjugated diene rubber having a Mooney viscosity (ML _{1 + 4} 100 ° C.) of 40 and ML _{1 + 4} 100 ° C./SV of 1.21 was obtained.

[Production Example 4] (Conjugated Diene Rubber (Polymer D))
An autoclave (a tank with a stirrer) having an internal volume of 11 L, an internal height-to-diameter ratio (L / D) of 4, an inlet at the bottom, an outlet at the top, a stirrer and a temperature control jacket Two reactors were connected in series, and the first reactor was a polymerization reactor and the second reactor was a coupling reactor.
In advance, impurities such as moisture were removed, 1,3-butadiene was mixed at 42.2 g / min, 1,2-butadiene at 0.008 g / min, and n-hexane at 198.8 g / min. Was continuously fed to the bottom of the first reactor while adjusting the temperature to 15 ° C. Further, n-butyllithium as an organolithium compound initiator is supplied to the bottom of the first reactor at a rate of 1.2 mmol / min, and the polymerization reaction is continued so that the internal temperature of the reactor outlet becomes 100 ° C. I let you.
The temperature of the second reactor was kept at 100 ° C., and the conjugated diene rubber solution flowing out from the top of the first reactor was continuously supplied from the bottom, and further, silicon tetrachloride as a coupling agent was added at 0.24 mmol / min. The coupling reaction was carried out at the rate added from the bottom of the second reactor. To the conjugated diene rubber solution flowing out from the top of the second reactor, 10.0 parts by weight of water per 100 parts by weight of the conjugated diene rubber is added, and then carbon dioxide is added in moles to the added n-butyllithium. The mixture was continuously added at a ratio of 1: 1.5, and stearic acid, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 2, 4-Bis [(octylthio) methyl] -O-cresol was continuously added so as to be 0.035 parts by mass, 0.1 parts by mass, and 0.1 parts by mass, respectively, per 100 parts by mass of the conjugated diene rubber. The coupling reaction was terminated. The obtained conjugated diene rubber solution was subjected to steam stripping to remove the solvent, and after dehydration, it was subsequently dried by a hot roll (110 ° C.), and the 5% styrene solution viscosity (SV) shown in Table 1 was 37 mPa · s. Polymer D, which is a conjugated diene rubber having a Mooney viscosity (ML viscosity _{1 + 4 at} 100 ° C.) of 45 and ML _{1 + 4 at} 100 ° C./SV of 1.22, was obtained.

[Production Example 5] (Conjugated Diene Rubber (Polymer E))
An autoclave (a tank with a stirrer) having an internal volume of 11 L, an internal height-to-diameter ratio (L / D) of 4, an inlet at the bottom, an outlet at the top, a stirrer and a temperature control jacket 2 reactors were connected in series, the first reactor was a polymerization reactor, and the two reactors were polymerization reactors without any coupling reaction.
In advance, impurities such as moisture were removed, 1,3-butadiene was mixed at 42.2 g / min, 1,2-butadiene at 0.008 g / min, and n-hexane at 198.8 g / min. Was continuously fed to the bottom of the first reactor while adjusting the temperature to 15 ° C. Further, n-butyllithium as an organolithium compound initiator is supplied to the bottom of the first reactor at a rate of 0.389 mmol / min, and the polymerization reaction is continued so that the internal temperature at the reactor outlet becomes 100 ° C. I let you.
The temperature of the second reactor is kept at 100 ° C., the conjugated diene rubber solution flowing out from the top of the first reactor is continuously supplied from the bottom, and the conjugated diene rubber flowing out from the top of the second reactor as it is To the solution, 10.0 g of water is added per 100 g of conjugated diene rubber, and then carbon dioxide gas is continuously added at a molar ratio of 1: 1.5 with respect to the added n-butyllithium. Stearic acid, n-octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 2,4-bis [(octylthio) methyl] -O-cresol, conjugated diene system The coupling reaction was terminated by continuously adding 0.035 g, 0.1 g, and 0.1 g per 100 g of rubber. The resulting diene rubber solution was stripped of the solvent by steam stripping, dehydrated and subsequently dried by a hot roll (110 ° C.), and the 5% styrene solution viscosity (SV) shown in Table 1 was 120 mPa · s, Mooney viscosity. Polymer E, which is a conjugated diene rubber, having a (ML _{1 + 4} 100 ° C.) of 42 and a ML _{1 + 4} 100 ° C./SV of 0.35 was obtained.

[Production Example 6] (Conjugated Diene Rubber (Polymer F))
An autoclave (a tank with a stirrer) having an internal volume of 11 L, an internal height-to-diameter ratio (L / D) of 4, an inlet at the bottom, an outlet at the top, a stirrer and a temperature control jacket 2 reactors were connected in series, the first reactor was a polymerization reactor, and the two reactors were polymerization reactors without any coupling reaction.
In advance, impurities such as moisture were removed, 1,3-butadiene was mixed at 42.2 g / min, 1,2-butadiene at 0.008 g / min, and n-hexane at 198.8 g / min. Was continuously fed to the bottom of the first reactor while adjusting the temperature to 15 ° C. Furthermore, n-butyllithium as an organolithium compound initiator is supplied to the bottom of the first reactor at a rate of 0.480 mmol / min, and the polymerization reaction is continued so that the internal temperature at the reactor outlet becomes 100 ° C. I let you.
The temperature of the second reactor is kept at 100 ° C., the conjugated diene rubber solution flowing out from the top of the first reactor is continuously supplied from the bottom, and the conjugated diene rubber flowing out from the top of the second reactor as it is To the solution, 10.0 g of water is added per 100 g of conjugated diene rubber, and then carbon dioxide gas is continuously added at a molar ratio of 1: 1.5 with respect to the added n-butyllithium. Stearic acid, n-octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 2,4-bis [(octylthio) methyl] -O-cresol, conjugated diene system The coupling reaction was terminated by continuously adding 0.035 g, 0.1 g, and 0.1 g per 100 g of rubber. The obtained diene rubber solution was stripped of the solvent by steam stripping, dehydrated and then dried by a hot roll (110 ° C.), and the 5% styrene solution viscosity (SV) shown in Table 1 was 60 mPa · s, Mooney viscosity. A polymer F, which is a conjugated diene rubber having a (ML _{1 + 4} 100 ° C.) of 28 and an ML _{1 + 4} 100 ° C./SV of 0.47, was obtained.
The conjugated diene polymer F having a 5% styrene solution viscosity of less than 70 mPa · s has a cold flow change rate of more than 50% and is expected to change its shape after bale molding.

[Example 1]
A rubber-reinforced polystyrene resin was produced by the bulk polymerization method shown below.
4.275 parts by mass of Polymer A and 5.225 parts by mass of “Diene 35AE” (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd., 5% styrene solution viscosity (SV) is 85 mPa · s, Mooney viscosity (ML _{1 + 4} 100 ° C. ) Was 33 and ML _{1 + 4} 100 ° C./SV was 0.39) was dissolved in 90.5 parts by mass of styrene and 5 parts by mass of ethylbenzene, and polymerization was performed at 120 ° C. with stirring for 6 hours. Thereafter, polymerization was carried out at 135 ° C., 150 ° C., and 170 ° C. for 2 hours without stirring. Further, heat treatment was performed at 220 ° C. for 30 minutes, and after cooling, the mixture was pulverized with a pulverizer having a mesh size of 5 mmφ and dried under reduced pressure at 80 ° C. for 3 hours to obtain a rubber-reinforced polystyrene resin. This pulverized product was injection-molded (mold temperature 60 ° C., nozzle tip temperature 220 ° C.) to prepare a test piece, and the physical properties were measured. The results are shown in Table 2.

[Example 2]
2.4 parts by mass of Polymer A and 5.6 parts by mass of “Diene 35AE” (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd., 5% styrene solution viscosity (SV) is 85 mPa · s, Mooney viscosity (ML _{1 + 4} 100 ° C.) ) Was 33 and ML _{1 + 4} 100 ° C./SV was 0.39) was dissolved in 92 parts by mass of styrene and 5 parts by mass of ethylbenzene, and polymerization was carried out at 120 ° C. with stirring for 6 hours. Thereafter, polymerization was carried out at 135 ° C., 150 ° C., and 170 ° C. for 2 hours without stirring. Further, heat treatment was performed at 220 ° C. for 30 minutes, and after cooling, the mixture was pulverized with a pulverizer having a mesh size of 5 mmφ and dried under reduced pressure at 80 ° C. for 3 hours to obtain a rubber-reinforced polystyrene resin. This pulverized product was injection-molded (mold temperature 60 ° C., nozzle tip temperature 220 ° C.) to prepare a test piece, and the physical properties were measured. The results are shown in Table 2.

[Example 3]
4.0 parts by mass of Polymer B and 4.0 parts by mass of “Diene 35AE” (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd., 5% styrene solution viscosity (SV) is 85 mPa · s, Mooney viscosity (ML _{1 + 4} 100 ° C. ) Is 33, ML _{1 + 4} 100 ° C./SV is 0.39) is dissolved in 92 parts by mass of styrene and 5 parts by mass of ethylbenzene, and further 0.5 parts by mass of mineral oil is added to obtain 120 ° C. The polymerization was carried out with stirring for 6 hours. Thereafter, polymerization was carried out at 135 ° C., 150 ° C., and 170 ° C. for 2 hours without stirring. Further, heat treatment was performed at 220 ° C. for 30 minutes, and after cooling, the mixture was pulverized with a pulverizer having a mesh size of 5 mmφ and dried under reduced pressure at 80 ° C. for 3 hours to obtain a rubber-reinforced polystyrene resin. This pulverized product was injection-molded (mold temperature 60 ° C., nozzle tip temperature 220 ° C.) to prepare a test piece, and the physical properties were measured. The results are shown in Table 2.

[Example 4]
2.4 parts by mass of Polymer C and 5.6 parts by mass of “Diene 35AE” (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd., 5% styrene solution viscosity (SV) is 85 mPa · s, Mooney viscosity (ML _{1 + 4} 100 ° C.) ) Was 33 and ML _{1 + 4} 100 ° C./SV was 0.39) was dissolved in 92 parts by mass of styrene and 5 parts by mass of ethylbenzene, and polymerization was carried out at 120 ° C. with stirring for 6 hours. Thereafter, polymerization was carried out at 135 ° C., 150 ° C., and 170 ° C. for 2 hours without stirring. Further, heat treatment was performed at 220 ° C. for 30 minutes, and after cooling, the mixture was pulverized with a pulverizer having a mesh size of 5 mmφ and dried under reduced pressure at 80 ° C. for 3 hours to obtain a rubber-reinforced polystyrene resin. This pulverized product was injection-molded (mold temperature 60 ° C., nozzle tip temperature 220 ° C.) to prepare a test piece, and the physical properties were measured. The results are shown in Table 2.

[Example 5]
0.9 parts by mass of Polymer C and 5.1 parts by mass of “Diene 35AE” (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd., 5% styrene solution viscosity (SV) is 85 mPa · s, Mooney viscosity (ML _{1 + 4} 100 ° C.) ) Was 33, and ML _{1 + 4} 100 ° C./SV was 0.39) was dissolved in 94 parts by mass of styrene and 5 parts by mass of ethylbenzene, and polymerization was carried out at 120 ° C. with stirring for 6 hours. Thereafter, polymerization was carried out at 135 ° C., 150 ° C., and 170 ° C. for 2 hours without stirring. Further, heat treatment was performed at 220 ° C. for 30 minutes, and after cooling, the mixture was pulverized with a pulverizer having a mesh size of 5 mmφ and dried under reduced pressure at 80 ° C. for 3 hours to obtain a rubber-reinforced polystyrene resin. This pulverized product was injection-molded (mold temperature 60 ° C., nozzle tip temperature 220 ° C.) to prepare a test piece, and the physical properties were measured. The results are shown in Table 2.

[Example 6]
4.0 parts by mass of the polymer C and 4.0 parts by mass of the polymer E were dissolved in 92 parts by mass of styrene and 5 parts by mass of ethylbenzene, and polymerization was performed at 120 ° C. with stirring for 6 hours. Thereafter, polymerization was carried out at 135 ° C., 150 ° C., and 170 ° C. for 2 hours without stirring. Further, heat treatment was performed at 220 ° C. for 30 minutes, and after cooling, the mixture was pulverized with a pulverizer having a mesh size of 5 mmφ and dried under reduced pressure at 80 ° C. for 3 hours to obtain a rubber-reinforced polystyrene resin. This pulverized product was injection-molded (mold temperature 60 ° C., nozzle tip temperature 220 ° C.) to prepare a test piece, and the physical properties were measured. The results are shown in Table 2.

[Example 7]
2.4 parts by mass of the polymer C and 5.6 parts by mass of the polymer F were dissolved in 92 parts by mass of styrene and 5 parts by mass of ethylbenzene, and polymerization was performed at 120 ° C. with stirring for 6 hours. Thereafter, polymerization was carried out at 135 ° C., 150 ° C., and 170 ° C. for 2 hours without stirring. Further, heat treatment was performed at 220 ° C. for 30 minutes, and after cooling, the mixture was pulverized with a pulverizer having a mesh size of 5 mmφ and dried under reduced pressure at 80 ° C. for 3 hours to obtain a rubber-reinforced polystyrene resin. This pulverized product was injection-molded (mold temperature 60 ° C., nozzle tip temperature 220 ° C.) to prepare a test piece, and the physical properties were measured. The results are shown in Table 2.
As in Example 2 and Example 4, the ratio of the conjugated diene polymer F was set to 70 wt% instead of “diene 35AE”, but the 5% SV of the conjugated diene polymer F was 60 mPa · s. The gel amount tends to decrease, and Izod also becomes lower. Therefore, it is preferable that the SV of (b) is ≧ 70 because the gel amount and Izod are further improved.

[Comparative Example 1]
8.0 parts by mass of the polymer C was dissolved in 92 parts by mass of styrene and 5 parts by mass of ethylbenzene, and polymerization was performed at 120 ° C. with stirring for 6 hours. Thereafter, polymerization was carried out at 135 ° C., 150 ° C., and 170 ° C. for 2 hours without stirring. Further, heat treatment was performed at 220 ° C. for 30 minutes, and after cooling, the mixture was pulverized with a pulverizer having a mesh size of 5 mmφ and dried under reduced pressure at 80 ° C. for 3 hours to obtain a rubber-reinforced polystyrene resin. This pulverized product was injection-molded (mold temperature 60 ° C., nozzle tip temperature 220 ° C.) to prepare a test piece, and the physical properties were measured. The results are shown in Table 2.
Since only conjugated diene rubber (Polymer C) having a low SV of 33 mPa · s with 5 wt% SV is used, the gel particle size is small and high gloss is obtained, but it also contains a conjugated diene rubber with high SV. Compared to Examples 4 to 7, the rubber component with less polystyrene inclusion is formed into dense particles, the gel amount is as low as 12.3 wt%, and the impact strength Izod is low as compared with Examples 4-7.

[Comparative Example 2]
5.6 parts by mass of polymer C and 2.4 parts by mass of “diene 35AE” (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd., 5% styrene solution viscosity (SV) is 85 mPa · s, Mooney viscosity (ML _{1 + 4} 100 ° C. ) Was 33 and ML _{1 + 4} 100 ° C./SV was 0.39) was dissolved in 92 parts by mass of styrene and 5 parts by mass of ethylbenzene, and polymerization was performed at 120 ° C. with stirring for 6 hours. Thereafter, polymerization was carried out at 135 ° C., 150 ° C., and 170 ° C. for 2 hours without stirring. Further, heat treatment was performed at 220 ° C. for 30 minutes, and after cooling, the mixture was pulverized with a pulverizer having a mesh size of 5 mmφ and dried under reduced pressure at 80 ° C. for 3 hours to obtain a rubber-reinforced polystyrene resin. This pulverized product was injection-molded (mold temperature 60 ° C., nozzle tip temperature 220 ° C.) to prepare a test piece, and the physical properties were measured. The results are shown in Table 2.
Since Comparative Example 2 is a blend of 70% by mass of conjugated diene polymer C and 30% by mass of “diene 35AE”, it is a little improved as compared with Comparative Example 1, but the ratio of polymer C is high. Furthermore, the gel amount is as low as 15.8 wt% and the Izod is low.

[Comparative Example 3]
2.4 parts by mass of polymer D and 5.6 parts by mass of “diene 35AE” (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd., 5% styrene solution viscosity (SV) is 85 mPa · s, Mooney viscosity (ML _{1 + 4} 100 ° C.) ) Was 33 and ML _{1 + 4} 100 ° C./SV was 0.39) was dissolved in 92 parts by mass of styrene and 5 parts by mass of ethylbenzene, and polymerization was performed at 120 ° C. with stirring for 6 hours. Thereafter, polymerization was carried out at 135 ° C., 150 ° C., and 170 ° C. for 2 hours without stirring. Further, heat treatment was performed at 220 ° C. for 30 minutes, and after cooling, the mixture was pulverized with a pulverizer having a mesh size of 5 mmφ and dried under reduced pressure at 80 ° C. for 3 hours to obtain a rubber-reinforced polystyrene resin. This pulverized product was injection-molded (mold temperature 60 ° C., nozzle tip temperature 220 ° C.) to prepare a test piece, and the physical properties were measured. The results are shown in Table 2.
The polymer D is a conjugated diene rubber containing halogen, and the gel particle size is increased and the gloss is inferior compared to Examples 2 and 4 using a conjugated diene rubber not containing halogen.

[Comparative Example 4]
8.0 parts by weight of “diene 35AE” (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd., 5% styrene solution viscosity (SV) is 85 mPa · s, Mooney viscosity (ML _{1 + 4} 100 ° C.) is 33, ML _{1 + 4} 100 ° C. / SV is 0.39) was dissolved in 92 parts by mass of styrene and 5 parts by mass of ethylbenzene, and polymerization was performed at 120 ° C. with stirring for 6 hours. Thereafter, polymerization was carried out at 135 ° C., 150 ° C., and 170 ° C. for 2 hours without stirring. Further, heat treatment was performed at 220 ° C. for 30 minutes, and after cooling, the mixture was pulverized with a pulverizer having a mesh size of 5 mmφ and dried under reduced pressure at 80 ° C. for 3 hours to obtain a rubber-reinforced polystyrene resin. This pulverized product was injection-molded (mold temperature 60 ° C., nozzle tip temperature 220 ° C.) to prepare a test piece, and the physical properties were measured. The results are shown in Table 2.
Only “Diene 35AE”, which is a conjugated diene rubber having a 5% SV of 85 mPa · s, has a gel particle diameter of 2.2 μm under the same bulk polymerization conditions as in the examples, and is inferior in gloss.

  The rubber-reinforced styrene-based resin composition obtained using the rubber composition of the present invention does not contain halogen as compared with conventional impact-resistant styrene-based resins. Improves the problem of corrosion and the difficulty of controlling the rubber particle size by affecting the grafting properties during production (reaction), and has excellent balance between gloss and impact resistance. Equipment, air conditioners, refrigerators and other household electrical appliances, OA office equipment and other general equipment, stationery, toys, leisure sports equipment, household goods, building materials / housing parts, food containers, etc. Yes and useful.

Claims (5)

As the component (a), the 5% by mass styrene solution viscosity (SV) is 20 to 55 mPa · s, and the ratio of the Mooney viscosity (ML _{1 + 4} 100 ° C.) to the 5% by mass styrene solution viscosity (SV) (ML _{1+ 4} conjugated diene rubber having 100 ° C / SV) of 0.8 to 1.8;
As the component (b), the 5 mass% styrene solution viscosity (SV) is 70 to 150 mPa · s, and the ratio between the Mooney viscosity (ML _{1 + 4} 100 ° C.) and the 5 mass% styrene solution viscosity (SV) (ML _{1+ 4} conjugated diene rubber having 100 ° C / SV) of 0.3 to 0.6,
A rubber composition comprising:
10 to 55 parts by mass of the component (a), 90 to 45 parts by mass of the component (b), and 10 halogens to 100 parts by mass of the total content of the component (a) and the component (b). A rubber composition for reinforcing a styrene-based resin, which is × 10 ⁻⁴ parts by mass or less. The rubber composition for reinforcing a styrene-based resin according to claim 1, wherein the mixture of the component (a) and the component (b) has a 5% by mass styrene solution viscosity (SV) of 40 to 70 mPa · s. The rubber composition for styrene resin reinforcement according to claim 1 or 2 , wherein the component (a) is a conjugated diene rubber polymerized with an alkyllithium initiator and coupled with an alkoxysilyl compound. A rubber-reinforced styrene-based resin composition using the rubber composition according to any one of claims 1 to 3 . A matrix made of a styrenic polymer;
As component (a), the 5% by mass styrene solution viscosity (SV) dispersed in the matrix is 20 to 55 mPa · s, and the Mooney viscosity (ML _{1 + 4} 100 ° C.) and 5% by mass styrene solution viscosity (SV) ) Conjugated diene rubber having a ratio (ML _{1 + 4} 100 ° C./SV) of 0.8 to 1.8;
As component (b), the 5% by mass styrene solution viscosity (SV) dispersed in the matrix is 70 to 150 mPa · s, and the Mooney viscosity (ML _{1 + 4} 100 ° C.) and 5% by mass styrene solution viscosity (SV). ) Conjugated diene rubber having a ratio (ML _{1 + 4} 100 ° C./SV) of 0.3 to 0.6;
10 to 55 parts by mass of the component (a) and 90 to 45 parts by mass of the component (b) with respect to 100 parts by mass of the total content of the component (a) and the component (b). A rubber-reinforced styrene-based resin composition having a halogen content of 10 × 10 ⁻⁴ parts by mass or less.