JPH11228742A - Conjugated diene rubber composition, method for producing the same, resin modifier, and resin composition - Google Patents

Abstract

(57) [Problem] To provide a conjugated diene-based rubber composition having a low gel content and being less likely to generate fish eyes in a sheet of the obtained resin composition when blended with a resin as a resin modifier. SOLUTION: In the presence of (A) (a) an organic active metal compound (for example, n-butyllithium) and (b) a specific allene compound (for example, 1,2-butadiene), a hydrocarbon solvent (for example, , Cyclohexane, etc.) and 100 parts by weight of a conjugated diene rubber obtained by continuous polymerization of a conjugated diene compound (eg, 1,3-butadiene) and (B) a sulfur-containing phenolic stabilizer (eg, 2,4- A conjugated diene rubber composition comprising 0.01 to 5.0 parts by weight of bis (n-octylthiomethyl) -6-methylphenol or the like is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a conjugated diene rubber composition which is improved in heat resistance and gelation prevention by being blended with a resin, a method for producing the composition, and a resin modification comprising the composition. And a resin composition containing the composition.

[0002]

2. Description of the Related Art Impact resistant polystyrene resin (HIP)
S) is generally produced by bulk polymerization, solution polymerization, or bulk suspension polymerization of a styrene monomer in the presence of various unvulcanized rubbers, and rubber particles are contained in a polystyrene resin matrix. By having a dispersed structure, the impact resistance of a hard and brittle polystyrene resin is significantly improved. Impact-resistant polystyrene resins have been used in a wide range of applications because they are inexpensive and have excellent processability and various physical properties.

[0003] However, in recent years, as the amount of food packaging materials used has increased and the applications have been diversified, there has been an increasing demand for reducing the amount of gel in impact-resistant polystyrene resins. If the gel is contained in the resin, it may cause pinholes in the film-shaped molded article or transfer failure during printing.

[0004] As rubber particles used in HIPS, conjugated diene rubbers are generally used. Methods for producing conjugated diene rubbers include a batch polymerization method and a continuous polymerization method. A conjugated diene rubber produced by a continuous polymerization method generally has more gel than a rubber produced by a batch polymerization method. However, a continuous polymerization method is preferred because of excellent production efficiency and quality stability. Therefore, 1,2-
Although gelation is prevented by polymerization in the presence of butadiene, there is a problem that the amount of gel is too large for HIPS applications.

[0005] In order to prevent gelation, it has been proposed to polymerize a conjugated diene rubber in the presence of a gel inhibitor containing an allene compound and an ether or amine compound (Japanese Patent Publication No. 1-47488, etc.). ). This method has the effect of suppressing the formation of a gel polymer during polymerization. However, higher quality is required, and a conjugated diene rubber having a lower gel amount is required.

[0006] Recently, sulfur-containing phenolic antioxidants having a high degree of heat degradation resistance have begun to be used, and low-cis polybutadiene rubber to which a sulfur-containing phenolic antioxidant, a monophenol having a molecular weight of 250 or less and an organic acid are added, has been developed. It has been proposed to disperse the resin in a resin (Japanese Patent Application Laid-Open No. 9-131334). It is known that this low cis polybutadiene rubber is excellent in heat deterioration resistance, but the effect of preventing gelation of an impact-resistant polystyrene resin containing the same is not sufficient.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a conjugated diene-based rubber composition which has a low gel content per se and does not easily generate fish eyes in a resin sheet when blended with a resin. A method for producing a rubber composition, a resin modifier containing the conjugated diene rubber composition as an active ingredient,
And a resin composition containing the same.

As a result of intensive studies, the present inventors have found that the above object can be achieved by blending a specific sulfur-containing phenolic stabilizer with a specific low cis-conjugated diene rubber.

[0009]

Thus, according to the present invention, (A) (a) an organic active metal compound and (b) a compound of the general formula (1)

Embedded image (R in the formula represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) A conjugated diene rubber obtained by continuously polymerizing a conjugated diene compound in a hydrocarbon solvent in the presence of an allene compound represented by the formula: 100 parts by weight and (B) general formula 2

Embedded image (Wherein, R ¹ and R ³ represent —CH ₂ —S—R ⁵ , R ⁵ represents an alkyl group having 20 or less carbon atoms, and R ² and R ⁴ represent a hydrogen atom or an alkyl having 15 or less carbon atoms. A conjugated diene rubber composition comprising 0.01 to 5.0 parts by weight of a sulfur-containing phenolic stabilizer represented by the following formula:

Further, according to the present invention, (1) (a) an organic active metal compound and (b)

Embedded image (R in the formula represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) in the presence of an allene compound represented by the following formula: (2) a step of continuously polymerizing a conjugated diene compound in a hydrocarbon solvent;
Stopping the polymerization reaction of the conjugated diene polymerization reaction solution obtained by the continuous polymerization; (3) per 100 parts by weight of the conjugated diene rubber contained in the stopped polymerization reaction solution, the general formula 2

Embedded image (Wherein, R ¹ and R ³ represent —CH ₂ —S—R ⁵ , R ⁵ represents an alkyl group having 20 or less carbon atoms, and R ² and R ⁴ represent a hydrogen atom or an alkyl having 15 or less carbon atoms. A sulfur-containing phenol-based stabilizer represented by the following formula: (4) a conjugated diene-based rubber containing a sulfur-containing phenol-based stabilizer by steam stripping. And (5) a method for producing the conjugated diene rubber composition, which comprises a drying step.

Further, according to the present invention, there are provided a resin modifier containing the conjugated diene rubber and a resin composition containing the conjugated diene rubber.

(Conjugated diene-based rubber composition) The conjugated diene-based rubber composition of the present invention is prepared by using (A) (a) an organic active metal compound and (b) an allene compound represented by the general formula (1).
100 parts by weight of a conjugated diene-based rubber obtained by continuously polymerizing a conjugated diene compound in a hydrocarbon solvent, and (B) a sulfur-containing phenol-based stabilizer represented by the following general formula (2): 0.01 to 5.
It is a conjugated diene rubber composition comprising 0 parts by weight.

(A) The conjugated diene rubber composition of the present invention
The conjugated diene rubber as a component is a conjugate obtained by continuously polymerizing a conjugated diene compound in a hydrocarbon solvent in the presence of (a) an organic active metal compound and (b) an allene compound represented by the general formula 1. It is a diene rubber.

There are no particular restrictions on the conjugated diene compound. For example, 1,3-butadiene, 2-methyl-1,
Examples thereof include 3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, and 1,3-pentadiene. Among these, 1,3-butadiene and 2-methyl-1,3-butadiene are preferable,
In particular, 1,3-butadiene is preferred. These conjugated diene compounds can be used alone or in combination of two or more.

In addition, a copolymerizable monomer may be copolymerized as long as the objects and effects of the present invention are not impaired. Examples of such a monomer include styrene, o-methylstyrene and p-methylstyrene. Methylstyrene, m-methylstyrene, 2,4
-Dimethylstyrene, ethylstyrene, p-tert-
Butylstyrene, α-methylstyrene, α-methyl-p
-Methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene,
-Methyl-1,4-dichlorostyrene, 2,4-dibromostyrene, vinylnaphthalene, and other aromatic vinyl monomers, dicyclopentadiene, 5-ethylidene-2
-Norbornene, 1,5-hexadiene and the like. When these are copolymerized, they may be used alone or in combination of two or more.

Usually, 50% by weight or more, preferably 7% by weight, of monomer units derived from a conjugated diene compound (hereinafter referred to as conjugated diene bonding units) out of all the monomer units of the conjugated diene rubber.
It is at least 0% by weight, more preferably at least 90% by weight.
Most preferred is a conjugated diene rubber obtained by polymerizing only a conjugated diene compound.

Although the molecular weight of the conjugated diene rubber used in the present invention is not particularly limited, it is usually 10,000 to 3,000.
0000, preferably 50,000 to 2,000,000.
00, most preferably 100,000-1,000,000.
00 range. If the molecular weight is excessively small, it becomes a liquid rubber and handling becomes difficult, so that it may be difficult to use it as a resin modifier. Conversely, if the molecular weight is excessively large, the viscosity of the rubber solution at the time of production increases, which is a problem in the production process.

The molecular weight distribution of the conjugated diene rubber is not particularly limited, but is usually 5.0 or less, preferably 4.0 or less, and most preferably 3.0 or less. If the molecular weight distribution is excessively large, the gloss of the resin when used as a resin modifier decreases.

The vinyl bond (1,2-vinyl bond and 3,4 vinyl bond) content of the conjugated diene-bonded unit in the conjugated diene rubber is 5 to 80% by weight of the total amount of the conjugated diene-bonded unit.
Is preferably, more preferably 7 to 50% by weight, and 10 to 4% by weight.
0% by weight is particularly preferred. If the vinyl bond content is too low, production is difficult, and if it is too high, the low-temperature impact strength deteriorates.

The 1,4-cis bond content of the conjugated diene-bonded unit in the conjugated diene-based rubber is not particularly limited, but is 50% by weight or less of the total amount of the conjugated diene-bonded unit because of easy production. Is at most 45% by weight, most preferably at most 40% by weight.

(Method for Producing Conjugated Diene Rubber) The (A) conjugated diene rubber used in the present invention is prepared by carbonizing in the presence of (a) an organic active metal compound and (b) an allene compound represented by the general formula 1. It is obtained by continuous polymerization of a conjugated diene compound in a hydrogen solvent.

The (a) organic active metal compound used in the present invention is exemplified by an organic alkali metal compound, an organic alkaline earth metal compound, an organic lanthanoid-based rare earth metal compound and the like.

Examples of the organic alkali metal compound include n-butyllithium, sec-butyllithium, t-butyllithium, and t-butyllithium.
Monoorganic lithium compounds such as -butyllithium, hexyllithium, phenyllithium, stilbenelithium, dilithiomethane, 1,4-dilithiobutane, 1,4
-Dilithio-2-ethylcyclohexane, 1,3,5-
Organic lithium compounds such as polyfunctional organic lithium compounds such as trilithiobenzene; organic naphthalene compounds such as sodium naphthalene; organic potassium compounds such as potassium naphthalene;

Examples of the organic alkaline earth metal compound include n-butylmagnesium bromide, n-hexylmagnesium bromide, ethoxy calcium, calcium stearate, t-butoxystrontium, ethoxy barium, isopropoxy barium, ethyl mercapto barium, t-butyl magnesium Butoxybarium, phenoxybarium, diethylaminobarium, barium stearate,
Ethyl barium and the like.

Examples of the organic lanthanoid-based rare earth metal compound include, for example, a composite catalyst composed of neodymium versatate / triethylaluminum hydride / ethylaluminum sesquichloride as described in JP-B-63-64444.

Among these organic active metal compounds, organolithium compounds are preferred, and monoorganic lithium compounds are particularly preferred.

The organic active metal compounds are each independently
Alternatively, two or more kinds can be used in combination.
The amount of the organic active metal compound used is usually 0.01 to 20 mmol, preferably 0.05 to 100 g per 100 g of all monomers.
-15 mmol, more preferably 0.1-10 mmol. Depending on the amount used, the molecular weight of the conjugated diene rubber, the solution viscosity of the conjugated diene rubber used as a resin modifier, and the like are adjusted.

The allene compound (b) used in the present invention has the general formula 1

Embedded image It is a compound represented by these. R in the formula represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a butyl group. Specific examples of the (b) allene compound used in the present invention include 1,2-propadiene, 1,2-butadiene, 1,2-pentadiene, 1,2-hexadiene,
1,2-heptadiene, 1,2-octadiene, 1,2
-Nonadiene, 1,2-decadiene and the like, among which 1,2-butadiene, 1,2-propadiene,
1,2-pentadiene and 1,2-hexadiene are preferred. The amount of the allene compound to be used is generally 0.01 to 50 mol, preferably 0.1 to 50 mol, per 1 mol of the organic active metal compound.
It is 20 mol, more preferably 0.3 to 10 mol. If the addition amount of the allene compound is too small, the gel amount in the rubber tends to increase, and if it is too large, the polymerization conversion rate decreases, so that the production efficiency tends to decrease and the molecular weight hardly increases.

The hydrocarbon solvent used in the present invention includes:
(A) No particular limitation is imposed as long as it dissolves the conjugated diene rubber and does not adversely affect the activity of the polymerization catalyst. For example, aromatic hydrocarbons such as benzene, toluene, and xylene; cyclohexane, methylcyclohexane Cycloaliphatic hydrocarbons such as cyclopentane; n-butane;
saturated aliphatic hydrides such as n-hexane and n-heptane; aliphatic unsaturated hydrocarbons such as cis-2-butene, trans-2-butene and butene-1; These inert organic solvents are used alone or in combination of two or more. The amount of the polymerization solvent used is such that the monomer concentration is usually 5 to 70% by weight, preferably 10 to 60% by weight, more preferably 20 to 50% by weight.
It may be adjusted so that If the amount of the polymerization solvent is too large or too small, productivity becomes a problem.

In the polymerization of the conjugated diene rubber used in the present invention, a polar compound such as a Lewis base and a branching agent can be added as needed during the polymerization reaction.

Examples of the polar compound include water and a Lewis base, among which a Lewis base is preferable. Examples of the Lewis base include ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether; tetramethylethylenediamine, trimethylamine, triethylamine,
Compounds such as tertiary amines such as pyridine and quinuclidine; alkali metal alkoxides such as potassium-t-amyl oxide and potassium-t-butyl oxide; phosphines such as triphenylphosphine; These Lewis bases are used alone or in combination of two or more, and are appropriately selected within a range not to impair the object of the present invention.

The branching agent is a compound selected from a polyvinyl aromatic compound and a tri- or higher functional polyhalogen compound.

Examples of the polyvinyl aromatic compound include divinylbenzene, trivinylbenzene, tetravinylbenzene, divinylxylene, trivinylxylene, divinyltoluene, diisopropenylbenzene, and divinylnaphthalene, and divinylbenzene is preferred. Since the polyvinyl aromatic compound does not hinder the catalytic action of the organic active metal compound, it may be added to the polymerization system from the beginning, or may be added after the progress or completion of the polymerization. It is preferable to do so because a small amount of addition is effective. The addition amount is usually from 0.02 to 30 mol, preferably from 0.05 to 5 mol, per 1 mol of the organic active metal compound, though it depends on the polymerization temperature and the degree of improvement of the cold flow property. If the amount is too large, a gel polymer tends to be formed, and if the amount is too small, the degree of improvement in cold flow properties tends to be low.

Examples of the trifunctional or higher polyhalogen compound include tetrahalides such as silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, carbon tetrachloride and tin tetrachloride;
Ethyl silicon trichloride, tribromobenzylsilane,
Trihalides such as 1,3,5-tri (bromomethyl) benzenetin; and the like, but tetrahalides, particularly silicon tetrachloride and tin tetrachloride are preferable. The polyhalogen compound is used in an amount of usually 0.1 to 1.0 equivalent, preferably 0.3 to 1.0 equivalent, of the terminal active organic metal of the polymer. If the addition amount is too small, the degree of improvement in cold flow property tends to be low, and if added in an amount of 1.0 equivalent or more, a polymer having an unreacted functional group at the terminal is obtained. It is necessary to stabilize, and the process is likely to be complicated. This polyhalogen compound can be added during or after the completion of the polymerization reaction.However, if added during the progress of the polymerization reaction, a partial deactivation reaction of the active terminal occurs. Is preferred.

(A) The conjugated diene rubber is produced by a continuous polymerization method. Average residence time is usually 0.1 to 10 hours, preferably 0.5 to 5 hours, more preferably 1 to 3 hours.
Time. If the average residence time is too short or too long, the productivity tends to decrease. The polymerization temperature is usually -10 to +1
The temperature is 50 ° C, preferably +20 to + 120 ° C. The polymerization pressure is usually 0 to 5 atm (gauge pressure). When such average residence time, polymerization temperature and polymerization pressure are adjusted, the polymerization conversion rate of the continuously withdrawn polymerization reaction liquid is usually 60 to 1
00% by weight, preferably 80 to 100% by weight, more preferably 90 to 100% by weight.

The conjugated diene rubber (A) thus obtained has the above-mentioned molecular weight and 1,4-cis bond content. (A) used in the conjugated diene rubber composition of the present invention
The method for recovering the conjugated diene rubber from the polymerization reaction solution is not particularly limited. For example, the solvent may be removed by steam stripping to coagulate to remove water.

The (B) sulfur-containing phenolic stabilizer used in the present invention is represented by the general formula 2

Embedded image An anti-aging agent represented by R ² and R ⁴ in the formula are a hydrogen atom or an alkyl group having 15 or less carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, se
c-butyl group, ter-butyl group, n-pentyl group, n
-Hexyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, 1,1,3,3-tetramethyloctyl group, 2-ethylhexyl Group, 1,1,3,3,5,5-
Hexamethylhexyl group, 1,1,5,5,9,9-hexamethyldecyl group, n-hexadecyl group, n-octadecyl group and the like are preferable, and n-dodecyl group is preferable.
It is an n-tridecyl group or an n-tetradecyl group.

R ¹ and R ³ in the formula are groups represented by —CH ₂ —S—R ⁵ . R ⁵ represents an alkyl group having 20 or less carbon atoms. Examples of such an alkyl group include the alkyl groups exemplified as examples of R ² and R ⁴ , n-octadecyl group and n
And a nonadecyl group.

Examples of the sulfur-containing phenolic stabilizer include:
Specifically, 2,4-bis (n-octylthiomethyl)
-6-methylphenol, 2,4-bis (1,1,3,
3-tetramethylbutylthiomethyl) -6-methylphenol, 2,4-bis (1,1,3,3,5,5-hexamethylhexylthiomethyl) -6-methylphenol, 2,4-bis [ 1,1,4,6,6-pentamethylhepty- (4) -ylthiomethyl] -6-methylphenol, 2,4-bis (n-octylthiomethyl) -6
2-alkylthiomethyl-4-alkylthiomethyl-6-alkylphenols such as ter-butyl-phenol and 2,4-bis (n-dodecylthiomethyl) -6-ter-butyl-phenol; 2,4-bis (2 '-
Ethylhexylthiomethyl) -3-methyl-6-ter
-Butylphenol, 2,4-bis (n-octylthiomethyl) -3,6-dimethylphenol, 2,4-bis (n-octylthiomethyl) -3-methyl-6-ter
2-alkylthiomethyl-3-methyl-4-alkylthiomethyl-6-alkylphenols such as -butylphenol, 2,4-bis (n-dodecylthiomethyl) -3-methyl-6-tert-butylphenol; Particularly preferred is 2,4-bis (n-octylthiomethyl) -6-methylphenol. This compound is commercially available (Irganox 1520, manufactured by Ciba-Geigy).

The conjugated diene rubber composition of the present invention
(A) Conjugated diene rubber 1 obtained by continuously polymerizing a conjugated diene compound in a hydrocarbon solvent in the presence of (a) an organic active metal compound and (b) an allene compound represented by the general formula 1.
(B) 0.01 to 5 parts by weight of the sulfur-containing phenol-based stabilizer represented by the general formula 1 with respect to 00 parts by weight.
Preferably 0.03 to 2 parts by weight, more preferably 0.03 parts by weight.
It contains 5 to 1 parts by weight.

The conjugated diene rubber composition of the present invention may further contain, if necessary, a compounding agent usually used in the resin industry. Examples of such compounding agents include rubbers, antioxidants other than sulfur-containing phenolic stabilizers, mineral oils, liquid paraffin, organic polysiloxanes, organic or inorganic fillers, stabilizers, plasticizers, lubricants, and ultraviolet rays. Absorbent, dye, pigment, release agent, antistatic agent,
And flame retardants. These compounding agents can be used alone or in combination of two or more, and the amount used is appropriately selected within a range not to impair the purpose of the present invention.

The rubber as a compounding agent does not satisfy the condition of (A) the conjugated diene rubber used in the present invention and includes, for example, (A) a low cis conjugated diene rubber other than the conjugated diene rubber; Those commonly used as toughening agents for resins, such as high cis polybutadiene rubber, styrene-butadiene block copolymer rubber, styrene-butadiene random copolymer rubber, polyisoprene rubber, and natural rubber, may be mentioned. These other rubbers can be used alone or in combination of two or more.
The amount used is usually 40% by weight or less, preferably 20% by weight, based on the total rubber components contained in the conjugated diene rubber composition.
%, More preferably 10% by weight or less.

Examples of the antioxidants other than the sulfur-containing phenol stabilizer include phenol stabilizers and phosphorus stabilizers.

The phenolic stabilizer is disclosed in JP-A-4-252.
243 and the like. Examples of the phenolic stabilizer other than the sulfur-containing phenolic stabilizer include, for example, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6 -Di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-
iso-butylphenol, 2-tert-butyl-
4,6-dimethylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-
4-methoxyphenol, 2,6-di-phenol-4
-Octadecyloxyphenol, n-octadecyl-
3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis- [methylene-3- (3', 5'-di-tert-butyl-4'-)
(Hydroxy-phenyl) propionate] -methane,
1,3,5-trimethyl-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) benzene and the like.

Phosphorus stabilizers are also known, for example, tris (nonylphenyl) phosphite, cyclic neopentanetetraylbis (octadecylphosphite), tris (2,4-di-tert-butylphenyl) Phosphite is exemplified.

In the present invention, the antioxidant does not necessarily have to be one kind, and a plurality of kinds may be used in combination.

Examples of the organic or inorganic filler include fibrous or granular fillers such as silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, and the like. Dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, curk, clay, mica, asbestos, glass fiber, glass flake, glass beads,
Calcium silicate, montmorillonite, bentonite,
Examples thereof include graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, and polyamide fiber.

There is no particular limitation on the flame retardant, and a halogen-based flame retardant is usually used. As the halogen-based flame retardant, various chlorine-based and bromine-based flame retardants can be used, but the flame retardant effect, heat resistance during molding, dispersibility in resin,
A brominated flame retardant is preferred from the viewpoint of affecting the physical properties of the resin. Examples of brominated flame retardants include, for example, hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, decabromodiphenyl, hexabromodiphenyl oxide, octabromodiphenyl oxide, decabromodiphenyl oxide, pentabromocyclohexane, tetrabromobisphenol A and the like. Derivatives [for example, tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A -Bis (allyl ether)], tetrabromobisphenol S and derivatives thereof [for example, tetrabromobisphenol S
-Bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2,3-dibromopropyl ether), etc.], tetrabromophthalic anhydride and its derivatives [eg, tetrabromophthalimide, ethylenebistetrabromophthalimide, etc.], ethylenebis (5,6-dibromonorbornene-2,3-dicarboximide), tris- (2,3-dibromopropyl-)
1) -Isocyanurate, adduct of Diels-Alder reaction of hexachlorocyclopentadiene, tribromophenyl glycidyl ether, tribromophenyl acrylate, ethylenebistribromophenyl ether,
Ethylene bispentabromophenyl ether, tetradecabromodiphenoxybenzene, brominated polystyrene,
Brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate, polypentabromobenzyl acrylate, octabromonaphthalene, hexabromocyclododecane, bis (tribromophenyl) fumaramide, N-methylhexabromodiphenylamine and the like can be mentioned.

The amount of the flame retardant to be added is usually 3 to 150 parts by weight, preferably 10 to 140 parts by weight, more preferably 15 to 12 parts by weight, per 100 parts by weight of the conjugated diene rubber (A).
0 parts by weight.

As a flame retardant aid for more effectively exhibiting the flame retardant effect of the flame retardant, for example, antimony trioxide,
Antimony-based flame retardants such as antimony pentoxide, sodium antimonate and antimony trichloride can be used. These flame retardant aids are used in a proportion of usually 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the flame retardant.

The mixing of these compounding agents and (A) the conjugated diene rubber is performed by adding the compounding agent to the polymerization reaction solution of the (A) conjugated diene rubber, and then mixing the rubber composition as a conjugated diene rubber. Coagulation and recovery may be performed using a single-screw or twin-screw extruder, various kneading devices such as a Banbury mixer, a roll, or a kneader, and may be compounded by a method suitable for each compounding agent. .

(Production Method of Conjugated Diene Rubber Composition) The production method of the conjugated diene rubber composition of the present invention is not limited in terms of the properties of the composition, but from the viewpoint of production efficiency,
From the viewpoint of preventing the deterioration of the conjugated diene rubber, (1)
(A) a step of continuously polymerizing a conjugated diene compound in a hydrocarbon solvent in the presence of an organic active metal compound and (b) an allene compound represented by the general formula 1, and (2) a conjugated diene polymerization obtained by continuous polymerization. Stopping the polymerization reaction of the reaction solution,
(3) a step of adding 0.01 to 5.0 parts by weight of a sulfur-containing phenolic stabilizer represented by the general formula 2 per 100 parts by weight of the conjugated diene-based rubber contained in the polymerization reaction solution in which the reaction has been stopped; 4) a step of coagulating a conjugated diene rubber containing a sulfur-containing phenolic stabilizer by a steam stripping method, and (5) a method of producing a conjugated diene rubber composition including a drying step.

(Continuous Polymerization Step) The continuous polymerization step of the production method of the present invention is carried out by the above-mentioned method (A) for producing a conjugated diene polymer.

(Polymerization reaction stopping step) From the continuous polymerization step,
The method for terminating the polymerization reaction of the continuously withdrawn polymerization reaction liquid is not particularly limited. Generally, a polymerization terminator such as an alcohol such as methanol or isopropanol is added to a polymerization reaction solution of an organic active metal compound 1 mo.
Usually 1 to 100 mol, preferably 1.2 to 1 per liter
The polymerization is terminated by adding 0 mol, more preferably 2 to 5 mol. If the addition amount of the polymerization terminator is too small, the reaction does not stop sufficiently and the gel tends to increase. Cheap.

As a method of terminating the polymerization, there is a method of adding an acid to the polymerization reaction solution. The acid used may be an inorganic acid,
Organic acids may be used.

Examples of the inorganic acid include acids formed by bonding an acid group containing a nonmetal such as chlorine, sulfur, nitrogen, and phosphorus with hydrogen;
For example, hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, carbonic acid and the like can be mentioned.

Organic acids are organic compounds having acidity, for example, carboxylic acids, sulfonic acids, phenol sulfinates,
Compounds having a functional group such as enol, imide, oxime and the like can be mentioned, and are preferably carboxylic acid organic compounds, more preferably fatty acids having 8 or more carbon atoms, rosin acids or hydrogenated products thereof, oxycarboxylic acids, aromatics It is a carboxylic acid or an amino acid.

Fatty acids having 8 or more carbon atoms include octylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, neopentylic acid, oleic acid, linoleic acid, linoleic acid, ricinoleic acid, behenic acid and tallow fatty acid And the like. Oxycarboxylic acid is a carboxylic acid having at least one hydroxy group and at least one carboxyl group in the molecule, such as glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, oxyvaleric acid, 2-hydroxystearic acid, and salicylic acid. , O-oxycinnamic acid and the like. Examples of the aromatic carboxylic acid include benzoic acid, chlorobenzoic acid, cinnamic acid, and phenylacetic acid. Amino acids have at least one amino acid in the molecule.
A compound having two carboxyl groups and at least one amino group, such as glycine, alanine, valine, leucine, aliphatic amino acids, serine, threonine oxyamino acids, cysteine, cystine and other sulfur-containing amino acids, aspartic acid, glutamic acid, and the like. Examples thereof include aromatic amino acids such as monoaminodicarboxylic acid, aminobenzoic acid, and anthranilic acid.

The amount of the acid used is usually 0.1 to 10 equivalents, preferably 0.3 to 5 equivalents, based on the amount of the organic active metal compound.
More preferably, it is 0.5 to 3 equivalents. It is not necessary to use a single compound as the acid, and a plurality of compounds may be used as a mixture.

(Sulfur-containing phenol-based stabilizer addition step) In order to prevent thermal deterioration of the conjugated diene-based rubber in the coagulation step by steam stripping and the subsequent drying step, a sulfur-containing phenol-based stabilizer was added before the coagulation step. It is preferred to add. However, if the sulfur-containing phenol-based stabilizer is contained in the polymerization reaction solution in the continuous polymerization step and the polymerization termination step, the polymerization reaction and the polymerization termination reaction may be inhibited, respectively. for that reason,
In addition, the sulfur-containing phenol-based stabilizer is preferably added to the reaction solution in which the polymerization reaction has been stopped in the polymerization stopping step, since it can be more easily and uniformly dispersed than kneaded in the dried rubber. Also, the object of the present invention,
As long as the effect is not impaired, a phenol-based stabilizer other than the sulfur-containing phenol-based stabilizer or a phosphorus-based stabilizer may be used in combination. The antioxidant used in combination is not necessarily one kind, and a plurality of kinds may be used in combination.

(Coagulation Step) The solvent and unreacted monomer are removed from the polymerization reaction solution in which the polymerization has been stopped by steam stripping. The method of steam stripping is not particularly limited, but usually, the solution or suspension is brought into contact with a part of high-pressure steam and / or hot water immediately before being introduced into the steam stripping tank.

To the water in the stripping zone, if necessary, a dispersant, an acid and the like are added.

The dispersant is generally a surfactant, for example, an alkylbenzene sulfonate (alkyl preferably has 9 to 20 carbon atoms), a higher alcohol sulfate salt (higher alcohols preferably have 6 to 20 carbon atoms). ), Fatty acids (preferably having 6 to 22 carbon atoms) or salts of rosin acids, polyoxyethylene fatty alcohol ether sulfates (fatty alcohols preferably having 12 to 20 carbon atoms), alkylphenol polyethylene oxide phosphates Or a salt thereof (alkyl preferably has 1 to 20 carbon atoms), a higher alcohol polyethylene oxide phosphate (a higher alcohol preferably has 6 to 20 carbon atoms) or a salt thereof,
An anionic surfactant such as a copolymer of diisobutylene and maleic anhydride or a salt thereof, a copolymer of styrene and maleic anhydride or a salt thereof (the salt is preferably N 2
a, K, or NH ₄ salts; amine salts or amidopyridinium salts of fatty acid amine salts (fatty acids preferably having 6 to 22 carbon atoms), alkylammonium halides (alkyl preferably having 1 to 20 carbon atoms) ),
A cationic surfactant such as an alkylamine benzyl halide (alkyl preferably having 6 to 22 carbon atoms);
Sorbitan fatty acid esters (fatty acids preferably have 6 to 22 carbon atoms), polyethylene oxide glycerin fatty acid esters (fatty acids preferably have 6 to 22 carbon atoms)
), Polyethylene oxide higher alcohol ethers (higher alcohols preferably have 6 to 20 carbon atoms), polyethylene oxide alkylphenol ethers (alkyl preferably has 1 to 20 carbon atoms),
Block polymer of polyethylene oxide and polypropylene oxide (preferably a number average molecular weight of 1000
As described above, preferably, the content of polyethylene oxide is 5 to 90% by weight.

These dispersants are added in an amount of generally 0.1 to 3000 ppm based on the water in the stripping zone. In addition to these surfactants, Li, Na,
Water-soluble salts of metals such as K, Mg, Ca, Al, Zn and the like can also be used as dispersants.

When performing the dehydration step described below, it is preferable to control the pH of the dehydrated water to be usually 6 to 12, preferably 7 to 11, and more preferably 8 to 9. Thereby, the progress of the corrosion of the equipment is suppressed, and the performance deterioration of the obtained conjugated diene rubber is suppressed. In the previous polymerization stopping step, as a result of adding the acid, it is unnecessary when the pH of the water dehydrated in the dehydration step can be controlled in the above range, but otherwise, in the coagulation step, the stripping zone It is preferable to control the pH by adding an acid to the water. The acid added to the water in the stripping zone may be an organic acid or an inorganic acid, and examples thereof include the same acids that can be used for terminating polymerization. pH
, The amount of addition is increased or decreased according to the change in pH.

The solvent is removed by steam stripping to obtain a crumb-like aqueous dispersion of the conjugated diene rubber composition.

(Dehydration step) By removing water from the crumb-shaped aqueous dispersion of the conjugated diene rubber composition, a conjugated diene rubber composition is obtained. However, if there is too much water to be removed, it is not efficient to directly remove the water in the drying step. If necessary, adjust the moisture content of the wet crumb to
The content is adjusted to 30% by weight, preferably 1.5 to 20% by weight, and most preferably 2 to 10% by weight, so that the treatment in the drying step can be performed efficiently. Therefore, before the drying step, a crumb-like conjugated diene-based rubber composition aqueous dispersion may be subjected to a dehydration step of dewatering with a compressed water squeezing machine such as a roll, a Banbury type dehydrator, and a screw extruder type squeezing dehydrator. preferable.

When obtaining the conjugated diene rubber composition of the present invention, a compressed water press such as a single screw or twin screw multi-screw extruder-type press dewatering machine is preferable in terms of dewatering efficiency and workability. . If the setting of the moisture content in the crumb as a result of the dehydration step is too small, the efficiency of the dehydration treatment becomes too long because the dehydration treatment time is too long, or the polymer is gelated and deteriorated by shearing with a water drawer, Process control of the dehydration process tends to be difficult. Also, if the water content is set too high, the amount of catalyst residue increases, and when used for a styrenic resin, it is likely to be present as a foreign substance in the resin. For example, the production efficiency tends to decrease. In the present invention, the crumb-like aqueous dispersion of the conjugated diene rubber composition obtained at the time of steam stripping is removed to some extent by filtration or the like, and the resulting slurry is turned into a rotary screen, a vibrating screen, a centrifugal dehydrator. For example,
It is preferable from the viewpoint of production efficiency that the water is drained to a water content of 35 to 60% by weight and then introduced into a compressed water squeezer.

(Drying Step) The rubber used as the crumb is
It is dried until the water content is usually less than 1% by weight, preferably 0.5% by weight or less, more preferably 0.1% by weight or less. For drying, a screw-type extruder or a dryer such as a kneader-type dryer, an expander dryer, or a hot-air dryer is generally used. A particularly suitable dryer is a hot-air dryer, and a preferable drying method includes a method using a hot-air dryer after an expander dryer.

The dried product rubber is the conjugated diene rubber composition of the present invention and is usually subjected to compression molding and treated as a veil.

(Modifier for Resin) The modifier for resin of the present invention contains the conjugated diene rubber composition of the present invention as an active ingredient. In particular, it is useful as an impact modifier for resins (toughening agent).

The resin modifier was prepared by preparing a 5% by weight styrene solution and using an Ostwald viscometer.
When the solution viscosity at ℃ is measured, it is usually 2000 cps or less,
Preferably 1500 cps or less, more preferably 100 cps
0 cps or less. If the solution viscosity is too high, problems such as difficulty in uniformly dispersing in the resin may occur.

The conjugated diene rubber composition of the present invention can be applied to a wide range of resins as a resin modifier.
Specific examples of the resin to be modified include, for example, epoxy resin, xylene resin, guanamine resin, diallyl phthalate resin, phenol resin, unsaturated polyester resin, polyimide, polyurethane, maleic resin, melamine resin, urea resin, and the like. Curable resin; acrylonitrile-acrylate-styrene resin, acrylonitrile-
Ethylene-styrene resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin,
Polystyrene resin, high impact polystyrene resin,
Polyaromatic vinyl resins such as methyl methacrylate-styrene resin; polyolefin resins such as polyethylene and polypropylene; engineering plastics such as polyphenylene ether, polyamide, polycarbonate, polyacetal and polyester; Among these, polyaromatic vinyl resins, unsaturated polyester resins, polyphenylene ethers, and the like are preferable, and polyaromatic vinyl resins are particularly preferable. These resins can be used alone or in combination of two or more.

(Resin Composition) The resin composition of the present invention is obtained by blending the resin modifier of the present invention with a resin. The compounding ratio of the resin modifier of the present invention to the resin is appropriately selected depending on the purpose of use, the type of the (a) conjugated diene rubber in the composition, and the amount ratio with other compounding agents. (A) conjugated diene rubber is usually 0.1 to 3 parts by weight.
0 parts by weight, preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight. When the compounding ratio of the conjugated diene rubber of the present invention is within this range, the effect of improving impact resistance is high, and the deterioration of the resin's original physical properties such as appearance properties such as gloss and transparency and tensile strength and rigidity are also small. It is suitable. When using the resin modifier of the present invention,
What is necessary is just to mix | blend a resin modifier so that (a) conjugated diene rubber | gum in a resin modifier may become this compounding ratio.

The method for producing the resin composition of the present invention is not particularly limited. For example, even if the resin and the resin modifier of the present invention are mechanically mixed, The resin may be polymerized in the presence.

For example, in the case of producing a polyaromatic vinyl resin composition, (a) an aromatic vinyl monomer or an aromatic vinyl monomer in the presence of a conjugated diene rubber or a resin modifier It is common to polymerize a mixture of the body and other monomers copolymerizable therewith.

Examples of the aromatic vinyl monomer include styrene, o-methylstyrene, p-methylstyrene, m
-Methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, Examples thereof include p-bromostyrene, 2-methyl-1,4-dichlorostyrene, 2,4-dibromostyrene, and vinylnaphthalene. Of these, styrene is preferred. These aromatic vinyl monomers can be used alone or in combination of two or more.

Other monomers copolymerizable with the aromatic vinyl monomer include, for example, unsaturated nitrile monomers such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile; methacrylic acid methyl ester, acrylic acid (Meth) acrylic acid ester monomers such as methyl ester; unsaturated fatty acid monomers such as acrylic acid, methacrylic acid, and maleic anhydride; and phenylmaleimide. Among these, unsaturated nitrile monomers, (meth) acrylate monomers and unsaturated fatty acid monomers are preferred, and non-corrosive nitrile monomers are particularly preferred. These other monomers copolymerizable with the aromatic vinyl monomer can be used alone or in combination of two or more.

The ratio of the aromatic vinyl monomer to the other monomer copolymerizable therewith is appropriately selected according to the intended use. Weight), usually 20:80 to 100: 0, preferably 40:80.
60 to 100: 0, more preferably 60:40 to 10
The range is 0: 0.

The method for polymerizing the polyaromatic vinyl resin is not particularly limited, but is usually carried out by radical polymerization. The polymerization mode is not particularly limited, and examples thereof include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and a multi-stage polymerization method such as a bulk-suspension two-stage polymerization method. And bulk-suspension two-stage polymerization methods are preferred. In particular, the bulk polymerization method is preferably a bulk continuous polymerization method.

When the resin composition of the present invention is produced by the bulk continuous polymerization method, for example, the resin composition of the present invention is
Dissolve in aromatic vinyl monomer or a mixture of aromatic vinyl monomer and other monomer copolymerizable with it, and if necessary, internal lubricant such as diluent solvent, liquid paraffin, mineral oil, etc. , An antioxidant, a chain transfer agent and the like. In the case of non-catalytic polymerization, polymerization is usually carried out at 80 to 200 ° C, and in the case of catalytic polymerization, polymerization is carried out usually at 20 to 200 ° C in the presence of a polymerization catalyst. The polymerization conversion of the monomer (aromatic vinyl monomer or a mixture of the aromatic vinyl monomer and another monomer copolymerizable therewith) is usually 6
The polymerization is stopped when the amount becomes 0% by weight or more, preferably 60 to 90% by weight. In the case of the present invention, catalytic polymerization is preferred.

The polymerization catalyst is appropriately selected according to the polymerization method. In the case of radical polymerization, an organic peroxide or an azo-based catalyst is usually used, preferably an organic peroxide. As the organic peroxide, for example, 1,1-bis (t
Peroxyketals such as -butylperoxy) cyclohexane and 1,1-bis (t-butylperoxy) -8,3,5-trimethylcyclohexane; di-t-
Dialkyl peroxides such as butyl peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; diacyl peroxides such as benzoyl peroxide and m-toluoyl peroxide; peroxycarbonates such as dimethylstilperoxydicarbonate Peroxyesters such as t-butyl peroxyisopropyl carbonate; ketone peroxides such as cyclohexanone peroxide;
hydroperoxides such as p-mentha hydroperoxide; and the like. These polymerization catalysts can be used alone or in combination of two or more. The amount of the polymerization catalyst used is 10
Usually, 0.001 to 5 parts by weight, preferably 0.005 to 3 parts by weight, more preferably 0.01 to 5 parts by weight with respect to 0 parts by weight.
1 part by weight.

Examples of the diluting solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and cyclopentane; n-butane, n
-Aliphatic hydrocarbons such as hexane and n-heptane;
Ketones such as methyl isopropyl ketone; and the like, and aromatic hydrocarbons are preferable. Each of these diluting solvents is used alone or in combination of two or more, and the amount of the diluting solvent is usually 0 to 25% by weight of all monomers.

Examples of the chain transfer agent include mercaptans such as n-dodecyl mercaptan and t-dodecyl mercaptan; 1-phenylbutyl-2-fluorene;
Terpenes such as dipentene; halogen compounds such as chloroform; α-methylstyrene dimer;

After completion of the polymerization operation, the resulting resin composition is
According to a conventional method, for example, unreacted monomers, diluting solvents, and the like can be removed and recovered by extruding using an extruder designed to remove the solvent by heating under reduced pressure or removing volatiles. The obtained resin composition is practically used after being pelletized or powdered as necessary.

In the bulk-suspension polymerization method, the polymerization is usually partially carried out in the same manner as in the bulk polymerization method until the polymerization conversion of the monomer reaches 30 to 50% by weight. The polymerized polymerization solution is suspended in water in the presence of a suspension stabilizer such as polyvinyl alcohol and carboxymethyl cellulose and / or a surfactant such as sodium dodecylbenzenesulfonate to complete the reaction.
The resulting impact-resistant resin composition is isolated by a method such as filtration and centrifugation, washed with water, dried, and pelletized or powdered as necessary.

In the resin composition of the present invention, the average particle size of the rubber (a) in the resin matrix, such as a conjugated diene rubber, is not particularly limited, but is usually 0.01 to 10 μm.
m, preferably 0.1-5 μm, more preferably 0.5
When it is within the range of ３3 μm, the improvement of impact resistance is extremely suitable.

[0088]

The present invention will be specifically described below with reference to examples and reference examples.

Example 1 (Preparation of Conjugated Diene Rubber Composition) Two 250-liter stainless steel polymerization reactors equipped with a stirrer, a reflux condenser and a jacket, which had been washed, dried and purged with nitrogen, were connected in series. Continuous polymerization was carried out as follows.

While continuously supplying a mixture of 75% by weight of cyclohexane and 25% by weight of 1,3-butadiene to the polymerization reactor at a rate of 70 kg / h, n-butyllithium was used as an organic active metal compound in the supply pipe. A cyclohexane solution of 1,2-butadiene as an allene compound, a cyclohexane solution of tetramethylethylenediamine as a polar compound in 0.1% by weight, and a cyclohexane solution of divinylbenzene as a branching agent in 1% by weight. 1300g / h, 7 each
90 g, 1173 g, and 525 g were continuously supplied, and the continuous polymerization was carried out for 48 hours while adjusting to 80 ° C. and a residence time of 2 hours and 30 minutes. The reaction mixture of polybutadiene produced from the second polymerization reactor was continuously extracted, and the polymerization reaction conversion was examined. As a result, a steady state was reached at 98%.

After it became steady, a 1 wt% methanol solution of methanol as a terminator was added to a rubber solution continuously withdrawn from the second polymerization reactor through a pipeline.
2,4-bis (n
10-octylthiomethyl) -6-methylphenol
980 g / h of 438 wt.
g, were continuously added and mixed with a line mixer. 100 kg / hour of steam of 12 kg / cm 2 (gauge pressure) is blown into this mixed solution, and this rubber is continuously received in an 800-liter coagulation tank, while stirring so that the weight ratio of rubber and water becomes 4/96. Add water,
The solvent and unreacted monomer were recovered by steam stripping to obtain a mixture of rubber coagulate and water. The mixture was continuously extracted, and water and a rubber coagulated product were separated using a 10-mesh wire mesh. The obtained coagulated rubber was dried using an extrusion dryer to obtain a polybutadiene rubber composition A. In addition, 2,4-bis (n-octylthiomethyl) -6-methylphenol was not detected in the water after the separation of the water and the rubber coagulated product. Table 1 shows the solution viscosity, vinyl bond amount, gel grade and the like of the polybutadiene rubber composition A.

(Production of resin composition) In a stainless steel reactor equipped with a stirrer, 180 g of a polybutadiene rubber composition A was dissolved in 1820 g of a styrene monomer as a sample, and a chain transfer agent (n-dodecyl mercaptan) was added to the styrene monomer. Added at a rate of 250 ppm;
The mixture was stirred for 1 hour and 20 minutes at ℃ to perform bulk polymerization. Next, the contents were taken out, and 1250 g of the contents and 3750 g of a 2% aqueous solution of polyvinyl alcohol were placed in an 8-liter stainless steel reaction vessel equipped with a stirrer, and the temperature was raised to 70 ° C.
Next, 2.5 g of benzoyl peroxide and 1.26 g of dicumyl peroxide were added, and 9 hours at 70 ° C.
Polymerization was carried out at 0 ° C. for 1 hour, at 110 ° C. for 1 hour, and at 130 ° C. for 4 hours. After completion of the polymerization, the mixture was cooled to room temperature, and the obtained impact-resistant polystyrene resin composition was filtered, collected, washed with water, and dried under reduced pressure at 60 ° C. for 6 hours.

The obtained polystyrene resin composition was treated with 18
The mixture was formed into a sheet by kneading with a roll at 0 ° C. and formed into a pellet by a sheet pelletizer. The obtained pellets were extruded into a sheet having a width of 50 cm and a thickness of 0.10 mm, and the fisheye grade was measured. The results are shown in Table 1.

Example 2 A 1% by weight cyclohexane solution of n-butyllithium as an organic active metal compound, a 1% by weight cyclohexane solution of 1,2-butadiene as an allene compound, 0.1% by weight cyclohexane of tetramethylethylenediamine as a polar compound The same treatment as in Example 1 was carried out except that the supply amounts of the solution and the 1 wt% cyclohexane solution of divinylbenzene as a branching agent were changed to 980 g, 744 g, 1050 g, and 490 g / hour, respectively. In a steady state, a polybutadiene rubber composition B was obtained. In addition, 2,4-bis (n-octylthiomethyl) -6-methylphenol was not detected in the water after the separation of the water and the rubber coagulated product. Table 1 shows the solution viscosity, the amount of vinyl bonds, the gel grade of the polybutadiene rubber composition B, the fisheye grade of the polystyrene resin composition containing the polybutadiene rubber composition B, and the like.

Example 3 Instead of 2,4-bis (n-octylthiomethyl) -6-methylphenol as an antioxidant, 2,4-bis (n-octylthiomethyl) -6-methylphenol and tris Except for using an equal weight mixture of -nonylphenyl phosphite, the mixture was treated in the same manner as in Example 2. As a result, the polymerization reaction conversion became 98% and the steady state was reached, whereby polybutadiene rubber composition C was obtained. The antioxidant was not detected in the water after the separation of the water and the rubber coagulate. Table 1 shows the solution viscosity, the amount of vinyl bonds, the gel grade of the polybutadiene rubber composition C, and the fisheye grade of the polystyrene resin composition containing the polybutadiene rubber composition C.

Example 4 The same treatment as in Example 2 was carried out except that the supply amount of a 1% by weight cyclohexane solution of 1,2-butadiene as an allene compound was changed to 200 g / h.
The state reached a steady state at 8%, and a polybutadiene rubber composition D was obtained. In addition, 2,4-
Bis (n-octylthiomethyl) -6-methylphenol was not detected. Table 1 shows the solution viscosity, vinyl bond amount, gel grade, fisheye grade of the polystyrene resin composition containing the polybutadiene rubber composition D, and the like of the polybutadiene rubber composition D.

Example 5 1 wt% cyclohexane solution of n-butyllithium as an organic active metal compound, 1 wt% cyclohexane solution of 1,2-butadiene as an allene compound, 0.1 wt% cyclohexane of tetramethylethylenediamine as a polar compound The same treatment as in Example 1 was carried out except that the supply amounts of the solution and the 1 wt% cyclohexane solution of divinylbenzene as a branching agent were changed to 610 g, 330 g, 1050 g, and 220 g / hour, respectively. The state became a steady state, and a polybutadiene rubber composition E was obtained. In addition, 2,4-bis (n-octylthiomethyl) -6-methylphenol was not detected in the water after the separation of the water and the rubber coagulated product. Table 1 shows the solution viscosity of the polybutadiene rubber composition E, the amount of vinyl bonds, the gel grade, the fisheye grade of the polystyrene resin composition containing the polybutadiene rubber composition E, and the like.

Example 6 As a sulfur-containing phenolic stabilizer, 2,4-bis (n
10-octylthiomethyl) -6-methylphenol
The same procedure as in Example 2 was carried out except that the supply amount of the toluene solution by weight was changed to 70 g / h, the polymerization reaction conversion became 98% and the steady state was reached.
I got It should be noted that 2,4
-Bis (n-octylthiomethyl) -6-methylphenol was not detected. Polybutadiene rubber composition F
Table 1 shows the solution viscosity, vinyl bond amount, gel grade, fisheye grade of the polystyrene resin composition containing the polybutadiene rubber composition F, and the like.

Comparative Example 1 A stabilizer n-octadecyl-3- (3 ', 5'-di-tert-butyl-) was used in place of the sulfur-containing phenolic stabilizer.
Except for using an equal weight mixture of 4-hydroxyphenyl) propionate (Irganox 1076, manufactured by Ciba Geigy) and a stabilizer, tris-nonylphenyl phosphite, the reaction was carried out in the same manner as in Example 2. This gave a polybutadiene rubber composition G. The antioxidant was not detected in the water after the separation of the water and the rubber coagulate. Table 1 shows the solution viscosity of the polybutadiene rubber composition G, the amount of vinyl bonds, the gel grade, the fisheye grade of the polystyrene resin composition containing the polybutadiene rubber composition G, and the like.

Comparative Example 2 The stabilizer 2,6- was used in place of the sulfur-containing phenolic stabilizer.
The same procedure as in Example 2 was repeated except that a weight mixture of di-tert-butyl-4-methyl-phenol and a stabilizer such as tris-nonylphenyl phosphite was used. Rubber composition H was obtained. The antioxidant was not detected in the water after the separation of the water and the rubber coagulate. Table 1 shows the solution viscosity, the amount of vinyl bonds, the gel grade of the polybutadiene rubber composition H, the fisheye grade of the polystyrene resin composition containing the polybutadiene rubber composition H, and the like.

Comparative Example 3 The same procedure as in Example 2 was carried out except that the 1% by weight solution of 1,2-butadiene in cyclohexane was not supplied. As a result, the polymerization reaction conversion became 98% and the steady state was reached. Obtained. It should be noted that 2,4-bis (n-octylthiomethyl) -6--6 was added to the water after separation of the water and the rubber coagulated product.
Methyl phenol was not detected. Table 1 shows the solution viscosity, the amount of vinyl bonds, the gel grade of the polybutadiene rubber composition I, and the fisheye grade of the polystyrene resin composition containing the polybutadiene rubber composition I.

Comparative Example 4 The procedure of Example 2 was repeated except that a 10% by weight toluene solution of 2,4-bis (n-octylthiomethyl) -6-methylphenol was not supplied. % Of the polybutadiene rubber composition J
I got Table 1 shows the solution viscosity, the amount of vinyl bonds, the gel grade of the polybutadiene rubber composition J and the fisheye grade of the polystyrene resin composition containing the polybutadiene rubber composition J.

[0103]

[Table 1]

The solution viscosity of the polybutadiene rubber composition was measured on a 5% by weight styrene solution at 25 ° C. using an Ostwald viscometer, and the vinyl content was measured by an infrared spectrophotometer (manufactured by JASCO Corporation, Japan). IR-700) was used to measure the infrared absorption spectrum and calculated by the Morero method.

[0105] The fisheye grade is determined by visually observing the appearance of the sheet.
0 to 10 pieces per m2, １０〜 to 10 to 20 pieces, × to 21 to 30 pieces, × to 30 or more pieces
X was evaluated.

The gel grade of the polybutadiene rubber was measured according to the following procedure.

5 g of polybutadiene rubber and 250 ml of xylene were added to a 500 ml Erlenmeyer flask with a stopper, and the rubber was dissolved by shaking for 6 hours with a shaker. afterwards,
Using a No. 2 filter paper having a diameter of 70 mm, the dissolved rubber solution was subjected to suction filtration. After filtering the whole amount, the Erlenmeyer flask was washed with 20 ml of xylene, and the washing solution was suction-filtered with the above-mentioned filter paper. After completion of the filtration, the filter paper was transferred to a petri dish, and a dye solution (0.1 g of oil-soluble dye Oil Brown GR dissolved in 100 g of xylene) was dropped on the filter paper with a dropper so that the whole was colored. The lid of the dish was displaced and opened halfway, and the solvent was evaporated.

The filter paper from which the solvent was completely evaporated was observed, and those having a gel size of less than 0.5 mm were classified as Class A,
B class, 1.0m
Those with m or more and less than 2.0 mm were evaluated as C class, and those with 2.0 mm or more were evaluated as D class. In the following, there are no more than 2 B-grade gels and no C- and D-grade gels, but not 1st-grade, 2nd-grade, no more than 17 gels, 3 C-grade gels or less and 3 D-grades Those having no gel and not primary or secondary are tertiary, the number of gels is 29 or less, the number of D-class gels is 3 or less, and those not 1-3 are quaternary, and the number of gels is 39.
If the number of gels is 3 or less and the number of D-class gels is 3 or less and not 1 to 4th grade, 5th grade, those with 40 to 49 gels are 6th grade, those with 50 to 59 gels are 7th grade. And those having 60 or more gels were evaluated as 8th grade.

From the comparison between Examples 2 and 3 and Comparative Examples 1, 2 and 4, the rubber composition of the present invention containing the sulfur-containing phenolic stabilizer (B) was It can be seen that the gel content is lower than that of the rubber composition containing no agent, and fish eyes are less likely to occur in the composition blended with the polyaromatic vinyl resin as a resin modifier.

Also, from the comparison between Example 2 and Comparative Example 3,
(B) The rubber composition of the present invention containing a conjugated diene rubber polymerized in the presence of an allene compound as a component has a higher gel content than a rubber composition containing a conjugated diene rubber polymerized in the absence of an allene compound. It can be seen that fisheye is less likely to occur in the composition in which the amount is small and the composition is mixed with a polyaromatic vinyl resin as a resin modifier.

[0111]

The rubber composition of the present invention has a low gel content, and when it is blended with a resin as a resin modifier, the resulting resin composition is less likely to generate fish eyes. Therefore, the impact-resistant resin composition obtained by being blended with the aromatic vinyl resin can be used as a high-quality resin film.

(Embodiments) As embodiments of the present invention, for example: (A) 100 parts by weight of a conjugated diene rubber obtained by continuously polymerizing a conjugated diene compound in a hydrocarbon solvent in the presence of (a) an organic active metal compound and (b) an allene compound represented by the general formula 1. 1. a conjugated diene rubber composition comprising (B) 0.01 to 5.0 parts by weight of a sulfur-containing phenolic stabilizer represented by the general formula 2. When the conjugated diene compound is 1,3-butadiene,
Methyl-1,3-butadiene, 2,3-dimethyl-1,
3-butadiene, 2-chloro-1,3-butadiene,
2. The rubber composition according to 1, which is 1,3-pentadiene, preferably 1,3-butadiene or 2-methyl-1,3-butadiene, and more preferably 1,3-butadiene. The conjugated diene rubber is such that the monomer unit derived from the conjugated diene compound is 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, of all the monomer units.
3. The rubber composition according to 1 or 2, which is particularly preferably 100% by weight. The conjugated diene rubber has a molecular weight of 10,000 or more, preferably 50,000 or more, more preferably 100,0 or more.
00 or more and 3,000,000 or less, preferably 2,0
00,000,000 or less, more preferably 1,000,000
4. The rubber composition according to any one of the following 1 to 3, 5. The rubber composition according to any one of 1 to 4, wherein the conjugated diene rubber has a molecular weight distribution of 5.0 or less, preferably 4.0 or less, more preferably 3.0 or less. The conjugated diene-based rubber is composed of 1,4 conjugated diene units.
A cis bond content of 50% or less, preferably 45% or less;
6. The rubber composition according to any one of 1 to 5, which is more preferably 40% or less; The conjugated diene rubber has a vinyl bond (1,2-vinyl bond and 3,4 vinyl bond) content of the conjugated diene bond unit of 5% or more, preferably 7% by weight or more, more preferably 10% by weight or more, 80%. Or less, preferably 50% or less,
7. The rubber composition according to any one of 1 to 6, which is more preferably 40% or less; An organic active metal compound, an organic alkali metal compound,
An organic alkaline earth metal compound, or an organic lanthanoid rare earth metal compound, preferably an organic lithium compound,
More preferably monoorganic lithium compound, even more preferably n-butyllithium, sec-butyllithium,
8. The rubber composition according to any one of 1 to 7, which is t-butyllithium, hexyllithium, phenyllithium, or stilbenelithium; Organic active metal compound is 0.01 mmol or more, preferably 0.05 mmol or more, more preferably 0.1 mmol or more, 20 mmol or less, preferably 100 mmol or less, per 100 g of all monomers used for polymerization of the conjugated diene rubber. 1
9. The rubber composition according to any one of 1 to 8, which is used for polymerization of 5 mmol or less, more preferably 10 mmol or less, The amount of the allene compound used is an organic active metal compound
0.01 to 50 mol, preferably 0.1 to 50 mol per 1 mol
1 to 20 moles, more preferably 0.3 to 10 moles
10. The rubber composition according to any one of items 9 to 11, The sulfur-containing phenolic stabilizer is usually 0.01 to 5 parts by weight, based on 100 parts by weight of the conjugated diene rubber,
Preferably 0.03 to 2 parts by weight, more preferably 0.03 parts by weight.
11. The rubber composition according to any one of 1 to 10, which is 5 to 1 part by weight, The rubber composition according to any one of 1 to 10, wherein the sulfur-containing phenol-based stabilizer is 2,4-bis (n-octylthiomethyl) -6-methylphenol.

13. (1) a step of continuously polymerizing a conjugated diene compound in a hydrocarbon solvent in the presence of (a) an organic active metal compound and (b) an allene compound represented by the general formula 1,
(2) a step of adding 0.01 to 5.0 parts by weight of a sulfur-containing phenolic stabilizer represented by the general formula 2 to a conjugated diene polymerization reaction solution obtained by continuous polymerization in which the reaction is stopped; A) a process for coagulating a conjugated diene rubber containing a sulfur-containing phenolic stabilizer by a steam stripping method, and (4) a method for producing a conjugated diene rubber composition according to any one of 1 to 12, comprising a drying step. , 14. The amount of inert organic solvent used is usually 5
14. The production method according to 13, wherein the amount is from 70 to 70% by weight, preferably from 10 to 60% by weight, more preferably from 20 to 50% by weight. (A) A polymerization reaction for obtaining a conjugated diene rubber obtained by conducting continuous polymerization for an average residence time of usually 0.1 to 10 hours, preferably 0.5 to 5 hours, more preferably 1 to 3 hours. 15. The production method according to any one of 13 to 14, 16. The production method according to any one of 13 to 15, wherein the polymerization temperature is usually -10 to 150 ° C, preferably 20 to 120 ° C, and the polymerization pressure is usually 0 to 5 atm (gauge pressure). The polymerization conversion of the polymerization reaction liquid continuously withdrawn is usually from 60 to 100% by weight, preferably from 80 to 100% by weight, more preferably from 90 to 100% by weight.
17. The production method according to any one of 6. The polymerization reaction solution contains a polymerization terminator in an amount of usually 1 to 100 mol, preferably 1. mol, per 1 mol of the organic active metal compound.
2 to 10 mol, more preferably 2 to 5 mol,
18. The production method according to any one of 13 to 17, wherein the polymerization is stopped. The polymerization reaction solution according to any one of 13 to 18, wherein a neutralizing agent is added in an amount of usually 0.1 to 10 equivalents, preferably 0.3 to 5 equivalents, more preferably 0.5 to 3 equivalents to the organic active metal compound. Rubber composition, 20. For steam stripping, add 0.1 to 3000 ppm of dispersant to the stripping zone.
20. The production method according to any one of 9 above, The aqueous dispersion of the crumb-like conjugated diene-based rubber composition obtained by steam stripping is dewatered with a compressed water drawer to give a water content of usually 1 to 30% by weight, preferably 1.5% by weight.
21. The production method according to any of 13 to 20, wherein the crumb is made into a hydrated crumb of 20 to 20% by weight, most preferably 2 to 10% by weight, and then dried. 22. The method according to any one of 13 to 21, wherein the conjugated diene rubber composition is dried until the water content is usually less than 1% by weight, preferably 0.5% by weight or less, more preferably 0.1% by weight or less. 23. 13. A resin modifier comprising the conjugated diene rubber composition according to any one of 1 to 12; 25. A resin composition containing the conjugated diene rubber according to any one of 1 to 12; In the presence of the resin modifier described in 24, obtained by polymerizing an aromatic vinyl monomer, or a mixture of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer. And an impact-resistant polyaromatic vinyl resin composition.

Claims (4)

[Claims] (A) (a) an organic active metal compound and (b) a general formula 1 (R in the formula represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) A conjugated diene rubber obtained by continuously polymerizing a conjugated diene compound in a hydrocarbon solvent in the presence of an allene compound represented by the formula: 100 parts by weight and (B) general formula 2 (Wherein, R ¹ and R ³ represent —CH ₂ —S—R ⁵ , R ⁵ represents an alkyl group having 20 or less carbon atoms, and R ² and R ⁴ represent a hydrogen atom or an alkyl having 15 or less carbon atoms. A conjugated diene rubber composition comprising 0.01 to 5.0 parts by weight of a sulfur-containing phenolic stabilizer represented by the following formula: (1) (1) (a) an organic active metal compound and (b)
General formula 1 (R in the formula represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) in the presence of an allene compound represented by the following formula: (2) a step of continuously polymerizing a conjugated diene compound in a hydrocarbon solvent;
Stopping the polymerization reaction of the conjugated diene polymerization reaction solution obtained by continuous polymerization; (3) per 100 parts by weight of the conjugated diene rubber contained in the stopped polymerization reaction solution, the general formula 2 (Wherein, R ¹ and R ³ represent —CH ₂ —S—R ⁵ , R ⁵ represents an alkyl group having 20 or less carbon atoms, and R ² and R ⁴ represent a hydrogen atom or an alkyl having 15 or less carbon atoms. A sulfur-containing phenol-based stabilizer represented by the following formula: (4) a conjugated diene-based rubber containing a sulfur-containing phenol-based stabilizer by steam stripping. And (5) a method for producing a conjugated diene rubber composition including a drying step. 3. A resin modifier comprising the conjugated diene rubber composition according to claim 1. 4. A resin composition containing the conjugated diene rubber according to claim 1.