JP2002212344A - Rubber-like polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rubber-like polymer composition having improved molding processability and dispersibility of additive and excellent heat build-up, etc., when compounded with silica as a reinforcing agent. SOLUTION: This rubber-like polymer composition comprises 3-500 pts.wt. of a fixed siloxane-modified polymer particle based on 100 pts.wt. of a rubber- like polymer. The polymer particle is composed of a basic particle constituted of a conjugated diene-based polymer and at least one selected from (1) a siloxane modification part chemically bonded to the conjugated diene-based polymer formed on the surface and/or in the vicinity of the surface of the basic particle, (2) a siloxane modification part containing an alkoxysilyl group or (3) the siloxane modification part and a protective layer covering at least a part of the siloxane modification part. The rubber-like polymer composition can further contain 1-200 pts.wt. of a reinforcing agent (preferably silica-based compound) based on 100 pts.wt. of the total of the rubber-like polymer and the siloxane modified polymer particle.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a rubber-like composition, and more particularly to a rubber-like composition containing a rubber-like polymer and siloxane-modified polymer particles as essential components.

[0002]

2. Description of the Related Art Hitherto, for example, a large amount of diene rubber has been used as a rubber material used for rubber products.
When a rubber product is obtained from this diene rubber, it has been proposed to reduce the heat buildup by using a rubber composition containing silica instead of carbon black as a reinforcing agent. However, the rubber composition containing silica has a problem that sufficient abrasion resistance and tensile strength cannot be obtained as compared with the rubber composition containing carbon black. One of the causes is considered to be that a sufficient reinforcing effect cannot be exerted because the dispersibility of silica in the diene rubber is smaller than that of carbon black.

Hitherto, in order to enhance the dispersibility of silica in a diene rubber, the use of a diene rubber into which a substituent having an affinity for silica has been introduced has been studied. For example, in the case of a diene rubber obtained by an emulsion polymerization method, a diene rubber having a tertiary amino group introduced therein (JP-A-1-101344).
However, in a diene rubber obtained by an anionic polymerization method, an alkylsilyl group is added to a molecular chain terminal (Japanese Patent Laid-Open No. 1-199501).
JP-A-5-23028), a halogenated silyl group (JP-A-5-23028)
No. 6) or a substituted amino group (JP-A-64-2294).
No. 0) has been proposed.

[0004] However, most of the diene rubbers into which these substituents are introduced are strongly agglomerated with the silica when mixed with the silica, thereby causing poor dispersion of the silica. It has the disadvantage that properties such as strength and abrasion resistance are not sufficiently improved. In order to improve the above drawbacks, Japanese Patent Application Laid-Open No. 9-2086
No. 32 proposes a method using a diene rubber in which a silicon-containing vinyl monomer is copolymerized.

However, all of these methods use a special diene rubber, and there is a problem that conventional versatile conjugated diene rubber cannot be used. Therefore, there has been a demand for a dispersing agent which can be used by being added to conventional general-purpose conjugated diene rubbers and which can improve the above-mentioned disadvantages.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to improve the processability of rubbery polymers such as general-purpose conjugated diene rubbers, and to enhance the dispersibility of additives when added. Another object of the present invention is to provide a rubbery polymer composition which is excellent in heat build-up when silica is blended as a reinforcing agent, exhibits high tensile strength and abrasion resistance, and has good processability.

[0007]

Means for Solving the Problems The present inventors have found that the above problems can be solved by blending predetermined siloxane-modified polymer particles with a rubber-like polymer, and have completed the present invention. That is, the rubber-like polymer composition according to claim 1 is based on 100 parts by weight of the rubber-like polymer and at least one siloxane-modified polymer selected from the following polymer particles (A), (B) and (C). It is characterized by containing 3 to 500 parts by weight of united particles. [Polymer particles (A)] Consisting of basic particles composed of a conjugated diene polymer and siloxane-modified portions formed on the surface and / or near the surface of the basic particles, wherein the siloxane-modified portions are formed of the polymer And a siloxane-modified polymer particle chemically bonded to at least one of an alkoxysilyl group, a hydroxysilyl group, and a polysiloxanyl group. [Polymer particles (B)] Siloxane-modified polymer particles formed by forming a siloxane-modified portion having an alkoxysilyl group on the surface and / or near the surface of the basic particles made of a conjugated diene polymer. [Polymer Particle (C)] A siloxane-modified portion having at least one group of an alkoxysilyl group, a hydroxysilyl group, and a polysiloxanyl group is formed on the surface and / or near the surface of the basic particle made of a conjugated diene polymer. Further, siloxane-modified polymer particles comprising a conjugated diene-based polymer and further forming a protective layer covering at least a part of the siloxane-modified portion.

[0008] The conjugated diene-based polymer constituting the basic particles of the siloxane-modified polymer particles is, as described in claim 2, 10 to 95% by weight of a conjugated diene-based monomer unit and an aromatic diene-based monomer. It is preferred that the composition be composed of 5 to 90% by weight of at least one of the unit and the vinyl cyanide monomer unit, and 0 to 85% by weight of the other monomer units.

[0009] The rubbery polymer composition may comprise reinforcing agents 1 to 20 based on 100 parts by weight of the total amount of the rubbery polymer and the siloxane-modified polymer particles.
0 parts by weight can be further contained. As the reinforcing agent, one composed of a silica-based compound is preferable, and in this case, the effect of the present invention is particularly well exhibited.

Hereinafter, the present invention will be described in detail. [1] About rubber-like polymer As the "rubber-like polymer" of the present invention, for example, ethylene-propylene rubber, acrylic rubber, butyl rubber, chlorosulfonated polyethylene, chlorinated polyethylene, silicone rubber, fluorine rubber , Urethane rubber, hydrin rubber, diene rubber, etc., of which diene rubber is preferable. As this diene rubber, for example,
Natural rubber (NR), polyisoprene rubber (IR), emulsion-polymerized styrene-butadiene copolymer rubber (SBR), solution-polymerized random SBR (bonded styrene 5 to 50% by weight, 1,2-vinyl bond amount in butadiene bond unit portion) 10-8
0%), high trans SBR (70-95% of 1,4-trans bond in butadiene bond unit portion), low cis polybutadiene rubber (BR), high cis BR, high trans BR
(Amount of 1,4-trans bond in butadiene bond unit portion is 7)
0-95%), styrene-isoprene copolymer rubber (SI
R), butadiene-isoprene copolymer rubber, solution-polymerized random styrene-butadiene-isoprene copolymer rubber (SIBR), emulsion-polymerized SIBR, emulsion-polymerized styrene-
Acrylonitrile-butadiene copolymer rubber (NSB
R), solution polymerized NSBR, emulsion polymerized acrylonitrile
Examples thereof include block copolymers such as butadiene copolymer rubber (NBR), high vinyl SBR-low vinyl SBR block copolymer rubber, and polystyrene-polybutadiene-polystyrene block copolymer, which can be appropriately selected according to required characteristics. These rubbers can be used alone or in combination of two or more.

Examples of conjugated diene monomers used to obtain these rubbery polymers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1, Examples thereof include 3-butadiene, 2-chloro-1,3-butadiene, and 1,3-pentadiene. Among these, 1,3-butadiene, 2-methyl-1,3
-Butadiene and the like are preferred, and 1,3-butadiene is more preferred. These conjugated diene monomers can be used alone or in combination of two or more.

Examples of aromatic vinyl monomers used for obtaining these rubbery polymers include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, and 4-methylstyrene. , 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-
Butylstyrene, 5-t-butyl2-methylstyrene,
Monochlorostyrene, dichlorostyrene, monofluoroethylene and the like can be mentioned, of which styrene is preferably used. These aromatic vinyl monomers can be used alone or in combination of two or more.

Examples of vinyl cyanide monomers used to obtain these rubbery polymers include (meth) acrylonitrile (referring to acrylonitrile and methacrylonitrile), crotonitrile, cinnamate nitrile and the like. Of these, (meth) acrylonitrile is preferred. These vinyl cyanide monomers can be used alone or in combination of two or more. Further, a monomer capable of introducing a polar functional group into the rubbery polymer may be copolymerized. Examples of the monomer into which a polar functional group can be introduced include the following monomers (1) to (6). These monomers into which polar functional groups can be introduced can be used alone or in combination of two or more.

(1) Cyano group-containing monomer The above-mentioned vinyl cyanide monomer, 2-cyanoethyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, 3-cyanopropyl (meth) acrylate and the like.
Among them, (meth) acrylonitrile is particularly preferably used.

(2) Carboxyl group-containing monomer (meth) acrylic acid, crotonic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, monomethyl maleate, monoethyl maleate, Carboxyl group-containing unsaturated monomers such as monomethyl itaconate, monoethyl itaconate and mono-2- (meth) acryloyloxyethyl hexahydrophthalate or anhydrides thereof; Among them, (meth) acrylic acid is particularly preferably used.

(3) Hydroxy group-containing monomers hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono ( Hydroxy (cyclo) alkyl mono (meth) acrylates such as meth) acrylate; 3-chloro-2-hydroxypropyl (meth) acrylate, 3-amino-2
-Substituted hydroxy (cyclo) alkylmono (meth) acrylates such as hydroxypropyl (meth) acrylate.

(4) Glycidyl group-containing monomers Allyl glycidyl ether, glycidyl (meth) acrylate, methyl glycidyl methyl acrylate, epoxidized cyclohexyl (meth) acrylate, and the like.

(5) Ester group-containing monomers Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) A) (cyclo) alkyl (meth) acrylates such as acrylates; alkoxy (cyclo) alkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate and p-methoxycyclohexyl (meth) acrylate; vinyl acetate, vinyl propionate And vinyl esters such as vinyl versatate.

(6) Other polar group-containing monomers N-methylolated unsaturated carboxylic acid amides such as N-methylol (meth) acrylamide and N, N-dimethylol (meth) acrylamide; 2-dimethylaminoethylacrylamide Acrylamides containing aminoalkyl groups such as amides; amides or imides of unsaturated carboxylic acids such as (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N, N-ethylenebis (meth) acrylamide, maleic amide, and maleimide N-monoalkyl (meth) acrylamides such as N-methylacrylamide, N, N-dimethylacrylamide, N, N
Aminoalkyl group-containing (meth) acrylates such as 2-dimethylaminoethyl (meth) acrylate; aminoalkoxyalkyl group-containing (meth) acrylates such as 2- (dimethylaminoethoxy) ethyl (meth) acrylate Vinyl halides such as vinyl chloride, vinylidene chloride, and fatty acid vinyl ester; diethylene glycol di (meth)
Multifunctional (meth) acrylates such as acrylate and trimethylolpropane tri (meth) acrylate.

The rubbery polymer in the present invention includes NR, BR, IR, SBR, SIBR, N
BR, NSBR, etc. are preferred, and BR, NBR, NSBR
And SBR are more preferred. As this SBR,
When the total amount of the conjugated diene monomer and the aromatic vinyl monomer is 100% by weight, the conjugated diene monomer is 45 to 9%.
5% by weight (more preferably 50 to 90% by weight, still more preferably 55 to 85% by weight), and 5 to 55% by weight of the aromatic vinyl monomer (more preferably 10 to 50% by weight, further preferably 15% by weight). -45% by weight). As the NBR, the total amount of the conjugated diene monomer and the vinyl cyanide monomer is 100
By weight, 45 to 99% by weight of the conjugated diene monomer
(More preferably 50 to 90% by weight, still more preferably 55 to 85% by weight), and the vinyl cyanide monomer is 1 to 5% by weight.
The copolymer is preferably 5% by weight (more preferably 2 to 50% by weight, and still more preferably 3 to 45% by weight). As NSBR, the total amount of the conjugated diene-based monomer, vinyl cyanide-based monomer and aromatic vinyl-based monomer is 100% by weight, and the conjugated diene-based monomer is 45 to 90% by weight (more Preferably, it is 45 to 85% by weight, more preferably 50 to 85% by weight, and the vinyl cyanide monomer is 1 to 40% by weight (more preferably, 2 to 3% by weight).
5% by weight, more preferably 3 to 30% by weight, and 5 to 50% by weight (more preferably 10 to 50% by weight) of the aromatic vinyl monomer.
To 45% by weight, more preferably 15 to 40% by weight).

[0021] The rubbery polymer of the present invention comprises BR, NBR, N
If it is SBR or SBR, its Mooney viscosity (M
(L _{1 + 4} , 100 ° C.) is preferably in the range of 10 to 200, more preferably 20 to 150, even more preferably 25 to 120. If the Mooney viscosity is too low, heat buildup and abrasion resistance decrease, and if it is excessively high, workability tends to decrease. Further, a rubbery polymer having a high Mooney viscosity may be oil-extended with an extension oil in advance to adjust the Mooney viscosity to an appropriate Mooney viscosity with good processability. The microstructure of the conjugated diene bond unit portion of BR, NBR, NSBR or SBR is not particularly limited, and is appropriately selected depending on the purpose of use. For example, the vinyl bond (1,2-vinyl bond and 3,4
-Vinyl bond) is usually in the range of 5 to 95%, preferably 7 to 50%, more preferably 10 to 30%. When the vinyl bond amount of the conjugated diene bond unit is within this range, heat generation characteristics and abrasion resistance are preferably balanced with hardness. Except for the vinyl bond in the conjugated diene bond unit portion, the bond is a 1,4-bond, a 1,4-cis bond,
And any of trans bonds.

[2] Regarding Siloxane-Modified Polymer Particles The rubber-like polymer composition of the present invention contains “siloxane-modified polymer particles” in addition to the above-mentioned rubber-like polymer. Less than,
The siloxane-modified polymer particles will be described. [2-1] Basic particles “Basic particles” in the siloxane-modified polymer particles of the present invention are composed of a conjugated diene-based polymer. This “conjugated diene-based polymer” refers to a polymer containing a conjugated diene-based monomer unit, and the homopolymerization of a conjugated diene-based monomer, or a conjugated diene-based monomer and other copolymerizable with it. Obtained by copolymerization of the following monomers. The proportion of the conjugated diene-based monomer unit in the conjugated diene-based polymer constituting the basic particles is preferably from 10 to 95% by weight, more preferably from 15 to 95% by weight.
９０90% by weight, more preferably 20-90% by weight. When the proportion of the conjugated diene-based monomer unit is less than 10% by weight, a sufficient effect may not be obtained when the polymer particles of the present invention are added to, for example, another resin or rubber.
On the other hand, when the proportion of the conjugated diene monomer unit exceeds 95% by weight, the polymerization reactivity decreases.

Examples of the conjugated diene-based monomer include “conjugated diene-based monomer used for obtaining rubbery polymer”
The above-mentioned compounds and the like can be used, and among them, 1,3-butadiene is particularly preferably used. This conjugated diene-based monomer can be copolymerized with the above-mentioned compounds exemplified as the “aromatic vinyl monomer used for obtaining the rubber-like polymer”. this house,
Styrene is particularly preferably used.

The conjugated diene-based polymer constituting the basic particles is copolymerized with a “functional group-containing monomer” having a functional group for chemically bonding the polymer to the siloxane-modified portion. Is preferred. Examples of the functional group include a carboxyl group, a cyano group, a hydroxyl group, a glycidyl group, an ester group, and the like. Examples of the functional group-containing monomers having these functional groups include the following.

(1) Cyano group-containing monomer Vinyl cyanide monomers such as (meth) acrylonitrile, crotonnitrile, and cinnamate nitrile; 2-cyanoethyl (meth) acrylate, 2-cyanopropyl (meth) acrylate , 3-cyanopropyl (meth) acrylate and the like. Among them, (meth) acrylonitrile is particularly preferably used.

(2) Carboxyl group-containing monomer (meth) acrylic acid, crotonic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, monomethyl maleate, monoethyl maleate, Carboxyl group-containing unsaturated monomers such as monomethyl itaconate, monoethyl itaconate and mono-2- (meth) acryloyloxyethyl hexahydrophthalate or anhydrides thereof; Among them, (meth) acrylic acid is particularly preferably used.

(3) Hydroxy group-containing monomers hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono ( Hydroxy (cyclo) alkyl mono (meth) acrylates such as meth) acrylate; 3-chloro-2-hydroxypropyl (meth) acrylate, 3-amino-2
-Substituted hydroxy (cyclo) alkylmono (meth) acrylates such as hydroxypropyl (meth) acrylate.

(4) Glycidyl group-containing monomers Allyl glycidyl ether, glycidyl (meth) acrylate, methyl glycidyl methyl acrylate, epoxidized cyclohexyl (meth) acrylate and the like.

(5) Ester group-containing monomer Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) A) (cyclo) alkyl (meth) acrylates such as acrylates; alkoxy (cyclo) alkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate and p-methoxycyclohexyl (meth) acrylate; vinyl acetate, vinyl propionate And vinyl esters such as vinyl versatate.

The preferred composition of the monomer unit in the conjugated diene polymer constituting the basic particles is 10 to 95% by weight (more preferably 15 to 95% by weight) of the conjugated diene monomer unit.
90% by weight, more preferably 20 to 85% by weight), 5 to 90% by weight of the aromatic vinyl monomer unit and / or vinyl cyanide monomer unit (more preferably 8 to 85% by weight).
% By weight, more preferably 10 to 80% by weight, and if necessary, other monomer units of 0 to 85% by weight (more preferably 0 to 60% by weight, further preferably 0 to 40% by weight). Is mentioned. If the proportion of the aromatic vinyl monomer unit and / or the vinyl cyanide monomer unit is less than 5% by weight, the effect of copolymerization is hardly exhibited. Also,
Since the base particles are too soft, when the rubber-like polymer composition of the present invention containing such polymer particles is added to, for example, a resin or rubber, it is difficult to exert the effect of improving the processability of the resin or rubber. Become.

Examples of the monomer forming the above “other monomer unit” include the following in addition to the above-mentioned functional group-containing monomer. N-methylolated unsaturated carboxylic amides such as N-methylol (meth) acrylamide and N, N-dimethylol (meth) acrylamide; aminoalkyl group-containing acrylamides such as 2-dimethylaminoethyl acrylamide; (meth) acrylamide; N-
Methoxymethyl (meth) acrylamide, N, N-ethylenebis (meth) acrylamide, maleic amide,
Amides or imides of unsaturated carboxylic acids such as maleimide; N-monoalkyl (meth) acrylamides such as N-methylacrylamide and N, N-dimethylacrylamide; N, N-dialkylacrylamides;

(Meth) acrylates containing an aminoalkyl group such as 2-dimethylaminoethyl (meth) acrylate; (meth) acrylates containing an aminoalkoxyalkyl group such as 2- (dimethylaminoethoxy) ethyl (meth) acrylate; Vinyl halide compounds such as vinyl chloride, vinylidene chloride and fatty acid vinyl ester; and polyfunctional (meth) acrylates such as diethylene glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate.

Before the formation of the siloxane-modified portion, the glass transition temperature (Tg) of the conjugated diene polymer constituting the basic particles is preferably 70 ° C. or lower, more preferably 50 ° C. or lower, still more preferably 30 ° C. or lower. It is below ° C. When Tg exceeds 70 ° C., when the rubber-like polymer composition of the present invention containing such polymer particles is added to, for example, another resin or rubber, a sufficient modifying effect may not be obtained. is there. Before forming the siloxane-modified portion, the toluene-insoluble content of the conjugated diene polymer constituting the basic particles is preferably 1% by weight or more, more preferably 5% by weight or more, and further preferably 1% by weight or more.
0% by weight or more. When the toluene insoluble content is less than 1% by weight, the effect of improving processability is hardly obtained when the polymer particles of the present invention containing such polymer particles are added to, for example, a resin or rubber. The toluene-insoluble content can be controlled by the polymerization temperature, the amount and type of the molecular weight regulator, the method of adding the monomer, and the like.

The basic particles in the siloxane-modified polymer particles can be obtained, for example, by a usual emulsion polymerization method using an aqueous medium. Here, “aqueous medium” means a medium containing water as a main component, and the content of water in the aqueous medium is usually 40% by weight or more, preferably 50% by weight or more. Other media, optionally used with water, include compounds such as esters, ketones, phenols, alcohols, and the like.

The conditions for the emulsion polymerization may be in accordance with known methods. For example, when the total amount of the monomers used is 100 parts, usually 100 to 500 parts of water is used, and the polymerization temperature is -20. The polymerization can be carried out at a temperature of from 100 to 100C (preferably from -10 to 90C, more preferably from -5 to 80C) and a polymerization time of from 0.1 to 30 hours (preferably from 2 to 25 hours). When this polymerization is carried out in the presence of a silicon compound having an alkoxysilyl group described later, the pH is adjusted to 3.
5 to 9 (more preferably 4 to 8, still more preferably 5 to
It is preferable to carry out under the condition of 7). If the pH is outside the above range, problems such as the formation of aggregates due to the hydrolysis-condensation reaction of the alkoxysilyl group during polymerization are likely to occur. Emulsion polymerization methods include a batch method in which monomers are charged at one time, a method in which monomers are divided or continuously supplied, a method in which a pre-emulsion of monomers is divided or continuously added, or these methods. A method in which the methods are combined stepwise can be adopted. In addition, one or two or more of molecular weight regulators, chelating agents, inorganic electrolytes, and the like used in ordinary emulsion polymerization can be used as necessary.

When an initiator is used for this emulsion polymerization, a persulfate such as potassium persulfate or ammonium persulfate; benzoyl peroxide, lauroyl peroxide, tert-butylperoxy-2-ethylhexanoate or the like; Organic peroxides: azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 2
An azo compound such as carbamoylazaisobutyronitrile; a redox system in which a radical emulsifier containing a radical emulsifying compound having a peroxide group is combined with a reducing agent such as sodium hydrogen sulfite or ferrous sulfate; Can be. When an emulsifier is used, one or more known anionic emulsifiers, nonionic emulsifiers, amphoteric emulsifiers and the like can be used, and a reactive emulsifier having an unsaturated double bond in the molecule can be used. Etc. may be used.

The molecular weight regulator used for the emulsion polymerization of the basic particles is not particularly limited. Specifically, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan , N-tetradecyl mercaptan, t-
Mercaptans such as tetradecyl mercaptan and thioglycolic acid; xanthogen disulfides such as dimethyl xanthogen disulfide, diethyl xanthogen disulfide and diisopropyl xanthogen disulfide; thiuram disulfides such as tetramethyl thiuram disulfide, tetraethyl thiuram disulfide and tetrabutyl thiuram disulfide; Halogenated hydrocarbons such as carbon tetrachloride, carbon tetrabromide and ethylene bromide; hydrocarbons such as pentaphenylethane and α-methylstyrene dimer; and acrolein, methacrolein, allyl alcohol and 2-ethylhexyl thioglycolate , Terpinolene, α-ternepine,
Examples thereof include γ-ternepine, dipentene, and 1,1-diphenylethylene. These can be used alone or in combination of two or more. Of these, mercaptans, xanthogen disulfides, thiuram disulfides, 1,1-diphenylethylene, α-methylstyrene dimer and the like are more preferably used.

The polymerization conversion of the monomer at the end of the emulsion polymerization is preferably at least 80%, more preferably at least 90%, further preferably at least 95%. The obtained basic particles are usually spherical particles, and preferably have an average particle diameter of 10 to 2,000 nm (more preferably, 20 to 1,000 nm). If the average particle size is outside this range, it is difficult to produce by emulsion polymerization.

[2-2] Siloxane-Modified Part A siloxane-modified part is formed on the surface and / or near the surface of the basic particles. Here, "surface and / or
"Or near the surface" means that the siloxane-modified portion is not completely buried in the base particles. Note that a siloxane-modified portion may also exist inside the basic particles. Further, the “siloxane-modified portion” refers to a functional group having one or more siloxane bonds (for example, an alkoxysilyl group, a hydroxysilyl group, and a polysiloxanyl group), or a structural part having this functional group (for example, one end of an alkyl group). To which an alkoxysilyl group is bonded). The siloxane-modified portion may exist on the surface of the basic particles and / or the entire area near the surface, or may be unevenly distributed on a part or a plurality of portions. Is preferably present. The ratio between the basic particles and the siloxane-modified portion is preferably 99.99 / 0.01 to 20/80 by weight, more preferably 99.5 / 0.5 to 25/75, and still more preferably. Is 99/1 to 30/70.
If the proportion of the siloxane-modified portion is less than the above range, the modifying effect may not be sufficiently obtained. On the other hand, if the proportion of the siloxane modified portion is too large, problems such as deterioration of the polymerization mode during the production of the polymer particles and generation of aggregates are likely to occur.

The siloxane-modified portion of the polymer particles (A) is chemically bonded (preferably covalently bonded) to the conjugated diene polymer forming the base particles, and is formed by an alkoxysilyl group, a hydroxysilyl group, or a polysiloxanyl. It has at least one of the groups, and preferably has at least an alkoxysilyl group. The at least one group may be directly bonded to the conjugated diene polymer or indirectly via a linking group such as an alkylene group. Further, the polymer particles (B)
Has a alkoxysilyl group, and the siloxane modified portion in the polymer particle (C) has at least one group of an alkoxysilyl group, a hydroxysilyl group, and a polysiloxanyl group (preferably, at least an alkoxysilyl group). . These siloxane-modified portions may or may not be chemically bonded to the conjugated diene-based polymer forming the base particles, but may be directly or indirectly chemically bonded. preferable.

The siloxane-modified portion may be (a) a silicon compound having at least one of an alkoxysilyl group, a hydroxysilyl group, and a polysiloxanyl group; It can be formed using a silicon compound having a functional group capable of generating at least one kind of the above group by causing a hydrolysis reaction, a hydrolysis condensation reaction, or the like with a compound, or the like. Here, the “silicon compound” refers to a compound having a silicon atom, and includes a so-called silane coupling agent. Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane. , Γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. Examples include a general silane coupling agent having a silyl group.

Examples of other silicon compounds include halogens such as methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, trifluoropropyltrichlorosilane, and heptadecafluorodecyltrichlorosilane. Silane compound: tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, Hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxy Can be used, and water glass; run heptadecaethyleneoxycetanol trifluoropropyl decyltrimethoxysilane, alkoxysilane compounds such as hexamethyldisilazane.

In forming the siloxane-modified portion chemically bonded to the polymer constituting the basic particles, the method of bonding the silicon compound to the polymer includes (1) adding the silicon compound to a reactive functional group in the polymer. How to react,
(2) a method in which a silicon compound is bonded to a polymer by a hydrogen abstraction reaction or the like; (3) a method in which a silicon compound having a polymerizable group is copolymerized with another monomer; There is a method of grafting a silicon compound by polymerizing a monomer.

In the above method (1), the reactive functional group for binding the silicon compound is preferably at least one selected from an amide group, an amine group, a carboxyl group, a sulfonic acid group, a glycidyl group and a hydroxyl group.
For the polymer having this reactive functional group, for the amide group, amine group, carboxyl group, glycidyl group, hydroxyl group, etc., for example, the above-mentioned monomer having these reactive functional groups is copolymerized or Can be obtained by grafting a compound having the group The polymer having a sulfonic acid group can be obtained, for example, by polymerizing a monomer in the presence of a reactive surfactant having this group. Further, by polymerizing a monomer using an initiator such as potassium persulfate, a polymer having a sulfate group bonded as an initiator residue can be obtained.

The amount of the reactive functional group contained in the polymer constituting the basic particles is 0.5 to 50% by weight of the polymer in terms of the compound used for introducing the reactive functional group. Preferably, it is 2 to 30% by weight. The basic particles in the polymer particles of the present invention may have the above-mentioned reactive functional group that is not used for bonding to the siloxane-modified part. Such polymer particles can be added to a resin or rubber to cause a crosslinking or graft reaction with them, and have good adhesion to a pigment or a substrate.

Among the siloxane-modified polymer particles used in the polymer composition of the present invention, those having a siloxane-modified portion having at least an alkoxysilyl group chemically bonded to the polymer constituting the basic particles are as follows: It can be suitably produced by the method (i) or (ii). (I) Using a basic particle made of a conjugated diene-based polymer having a functional group (a), a silicone compound having a functional group (b) and an alkoxysilyl group capable of reacting with the functional group (a) is used as the base particles. A siloxane-modified part by reacting with the functional group (a) of the above. (Ii) A method of forming a siloxane-modified portion by grafting a silicon compound having a functional group (c) and an alkoxysilyl group capable of being grafted to a conjugated diene polymer forming a basic particle to the conjugated diene polymer. .

Here, the functional group (a) of the polymer constituting the basic particles and the functional group (b) of the silicon compound
May be appropriately selected from an ester group, a glycidyl group, an alkoxy group, an amide group, an amine group, a carboxyl group, a sulfonic acid group, a sulfuric acid group, a hydroxyl group, and the like, and may be combined.
The functional group (c) of the silicon compound should be selected from an amide group, an amine group, a carboxyl group, a sulfonic acid group, a sulfate group, a glycidyl group, a hydroxyl group, a vinyl group, an acryloyl group, a methacrylol group, and a mercapto group. Can be. Furthermore, some or all of the alkoxysilyl groups bound to the base particles may be reacted with each other or with other compounds to form hydroxysilyl groups and / or polysiloxanyl groups.

[2-3] Regarding the protective layer The siloxane-modified polymer particles used in the polymer composition of the present invention cover at least a part of the siloxane-modified portion on the surface of the basic particle on which the siloxane-modified portion is formed. And a protective layer made of a conjugated diene polymer. The protective layer preferably covers 80% by area or more of the basic particles on which the siloxane-modified portion is formed (hereinafter, also referred to as “siloxane-modified basic particles”).
It is more preferable to cover 95% by area or more. Also,
The ratio of the total weight of the base particles and the siloxane-modified portion to the weight of the protective layer is preferably from 50/50 to 95/5, and more preferably from 60/40 to 90/10. The polymer constituting the protective layer may or may not be chemically bonded to the base particles and / or the siloxane-modified portion, but is preferably generally not bonded.

The protective layer can be formed, for example, by polymerizing a conjugated diene monomer and, if necessary, other monomers in the presence of siloxane-modified basic particles. For example, the monomer used for forming the protective layer or its pre-emulsion may be dropped at once, divided or continuously into an aqueous medium in which siloxane-modified basic particles are dispersed. The amount of the siloxane-modified basic particles used at this time is preferably 1 to 60% by weight (more preferably 2 to 50% by weight) based on the aqueous medium. When an initiator or an emulsifier is used for the polymerization, the same one as used in the production of the basic particles can be used. The conditions such as the polymerization time may be the same as in the production of the basic particles. When obtaining a siloxane-modified polymer particle having an alkoxysilyl group, the polymerization for forming the protective layer is performed at pH 3.5 to 9 (more preferably 4 to 8,
It is more preferable to carry out in steps 5 to 7). pH
Is out of the above range, a hydrolysis-condensation reaction of the alkoxysilyl group proceeds during polymerization, and a part or all of this group is easily lost. The average particle diameter of the siloxane-modified polymer particles having a protective layer is preferably from 10 to 10,000 nm (more preferably from 30 to 5,000 nm).
Particles having a particle size outside this range are difficult to produce by emulsion polymerization.

When the siloxane-modified polymer particles having the protective layer are added to, for example, a resin or rubber and kneaded, the protective layer is damaged or peeled off due to a rise in temperature or shear during kneading, and the siloxane-modified portion is exposed to the surface. When the siloxane-modified portion has a reactive functional group such as an alkoxysilyl group, the reactive functional group can be cross-linked or graft-reacted with a resin or rubber.

The amount of the siloxane-modified particles used in the rubbery polymer composition of the present invention [Polymer particles (A) to
(If (C) contains more than one, the total amount used)
Is from 3 to 500 parts by weight (preferably from 3 to 450 parts by weight, more preferably from 3 to 500 parts by weight, based on 100 parts by weight of the rubbery polymer).
400 parts by weight, more preferably 3 to 100 parts by weight). If the amount is too small, the desired effect cannot be obtained.
On the other hand, if the addition amount is too large, the cost increases, and the stability, tensile strength, abrasion resistance and the like may be reduced.

[3] Other components The composition according to claim 1 or 2 further comprises, in addition to the above essential components, a reinforcing agent, a crosslinking agent (however, in the case of sulfur-based crosslinking, vulcanization), Other additives such as a vulcanization accelerator, a vulcanization activator, an antioxidant, an activator, a plasticizer, a lubricant, and a filler can be contained in necessary amounts. Also,
The composition according to claim 3, wherein the reinforcing agent is also an essential component among the above, and the content thereof is 1-2 with respect to 100 parts by weight of the total amount of the rubbery polymer and the siloxane-modified polymer particles.
00 parts by weight (preferably 10 to 150 parts by weight, more preferably 30 to 120 parts by weight). The reinforcing agent is not particularly limited, and for example, a silica-based compound, carbon black, or the like can be used.

The silica-based compound is not particularly restricted but includes, for example, dry-process white carbon, wet-process white carbon, colloidal silica, and JP-A-62-6.
And precipitated silica disclosed in Japanese Patent No. 2838. Among them, wet-process white carbon containing hydrated silicic acid as a main component is particularly preferable. These silica compounds can be used alone or in combination of two or more.

Although the specific surface area of the silica compound is not particularly limited, it is usually 50 to 50% in terms of nitrogen adsorption specific surface area (BET method).
400 meters ² / g, preferably when 50 to 300 m ² / g, more preferably in the range of 70~300m ² / g, reinforcing property, is sufficiently accomplished suitably improved, such as abrasion resistance and heat build- . Here, the nitrogen adsorption specific surface area is AST
It is a value measured by the BET method according to MD4820-93.

The carbon black is not particularly limited. For example, furnace black, acetylene black, thermal black, channel black, graphite and the like can be used. Among these, furnace black is particularly preferred, and specific examples thereof include S
AF, ISAF, ISAF-HS, ISAF-LS, I
ISAF-HS, HAF, HAF-HS, HAF-L
Examples include various grades such as S and FEF. These carbon blacks can be used alone or in combination of two or more.

The nitrogen adsorption specific surface area of carbon black (N
₂ SA) is not particularly limited, but is usually 5 to 200 m ² /
g, preferably in the range of 50 to 150 m ² / g, more preferably in the range of 80 to 130 m ² / g, since the tensile strength and abrasion resistance are improved at a high level, which is suitable. The DBP adsorption amount of carbon black is not particularly limited,
Usually 5 to 300 ml / 100 g, preferably 50 to 20
0 ml / 100 g, more preferably 80-160 ml /
When it is in the range of 100 g, the tensile strength and abrasion resistance are improved at a high level, which is preferable.

As carbon black, JP-A-5-23
No. 0290, the adsorption (CTAB) specific surface area of cetyltrimethylammonium bromide is 110 to 110.
Abrasion resistance can be further improved by using high-structure carbon black having a DBP (24M4DBP) oil absorption of 110 to 130 ml / 100 g after repeatedly applying compression at 170 m ² / g at a pressure of 24,000 psi four times. .

In order to achieve the object of the present invention to a high degree,
As the reinforcing agent, it is preferable to use the silica compound alone or in combination with the silica compound and carbon black. The mixing ratio when the silica compound and the carbon black are used in combination is appropriately selected according to the use and purpose, but usually, the silica compound: carbon black =
10: 90-99: 1, preferably 30: 70-95:
5, more preferably 50:50 to 90:10 (weight ratio)
It is. When a silica-based compound is used as a reinforcing agent, the balance between processability and reinforcing property can be further improved by using a silane coupling agent in combination as needed. The amount of the silane coupling agent is preferably less than 20% by weight, more preferably less than 10% by weight, based on the weight of the silica-based compound. Preferred silane coupling agents include the silane coupling agents exemplified as silicon compounds for forming the siloxane-modified portion of the siloxane-modified polymer particles.

The crosslinking agent is not particularly restricted but includes, for example, sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur and highly dispersible sulfur; and sulfur halide such as sulfur monochloride and sulfur dichloride. Organic peroxides such as dicumyl peroxide and di-t-butyl peroxide; quinone dioximes such as p-quinone dioxime and p, p'-dibenzoylquinone dioxime; triethylenetetramine and hexamethylenediaminecarbamate , 4,4'-
Organic polyamine compounds such as methylenebis-o-chloroaniline; alkylphenol resins having a methylol group; and the like. Of these, sulfur is preferred, and powdered sulfur is particularly preferred. These crosslinking agents are used alone or in combination of two or more.

The compounding ratio of the crosslinking agent is 100
It is usually in the range of 0.1 to 15 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to parts by weight. When the compounding ratio of the cross-linking agent is in this range, it is particularly preferable because it has excellent tensile strength and abrasion resistance, and also has excellent properties such as heat resistance and residual strain.

Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolesulfenamide,
-T-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N, N'-diisopropyl-2-
Sulfenamide-based vulcanization accelerators such as benzothiazolesulfenamide; guanidine-based vulcanization accelerators such as diphenylguanidine, diortitolylguanidine, ortho-tolylbiguanidine; Thiourea-based vulcanization accelerators such as thiourea and trimethylthiourea; 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc salt, 2-mercaptobenzothiazole sodium salt,
Thiazole vulcanization accelerators such as mercaptobenzothiazole cyclohexylamine salt and 2- (2,4-dinitrophenylthio) benzothiazole; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, Thiuram-based vulcanization accelerators such as dipentamethylenethiuram tetrasulfide; sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium di-n-butyldithiocarbamate, lead dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, -Zinc n-butyldithiocarbamate, zinc pentamethylenedithiocarbamate, zinc ethylphenyldithiocarbamate, Acceleration of dithiocarbamic acid vulcanization such as tellurium tildithiocarbamate, selenium dimethyldithiocarbamate, selenium diethyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, diethylamine diethyldithiocarbamate, piperidine pentamethylenedithiocarbamate, and pipecoline methylpentamethylenedithiocarbamate. Vulcanization accelerators such as sodium isopropylxanthogenate, zinc isopropylxanthogenate, and zinc butylxanthogenate; and the like.

Each of these vulcanization accelerators is used alone.
Alternatively, two or more kinds are used in combination, but those containing at least a sulfenamide-based vulcanization accelerator are particularly preferable. The compounding ratio of the vulcanization accelerator is 100% for the rubbery polymer.
It is usually in the range of 0.1 to 15 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to parts by weight.

The vulcanization activator is not particularly limited. For example, higher fatty acids such as stearic acid and zinc oxide can be used. As zinc oxide, for example,
It is preferable to use those having a high surface activity and a particle size of 5 μm or less.
Active zinc white of 5 to 0.2 μm and zinc white of 0.3 to 1 μm can be exemplified. As the zinc oxide, a zinc oxide surface-treated with an amine-based dispersant or wetting agent can be used.

These vulcanization activators can be used alone or in combination of two or more.
The mixing ratio of the vulcanization activator is appropriately selected depending on the type of the vulcanization activator. For example, when a higher fatty acid is used, usually 0.05 to 100 parts by weight of the rubbery polymer is used.
15 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight. When zinc oxide is used, it is usually 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the rubbery polymer.
More preferably, it is 0.5 to 2 parts by weight. When the mixing ratio of zinc oxide is within this range, properties such as workability, tensile strength, and wear resistance are highly balanced and suitable.

Examples of other compounding agents include, for example, bis- (3- (trimethoxysilyl) propyl) disulfide and bis- (3
-(Triethoxysilyl) propyl) disulfide, γ
Coupling agents such as silane coupling agents such as trimethoxysilylpropyl dimethylthiocarbamyl tetrasulfide and γ-trimethoxysilylpropyl benzothiazyl tetrasulfide; activators such as diethylene glycol, polyethylene glycol and silicone oil; calcium carbonate; Fillers such as talc and clay; process oils and waxes.

[4] Applications The rubber-like polymer composition of the present invention can be used for rubber products in various fields by utilizing the above-mentioned properties. For example,
Rubber industrial products such as rubber rolls, milling rolls, belts, hoses, sponges, rubber plates, rubberized cloth; footwear components such as transparent bottoms, general color bottoms, sponge bottoms; treads, base treads, sidewalls, rubber chafers And tire members for large vehicles such as inner liners and general vehicles, and sanitary materials such as sanitary skins and medical supplies.

[5] Method for producing rubber-like polymer composition The rubber-like polymer composition of the present invention can be obtained by kneading each component according to a conventional method. For example, after mixing a siloxane-modified polymer particle and, if necessary, a reinforcing agent and other additives (excluding a crosslinking agent and a vulcanization accelerator) with a rubbery polymer, the mixture is mixed with a crosslinking agent and a vulcanization accelerator. The rubbery polymer composition can be obtained by mixing the agents. Further, after mixing the aqueous dispersion of the siloxane-modified polymer particles and the aqueous dispersion of the rubber-like polymer at a predetermined ratio, coagulated according to a conventional method, washed and dried if necessary, and obtained by drying. A wet mixed rubber in which siloxane-modified polymer particles are dispersed in a rubber polymer in advance may be prepared, and the wet mixed rubber may be subjected to a crosslinking treatment or the like to obtain the rubber polymer composition of the present invention. Siloxane-modified polymer particles and additives (provided that
The mixing temperature of the rubber-like polymer and the cross-linking agent and the vulcanization accelerator are usually 80 to 200 ° C, preferably 100 to 190 ° C,
The mixing temperature is more preferably 140 to 180 ° C, and the mixing time is usually 30 seconds or more, and preferably 1 to 30 minutes. Mixing of a crosslinking agent and a vulcanization accelerator is usually 100 ° C. or less,
It is preferably carried out after cooling to room temperature to 80 ° C., and then press-crosslinking usually at a temperature of 120 to 200 ° C., preferably 140 to 180 ° C. to obtain the rubbery polymer composition of the present invention.

[0068]

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on weight unless otherwise specified.

(1) Production of aqueous dispersion of siloxane-modified polymer particles (1-1) Production of aqueous dispersion of basic particles In an autoclave equipped with a stirrer and capable of controlling temperature, 315 parts of water, dodecyldiphenyl oxide sulfone 5.0 parts of sodium silicate, 0.3 part of potassium persulfate, 0.1 part of sodium bisulfite and the first-stage monomer components shown in Table 1 were charged together and reacted at 70 ° C. for 3 hours. It was confirmed that the polymerization conversion was 80% or more. Thereafter, the second-stage monomer components shown in Table 1 were charged all at once and reacted at the same temperature for 15 hours to obtain aqueous dispersions A-1 and A-2 of the basic particles.

In an autoclave equipped with a stirrer and capable of controlling the temperature, 220 parts of water, 6.0 parts of sodium dodecyldiphenyloxidesulfonate, 0.033 part of sodium salt of EDTA, and 0.1 part of sodium formaldehyde were added.
053 parts, ferrous sulfate heptahydrate 0.013 parts, paramenthane hydroperoxide 0.053 parts and the monomer components shown in Table 2 were charged all at once and reacted at 10 ° C for 9 hours. After confirming that the polymerization conversion rate is 90% or more,
By adding 0.2 part of N, N-diethylhydroxylamine as a polymerization terminator to terminate the reaction, aqueous dispersions A-3 and A-4 of basic particles were obtained. The final polymerization conversion, the average particle diameter of the basic particles, the Tg, and the toluene-insoluble content of the aqueous dispersions A-1 to A-4 are shown in Tables 1 and 2.

The average particle size, Tg and toluene insoluble content were measured by the following methods. Average particle size Otsuka Electronics Co., Ltd., "Laser particle size analysis system PA
R III ". Glass transition temperature After the obtained basic particles were purified and dried, they were measured according to the ASTM method using a differential scanning calorimeter (DSC: manufactured by DuPont). Toluene-insoluble content The obtained aqueous dispersions A-1 to A-4 of the base particles were adjusted to pH 8.0.
After solidification with isopropanol, the obtained solid was washed with methanol and dried. About 0.3 g of this solid content (total solid content A) was immersed in 100 ml of toluene at room temperature for 20 hours. Filtration was performed using a bi-qualitative filter paper. A part (Cml) of the filtrate was accurately collected and evaporated and coagulated, and the obtained residual solid content (toluene-soluble content B) was weighed, and the toluene-insoluble content was determined by the following formula. Toluene insoluble matter (%) = [{AB-(100 / C)}
/ A] × 100 (%)

(1-2) Production of Aqueous Dispersion of Polymer Particles (A) An aqueous dispersion of basic particles of the type and amount (in terms of solid content) shown in Table 3 was adjusted to pH 6.0 with 1N hydrochloric acid. The silane coupling agents shown in Table 3 were continuously added dropwise with stirring in a reactor at 25 ° C. in a nitrogen atmosphere, and the mixture was stirred at the same temperature for 0.5 hour. After that, put the reactor in a water bath for 65 minutes.
C. for 4.0 hours, then cooled to room temperature, and removed aggregates using a 200-mesh wire net to obtain siloxane-modified polymer particles (corresponding to the polymer particles (A) according to claim 1). A) to obtain aqueous dispersions S-1 to S-4.
Table 3 shows the average particle diameter of the siloxane-modified polymer particles.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

(1-3) Production of aqueous dispersion of polymer particles (B) Using aqueous dispersions A-1 and A-2 of basic particles, aqueous dispersions S-5 and S-6 of siloxane-modified polymer particles were prepared. Manufactured. That is, an aqueous dispersion of basic particles of the type and amount (in terms of solid content) shown in Table 4 was adjusted to pH 6.0 with 1N hydrochloric acid,
The silane coupling agents shown in Table 4 were continuously added dropwise with stirring in a reactor in a nitrogen atmosphere at 25 ° C., and the mixture was stirred at the same temperature for 0.5 hour. Thereafter, the reactor was kept in a water bath at 65 ° C. for 2.0 hours, and then cooled to room temperature. After cooling, methyltriethoxysilane was continuously added dropwise, and the mixture was stirred at the same temperature for 0.5 hour, then placed in a water bath and kept at 60 ° C. for 5.0 hours to generate a polysiloxanyl group. Thereafter, the mixture was cooled to room temperature and aggregates were removed with a 200-mesh wire gauze, and an aqueous dispersion S-5 of siloxane-modified polymer particles (corresponding to the polymer particles (B) according to claim 1). , 6. Table 4 also shows the average particle diameter of the siloxane-modified polymer particles.

[0077]

[Table 4]

(1-4) Production of aqueous dispersion of polymer particles (C) Using aqueous dispersions A-1 to A-4 of basic particles, an aqueous dispersion S- of siloxane-modified polymer particles having a protective layer was prepared. 7-1
0 was produced. That is, the type and amount (in terms of solid content) of the aqueous dispersion shown in Table 5 were adjusted to pH 6.0 with 1N hydrochloric acid, and stirred in a reactor at 25 ° C. in a nitrogen atmosphere.
Was dropped continuously and stirred at the same temperature for 0.5 hour. Thereafter, the reactor was placed in a water bath and kept at 70 ° C. for 4.0 hours, and then cooled to room temperature, and aggregates were removed using a 200-mesh wire net, thereby obtaining an aqueous dispersion of siloxane-modified polymer particles. D-
1-4 were obtained. The solid content concentration of this aqueous dispersion and the average particle size of the siloxane-modified polymer particles are also shown in Table 5. Next, a protective layer is formed on the siloxane-modified polymer particles. That is, in the autoclave, the amounts shown in Table 6 of the aqueous dispersions D-1 to D-4 (in terms of solid content), 0.3 parts of potassium persulfate, 0.1 part of sodium bisulfite, and the monomers shown in Table 6 An aqueous dispersion of siloxane-modified polymer particles having a protective layer (corresponding to the polymer particles (C) according to claim 1) is prepared by charging the components at a time and reacting at 70 ° C for 5.0 hours. S-7 to 10 were obtained. Table 6 shows the final polymerization conversion and the average particle size of the polymer particles having the protective layer.

[0079]

[Table 5]

[0080]

[Table 6]

(2) Production of Conjugated Diene Rubber A polymerization vessel was charged with 200 parts of water, 4.5 parts of a rosin acid soap, and a monomer having the composition shown in Table 7. Thereafter, the temperature of the polymerization vessel was set at 5 ° C., and p-
The polymerization was stopped by adding 0.1 part of menthane hydroperoxide, 0.07 part of sodium ethylenediaminetetraacetate, 0.05 part of ferrous sulfate heptahydrate, and 0.15 part of sodium formaldehyde sulfoxylate. Thereafter, unreacted monomers were recovered by steam stripping to obtain aqueous dispersions R-1 to R-4 of a conjugated diene rubber (rubber-like polymer).

[0082]

[Table 7]

(3) Wet mixing of siloxane-modified polymer particles with conjugated diene rubber Aqueous dispersions of siloxane-modified polymer particles S-1 to S-10
And aqueous dispersions R-1 to R-4 of the conjugated diene rubber were mixed so as to have a weight ratio shown in Table 8 in terms of solid content. Thereafter, the total amount (solid content) of the siloxane-modified polymer particles and the conjugated diene rubber contained in the mixed aqueous dispersion
Aroma oil was blended in an amount of 37.5 parts per 100 parts, coagulated with sulfuric acid and salt to form crumbs, dried with a hot air drier, and contained rubber in the weight ratio shown in Table 8. The wet mixed rubbers of Examples 1 to 15 were obtained. According to this wet mixing, the siloxane-modified polymer particles and the conjugated diene-based rubber can be more uniformly mixed as compared with the case of mixing in a dry manner.

(4) Preparation of Rubber Composition and Crosslinked Rubber The wet mixed rubber obtained above was kneaded by a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) according to the compounding recipe shown in Table 8, and the mixture was mixed with each other. 1 to 15 rubbery polymer compositions were obtained. Thereafter, crosslinking was performed at 160 ° C. for 20 minutes by a crosslinking press to obtain crosslinked rubbers of Examples 1 to 15. On the other hand, only the conjugated diene rubber was used without using the siloxane-modified polymer particles, or in the same manner as in Examples 1 to 15, except that the amount of the siloxane-modified polymer particles used was within the range of the present invention, The rubbery polymer compositions of Comparative Examples 1 to 9 were prepared according to the formulation shown in Table 8, and were crosslinked in the same manner as in Examples. The physical properties of the rubbery polymer compositions and crosslinked rubbers of Examples 1 to 15 and Comparative Examples 1 to 9 were measured. The results are also shown in Table 8.

The ingredients used in the above formulation are shown below. Silica; manufactured by Nippon Silica Co., Ltd., trade name "Nipsil VN
3 "Silane coupling agent; Degussa Corporation, trade name" Si6
9 "Toshiba Silicone Co., Ltd., product name" TSL8380 "Anti-aging agent; Ouchi Shinko Chemical Co., Ltd., trade name" Nocrack 810NA "Vulcanization accelerator (a); Ouchi Shinko Chemical Co., Ltd., trade name "Noxeller CZ" Vulcanization accelerator (b); manufactured by Ouchi Shinko Chemical Co., Ltd., trade name "Noxeller D" carbon black; manufactured by Mitsubishi Chemical Corporation, trade name "Diablack N220"

The physical properties of each monomer were measured by the following methods. Processability Evaluated by the winding property of the rubber-like polymer composition around the roll when the composition was kneaded with the roll. The evaluation criteria are as follows. 10 points: no lifting from the roll surface (excellent) 8 points: slight lifting to the roll surface to some extent (good) 5 points: wrapped around the roll, but easily lifted (poor) 1 point; hardly wrapped around the roll (very poor) Mooney viscosity [(ML _{1 + 4} (100 ° C.)] Measured at 1000 ° C. in accordance with JIS K 6300
The measurement was performed under the conditions of preheating for 1 minute and measurement for 4 minutes. Tensile measurement According to JIS K 6301, using a No. 3 type test piece,
The elongation at break EB (%) and the tensile strength TB (MPa) were measured under the conditions of a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min. Abrasion resistance Measured using a pico abrasion tester according to ASTM D2228. The evaluation results are expressed as severe wear (0 points) to extremely small wear (5 points).

[0087]

[Table 8]

According to the evaluation results shown in Table 8, Examples 1 to
It can be seen that all of the rubber-like polymer compositions of No. 15 are excellent in workability and abrasion resistance, and the physical properties of the crosslinked rubber are good. On the other hand, Comparative Examples 1 to 4 using only conjugated diene rubbers
In No. 4, the processability of the rubbery polymer composition was low, and the tensile strength and abrasion resistance of the crosslinked rubber were insufficient. In Comparative Example 5 in which the amount of the siloxane-modified polymer particles was small, the effect of improving the processability was insufficient. In Comparative Examples 6 to 9 using the polymer particles A-1 to A-4 before the siloxane modification, some of the workability was improved, but all of them had insufficient wear resistance.

[0089]

The rubbery composition of the present invention has improved moldability by containing predetermined siloxane-modified polymer particles. Further, since the dispersibility of the additive is improved, the effect of adding the additive is sufficiently exhibited. The rubber composition of the present invention is excellent in heat generation, tensile strength, abrasion resistance, moldability, and the like, particularly when the additive is a reinforcing agent composed of a silica-based compound.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 15/00 C08L 15/00 F term (Reference) 4J002 AC01W AC03W AC06W AC07W AC08W AC11W AC11X BB15W BB18W BB24W BB27W BD12W BG04W BN14X BN21X BP01W CK02W CP03W DA036 DJ016 FD016 FD140 FD150 FD200 GB01 GC00 GN01 4J011 AA05 DA01 PA54 PB06 PB40 PC02 PC06 4J026 AA11 AA12 AA13 AA14 AA17 AA67 AA68 BAA11AC11 BA10AC11 BA10AC11 JA51

Claims (4)

[Claims] At least one siloxane-modified polymer particle selected from the following polymer particles (A), (B) and (C) per 100 parts by weight of a rubbery polymer.
A rubber-like polymer composition comprising parts by weight. [Polymer particles (A)] Consisting of basic particles composed of a conjugated diene polymer and siloxane-modified portions formed on the surface and / or near the surface of the basic particles, wherein the siloxane-modified portions are formed of the polymer And a siloxane-modified polymer particle chemically bonded to at least one of an alkoxysilyl group, a hydroxysilyl group, and a polysiloxanyl group. [Polymer particles (B)] Siloxane-modified polymer particles formed by forming a siloxane-modified portion having an alkoxysilyl group on the surface and / or in the vicinity of the surface of basic particles made of a conjugated diene polymer. [Polymer Particle (C)] A siloxane-modified portion having at least one group of an alkoxysilyl group, a hydroxysilyl group, and a polysiloxanyl group is formed on the surface and / or near the surface of the basic particle made of a conjugated diene polymer. Further, siloxane-modified polymer particles comprising a conjugated diene-based polymer and further forming a protective layer covering at least a part of the siloxane-modified portion. 2. The conjugated diene-based polymer constituting the basic particles contains at least 10 to 95% by weight of a conjugated diene-based monomer unit, at least an aromatic diene-based monomer unit and a vinyl cyanide-based monomer unit. The rubbery polymer composition according to claim 1, comprising 5 to 90% by weight and 0 to 85% by weight of other monomer units. 3. A reinforcing agent 1 based on 100 parts by weight of the total of the rubbery polymer and the siloxane-modified polymer particles.
3. The composition according to claim 1, further comprising up to 200 parts by weight.
A rubber-like polymer composition as described in the above. 4. The rubber-like polymer composition according to claim 3, wherein the reinforcing agent comprises a silica compound.