JPH0196233A - Rubber composition for tire - Google Patents

Abstract

PURPOSE:To obtain the titled composition having improved impact resilience, abrasion resistance, low heat build-up, etc., and suitable for tire tread, etc., by compounding a rubber raw material containing a diene (co)polymer at a specific ratio with carbon black and a vulcanizing agent. CONSTITUTION:The objective composition can be produced by compounding (A) 100pts.wt. of a rubber raw material containing >=20wt.% of a diene (co)polymer containing 70-90wt.% of trans-bond in diene part and produced by modifying a diene (co)polymer with at least one compound selected from an isocyanate compound and/or isothiocyanate compound, isocyanuric acid derivative and/or thiocarbonyl-containing compound corresponding to said derivative, a urea compound, an amide compound and/or imide compound, and N-alkyl-substituted oxazolidinone compound, a pyridyl-substituted ketone compound and/or pyridyl- substituted vinyl compound and a lactam compound with (B) 20-100pts.wt. of carbon black and (C) 0.1-5pts.wt. of a vulcanizing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a tire rubber composition suitable for tire treads and the like.

[Conventional technology]

In recent years, due to the desire for energy conservation in automobiles, various attempts have been made to reduce the rolling resistance of tire rubber members, particularly tire tread rubber members. In order to reduce the rolling resistance of the tire, it is sufficient to reduce the energy loss of the vulcanized rubber, and the evaluation indicators for vulcanized rubber include rebound resilience at 50 to 80°C, t at 50 to 80°C.
and δ, Gutdrich heating, etc. are used, and the raw rubber has high rebound elasticity at 50 to 80°C, or
Rubbers with a small tan δ at ~80°C or with a small Gradlich heat generation are preferred.

In recent years, styrene-butadiene copolymers of various structures polymerized with organolithium catalysts and styrene-butadiene copolymers whose polymer terminals are modified with functional groups have been proposed as raw material rubbers with high impact resilience.

For example, styrene-butadiene copolymer obtained by modifying or coupling the polymer terminal with a tin compound, styrene-butadiene copolymer obtained by modifying the polymer terminal with a nitrogen-containing compound such as an isocyanate compound, an oxazolidinone compound, or a dialkylaminobenzophenone compound. Copolymers and the like have been proposed.

However, the styrene-butadiene copolymer obtained using an organolithium catalyst as an initiator has a range of 10 to 90% vinyl bonds and 5 to 70% trans bonds in the butadiene moiety by adding a Lewis base or other additives. However, compared to, for example, a styrene-butadiene copolymer obtained by emulsion polymerization with 17% vinyl bonds and 67% trans bonds, the tensile strength of the vulcanizate is insufficient, and the wear resistance is poor. They were also inferior in terms of gender.

In addition, the styrene-butadiene copolymer whose polymer terminal is modified with a functional group as described above does not have elongated crystallinity, so
It has a problem of low high temperature tensile strength.

[Problem that the invention seeks to solve]

The present invention was made against the background of the above-mentioned conventional technical problems, and an object of the present invention is to provide a rubber composition for tires that simultaneously satisfies rebound resilience, abrasion resistance, mechanical properties, and low heat build-up.

[Means for solving problems]

That is, the present invention provides (a) an isocyanate compound and/or an isothiocyanate compound, (a) an isocyanuric acid derivative and/or a thiocarbonyl-containing compound corresponding to the derivative, (c) a urea compound, (d) an amide compound, and/or or modified with at least one compound selected from the group of imide compounds, (e) N-alkyl-substituted oxazolidinone compounds, (f) pyridyl-substituted ketone compounds and/or pyridyl-substituted vinyl compounds, and (g) lactam compounds, 20% by weight of a diene (co)polymer with a trans bond content of 70% to 90% in the diene portion
To 100 parts by weight of the rubber raw material containing the above, 20 to 100 parts by weight of carbon blank and 0.0 parts by weight of vulcanizing agent.
The present invention provides a rubber composition for tires, characterized in that it contains 1 to 5 parts by weight.

When obtaining a rubber composition for tires, the present invention further improves initial properties such as rebound resilience, abrasion resistance, low heat generation, and mechanical properties by reacting a specific compound with a polymer immediately after polymerization. An improved diene (co)polymer is used as the raw material rubber.

The catalyst system used in producing the diene (co)polymer used in the present invention is preferably an organic magnesium compound and/or an alkali metal compound (hereinafter referred to as the component (h)). , (1) Organic alkaline earth metal compounds (excluding organic magnesium compounds,
(hereinafter referred to as "component (L)"), and 0) an organoaluminum compound (hereinafter referred to as "component (J)") as the main components.

First, examples of the organomagnesium compound which is one of the compounds of component (h) include dicycloalkylmagnesium compounds and diallylmagnesium compounds.
Specifically, dimethylmagnesium, dipropylmagnesium, diptylmagnesium, ethylbutylmagnesium, ethylhexylmagnesium, didecylmagnesium, dioctylmagnesium, didecylmagnesium,
Didodecylmagnesium, dicyclohexylmagnesium, dicyclopentylmagnesium, diphenylmagnesium, ditolylmagnesium, ethylmagnesium bromide, ethylmagnesium chloride, allylmagnesium bromide, propylmagnesium bromide, n-butylmagnesium chloride, phenylmagnesium bromide, phenylmagnesium such as iodide.

Further, as the organic alkali metal compound which is the other compound of component (h), ethyllithium, propyllithium, n-butyllithium, 5ec-butyllithium, m-
Butyllithium, hexyllithium, 1,4-dilithiobutane, alkyllithium such as the reaction product of butyllithium and divinylbenzene, alkylene dilithium, phenyllithium, stilbenzenedilithium, isopropenylbenzenedilithium, sodium naphthalene, potassium naphthalene, lithium Examples include naphthalene.

These organomagnesium compounds or organic alkali metal compounds (hl components) can be used alone or in combination.

(The amount of the hl component used varies depending on the molecular weight and Mooney viscosity of the produced (co)polymer, but is usually 0.05 to 10 mmol, preferably 0.1 to 8 mmol, per 100 g of monomer.

In addition, the organic alkaline earth metal compounds (excluding the above magnesium compound) used as component (1) include:
Organometallic compounds of barium, calcium, or strontium, specifically barium jetoxide, barium jetoxide, barium diisopropoxide, barium diphenoxide, barium di-5ec-butoxide, barium diphenoxide, barium di(l,1- dimethylpropoxide), barium di(1,2-dimethylpropoxide), barium di(l,1-dimethylbutoxide), barium di(1,1-dimethylbentoxide),
Barium di(2-ethylhexanoxide), barium di(1-methylhebutoxide), barium diphenoxide, barium di(p-methylphenoxyto), barium di(p-butylphenoxyto), barium di(0-methylphenoxyto), Barium di(p-octylphenoxide), barium di(p-nonylphenoxide), barium di(p-dodecyl phenoxide), barium di(α
-naphthoxide), barium di(β-naphthoxide),
Barium (O-methoxyphenoxide), barium di(
m-methoxyphenoxide), barium di(p-methoxyphenoxide), barium (0-ethoxyphenoxide), barium di(4-methoxy-1-naphthoxide)
Examples include barium compounds such as (however,
R1-R5 are a hydrogen atom or an alkyl group or an alkoxyl group having 1 to 20 carbon atoms) is preferable from the viewpoint of performance.

Furthermore, a partial hydrolyzate in which 0.1 to 0.5 equivalents of alkoxide groups or phenoxyto groups per barium atom are substituted with hydroxy groups may also be used.

Further, as the component (1), a calcium compound or a strontium compound corresponding to the barium compound can be mentioned.

(The amount of component 11 used is 0.01 to 20 equivalents, preferably 0.1 to 10 equivalents, per gram atom of the metal atom of the magnesium compound or organic alkali metal compound used as component (h).

Furthermore, the organoaluminum compound that is component (J) is
General formula AIR"R'R" (where Rh, R'
r and R8 are the same or different and are a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and are not all hydrogen atoms, specifically trimethylaluminum, triethylaluminum, triisopropyl Examples include aluminum, tributyl aluminum, triisobutyl aluminum, trihexyl aluminum, tricyclohexyl aluminum, diisobutyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, ethyl aluminum sibide, propyl aluminum sibide, isobutyl aluminum sibide.

The amount of component U) used is 0.02 to 2.0 equivalents, preferably 0.5 to 1.0 equivalent per gram atom of the metal atom of the magnesium compound or organic alkali metal compound used as component (h). It is equivalent.

As catalyst components, the above (hl, (1),
In addition to component ('') and (k), a conjugated diene may be used as necessary in a ratio of 0.05 to 20 mol per 1 mol of component ((k).The conjugated diene used for catalyst preparation is ,
The same monomers used for polymerization, such as isoprene, 1.3-butadiene, and 1.3-pentadiene, are used.

Although the conjugated diene is not essential as a catalyst component, the catalytic activity of the catalyst component is further improved by using it in combination.

To prepare the catalyst, for example, components (h) to U) dissolved in an inert solvent are reacted, and if necessary, a conjugated diene is reacted. At that time, the order of addition of each component may be arbitrary. It is preferable to mix, react, and age each of these components in advance in order to improve polymerization activity and shorten the polymerization initiation induction period. good.

Examples of polymerization solvents include inert organic solvents, such as aromatic hydrocarbon solvents such as benzene, toluene, and xylene, aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-butane, and cyclohexane, and methyl cyclohexane. Alicyclic hydrocarbon solvents such as penkune, cyclohexane, and mixtures thereof can be used.

The polymerization temperature is usually -20°C to 150°C, preferably 30 to 120°C. The polymerization reaction may be carried out batchwise or continuously.

Note that the monomer concentration in the solvent is usually 5 to 50% by weight,
Preferably the device at 10-35% heavy visibility.

In addition, in order to prevent deactivation of the catalyst system and polymer of the present invention in order to produce the copolymer, it is necessary to minimize the incorporation of compounds with deactivation effects such as oxygen, water, or carbon dioxide into the polymerization system. Consideration is required.

Conjugated dienes that can be polymerized with the catalyst system of the present invention include 1.
3-butadiene, isoprene, 2,3-dimethyl-1,
Examples include 3-butadiene, 1,3-pentadiene, myrcene, etc., which can be used alone or in combination of two or more, with 1,3-butadiene being particularly preferred.

In addition, the diene (co)polymer used in the present invention includes:
In addition to the conjugated dienes, there are vinyl aromatic compounds such as styrene, α-methylstyrene, p-methylstyrene, 0-methylstyrene, p-butylstyrene, and vinylnaphthalene, as well as vinylpyridine, acrylonitrile, methacrylonitrile, and methyl(methacrylonitrile). ) Acrylates, acrylic esters, etc. can be copolymerized, preferably vinyl aromatic compounds, especially styrene is most preferred.

In the present invention, first, a conjugated diene is homopolymerized or an aromatic vinyl compound such as styrene and a conjugated diene are copolymerized in an inert organic solvent using a catalyst system consisting of the components (N to 0). (Co)polymers can be produced. The (co)polymer thus obtained has 70 to 90% trans bonds in the diene moiety, preferably 75%
It is preferable that the content of the bound aromatic vinyl compound is 5 to 45% by weight, more preferably 10 to 35% by weight, and that the styrene chains are random. If the trans bond in the diene portion is less than 70%, the tensile strength and abrasion resistance will be poor, while if it exceeds 90%, the anti-ta elasticity will be reduced. Further, the aromatic vinyl compound content of the produced (co)polymer is preferably 5 to 45% by weight from the viewpoint of the tensile strength and impact resilience of the vulcanized rubber.

Furthermore, the produced (co)polymer has random styrene chains, for example 1. M.

The oxidative decomposition method of Kolthoff et al. (J, Po 1 y
merSci, 1.429 (1946)) in the copolymer is 10% by weight or less, preferably 5% by weight or less, and if the long chain block polystyrene exceeds 10% by weight, addition The rebound resilience of sulfur is reduced.

The rubber composition for tires of the present invention is a novel (co)polymer that is modified by reacting a specific compound to the polymer end of the (co)polymer obtained in this way and introduces a functional group.
It is made by blending a co)polymer.

This modification provides the effect of improving anti-↑Ω elasticity, abrasion resistance, heat generation properties, and mechanical properties.

In the present invention, the specific compounds to be reacted after producing the (co)polymer include (a) an isocyanate compound and/or an isothiocyanate compound (hereinafter referred to as "component (a)"), (b) an isocyanuric acid derivative, and / or a thiocarbonyl-containing compound corresponding to the derivative (hereinafter referred to as “
(b) component"), (c) urea compound (hereinafter referred to as "(c) component"), (c) urea compound (hereinafter referred to as "(c
(d) amide compound and/or imide compound (hereinafter referred to as "(d) component"), (e) N
-Alkyl-substituted oxazolidinone compound (hereinafter referred to as “(e)
(hereinafter referred to as "component (f)"), (fl pyridyl-substituted ton compound and/or pyridyl-substituted vinyl compound (hereinafter referred to as "component (f)"), and (gl lactam compound (hereinafter referred to as "component (f)"),
At least one compound selected from the group (referred to as "component (g)") can be mentioned.

Among these compounds, specific examples of the isocyanate compound or isothiocyanate compound that is component (a) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polymeric Types of diphenylmethane diisocyanate, (c-MDI), phenyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, butyl isocyanate, 1,3,5-benzene triisocyanate, phenylisothiocyanate, phenyl- Examples include 1,4-diisothiocyanate.

(Specific examples of isocyanuric acid derivatives that are bl components and thiocarbonyl-containing compounds corresponding to these derivatives include carbamic acid derivatives such as methyl carbamate, N,N-diethyl methyl carbamate, isocyanuric acid, N,N',
Mention may be made of isocyanuric acid derivatives such as N'-)limethylisocyanuric acid and thiocarbonyl-containing compounds corresponding to these derivatives.

(Specific examples of the urea compound that is the c1 component include N.

N'dimethylurea, N,N'-diethylurea, N.

Examples include N,N',N'-tetramethylurea, N,N-dimethyl-N', and N'-diphenylurea.

(Specific examples of amide compounds or imide compounds that are dl components include N,N-dimethylformamide, acetamide, N,N-diethylacetamide, aminoacetamide, N,N-dimethyl-N',N'-dimethylaminoacetamide) ,N.

N-dimethylaminoacetamide, N,N-ethylaminoacetamide, N,N-dimethyl-N'-ethylaminoacetamide, acrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, nicotinamide, isonicotinamide , picolinic acid amide, N, N-dimethylisonicotinamide, succinic acid amide, phthalic acid amide, N, N, N', N'-tetramethylphthalic acid amide, oxamide, N, N, N', N'-
Amide compounds such as tetramethyl oxamide, 2-furancarboxylic acid amide, N,N-dimethyl-2-furancarboxylic acid amide, quinoline-2-carboxylic acid amide, N-ethyl-N-methyl-quinolinecarboxylic acid amide, Succinimide, N-methylsuccinimide, maleimide,
Imide compounds such as N-methylmaleimide, phthalimide, and N-methylphthalimide can be mentioned.

(Specific examples of N-alkyl-substituted oxazolidinone compounds that are el components include 1,3-diethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, 1,1-dipropyl-2-imidazolidinone, Lysinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-propyl-2-imidazolidinone, 1-methyl-
3-butyl-2-imidazolidinone, 1-methyl-3-
(2-methoxyethyl)-2-imidazolidinone, 1-
Examples include methyl-3-(2-ethoxyethyl)-2-imidazolidinone and 1,3-di(2-ethoxyethyl)-2-imidazolidinone.

Specific examples of the pyridyl-substituted ketone compound or pyridyl-substituted vinyl compound as component (f) include methyl-2
-pyridyl ketone, methyl-4-pyridyl ketone, propyl-2-pyridyl ketone, di-4-pyridyl ketone,
Examples include propyl-3-pyridylketone, 2-benzoylpyridine, 2-vinylpyridine, and 4-vinylpyridine.

Specific examples of the lactam compound as component (g) include N
-methyl-2-pyrrolidone, 2-piperidone, N-methyl-2-piperidone, 2-quinolone, N-methyl-quinolone, and the like.

The compounds consisting of the above (a) to (chamber components) may be used alone or in combination of two or more.

The amount of these compounds used is per gram atomic equivalent of magnesium atom or alkali metal atom in component (h),
The amount is usually 0.2 to 10 equivalents, preferably 0.5 to 5.0 equivalents, based on functional groups such as isocyanate groups, isothiocyanate groups, carbonyl groups, vinyl groups, and aldehyde groups.
If the amount is less than 0.2 equivalents, the impact resilience and low heat build-up of the vulcanized rubber will be poor, while if it exceeds 10 equivalents, the amount of unreacted substances will increase, causing odor or accelerating the vulcanization rate. This is not preferable because the effects of anti-+a elasticity and low heat generation properties of the vulcanizate are reduced.

In addition to the above-mentioned (a) to (gl component compounds), in order to widen the molecular weight distribution of the resulting diene polymer and to reduce the cold flow of raw rubber, difunctional or higher-functional tin halide compounds and halogen (k
) metal halide compound (hereinafter referred to as "open bone J"),
It can also be added in an amount of 0.05 to 5 equivalents, preferably 0.1 to 1.5 equivalents, based on halogen atoms, per 1 g atomic equivalent of magnesium atoms or alkali metal atoms in the component (h).

(Examples of kl components include dibutyldichlorotin, diphenyldichlorotin, methyltrichlorosilicontetrachlorotin, bis(trichlorostannyl)ethane, dibutyldichlorosilicon, methyltrichlorosilicon, tetrachlorosilicon, tin carboxylate compounds, etc.) These compounds can be used alone or in combination.

The reaction temperature between the (co)polymer and the compound is usually room temperature to 120°C, preferably 50 to 100°C, and the reaction time is usually several seconds to several hours.

After the reaction is complete, steam is blown into the polymer solution to remove the solvent, or a poor solvent such as methanol is added to solidify the modified (co)polymer, and then the (co)polymerized polymer is dried by hot rolls or under reduced pressure. You can get a combination. Alternatively, the polymer solution can be directly removed from the solvent under reduced pressure (co-).
Polymers can also be obtained.

Further, the molecular weight of the (co)polymer obtained in the present invention can be varied over a wide range, but the weight average molecular weight in terms of polystyrene is usually 5X10' to 1
00x104, preferably 10x10' to 80xlO'
If it is less than 5X10', the tensile strength, abrasion resistance, rebound resilience, and heat generation property of the vulcanized rubber will be poor, while if it exceeds 100XIO', the processability will be poor and excessive torque will be applied during kneading with rolls or Banbury. This is undesirable because it causes problems such as high temperature of the compound, which causes deterioration, and poor dispersion of carbon black, which impairs the manufacturing method of vulcanized rubber.

In addition, when the diene (co)polymer obtained in the present invention is used particularly as an industrial rubber product, its Mooney viscosity C
MLr, a (1100°C) is usually in the range of 20 to 150, preferably 30 to 80, and for the same reason as the weight average molecular weight, if it is less than 20, the physical properties of the vulcanized rubber will be poor, while if it exceeds 150, the physical properties of the vulcanized rubber will be poor. This results in poor workability.

The tire rubber composition of the present invention includes the diene (co)polymer alone or blended with other synthetic rubber or natural rubber as a raw material rubber, extended with process oil if necessary, Next, carbon black, which is a filler,
It is made by adding ordinary vulcanized rubber compounding agents such as a vulcanizing agent and a vulcanization accelerator.

In this case, in order to exhibit the excellent characteristics of the diene-based (co)polymer blended in the present invention, the diene-based (co)polymer of the present invention should preferably be present in an amount of 20% by weight or more in the raw material rubber. must be contained in an amount of 30% by weight or more.

Other synthetic rubbers that can be blended include cis-1,4-polyisoprene, emulsion-polymerized styrene-butadiene copolymer, solution-polymerized styrene-butadiene copolymer, and low cis-1°4-polybutadiene 1. , high cis-1,4-polybutadiene, ethylene-propylene-
Examples include diene copolymers, chloroprene, halogenated butyl rubber, acrylonitrile-butadiene rubber (NBR), and the like.

Processing oils used for oil extension include, for example, paraffinic, naphthenic, and aromatic oils, but aromatic oils are preferred for applications where tensile strength and abrasion resistance are important. For applications where low-temperature properties are important, naphthenic or paraffinic materials are used, and the amount used is 5 to 100 parts by weight per 100 parts by weight of raw rubber, and if it is less than 5 parts by weight, workability during kneading will be impaired. If the amount exceeds 100 parts by weight, the tensile strength and impact resilience of the vulcanized rubber will be significantly reduced.

Furthermore, the carbon blank used is HAF
, l5AFSSAF, etc., and preferably has an iodine adsorption amount (IA) of 60 μ/g or more and a dibutyl phthalate oil absorption amount (DBP) of 80 m1! /1
00g or more of carbon black is used. The amount of carbon black to be used is 20 to 100 parts by weight, preferably 30 to 80 parts by weight, based on 100 parts by weight of the raw rubber. If it is less than 20 parts by weight, the tensile strength and abrasion resistance of the vulcanizate are insufficient. On the other hand, if the amount exceeds 100 parts by weight, rebound properties, heat generation properties, etc. will decrease.

Furthermore, sulfur is usually used as a vulcanizing agent;
The amount used is O81 to 100 parts by weight of raw rubber.
If it is less than 0.1 part by weight, the tensile strength, abrasion resistance, and rebound resilience of the vulcanized rubber will decrease, while if it exceeds 5 parts by weight, it will become hard and the rubber elasticity will decrease. Lost.

Furthermore, the vulcanization accelerator is not particularly limited, but preferably M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (
Examples include thiazole-based vulcanization accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide (N-cyclohexyl-2-benzothiazylsulfenamide), and the amount used is 0.000 parts by weight per 100 parts by weight of raw rubber.
The amount is 1 to 5 parts by weight, preferably 0.2 to 3 parts by weight.

The tire rubber composition of the present invention may optionally contain fillers other than carbon blank such as silica, calcium carbonate, titanium oxide, zinc oxide, stearic acid, antioxidants,
Additives such as ozone deterioration inhibitors can also be blended.

The rubber composition for tires of the present invention is obtained by kneading using a kneading machine such as a roll or an internal mixer, and after molding, vulcanization is performed to form a tire tread.
In addition to tire applications such as undertreads, carcass, sidewalls, and bead parts, it can also be used for hoses, belts, shoe soles, window frames, sealing materials, anti-vibration rubber, and other industrial products. It is suitably used as rubber for tire treads.

〔Example〕

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

In the examples, parts and % mean parts by weight and % by weight unless otherwise specified.

Moreover, various measurements in the examples were based on the following methods.

The reaction between the polymer immediately after polymerization using the catalyst system and a specific compound was confirmed by GPC analysis and infrared analysis using changes in Mooney viscosity before and after the reaction, or a model reaction with a number average molecular weight of several thousand.

Mooney viscosity was measured at a temperature of 100° C. after 1 minute of preheating and 4 minutes of measurement (according to JIS K6300).

The microstructure of the (co)polymer was determined by infrared absorption spectroscopy (
Morello method).

A vulcanizate obtained by kneading and compounding the (co)polymer of the present invention or a commercially available rubber using a 230eC Brabender and a 6-inch roll according to the formulation shown below, followed by vulcanization at 145°C for a predetermined period of time. Various measurements were performed using the .

Star Gold Prescription (Part) Polymer
100 carbon black (HAF
) 50 aromatic oils
10 Stearic acid 2 Zinc white 3 Anti-aging agent (810
NA) Cap 1 Vulcanization accelerator (cZ")"
0. 6〃 (M)'″3
0.6 (D) 1140.4” (NOBS) 85 0.5 Sulfur
1.5$1) N-phenyl=N'-isopropyl-p-phenylenediamine *2) N-cyclohexyl-2-benzothiazoline sulfenamide *3) 2-mercaptobenzothiazole $4) 1.3-
Diphenylguanidine *5) N-oxydiethylene-2-benzothiazolesulfenamide Tensile properties and impact resilience were measured according to JIS K6301.

Abrasion resistance was determined according to ASTM D2228 (Pico method). The Pico abrasion index was determined using the abrasion (2) of a vulcanized product of styrene-butadiene copolymer (manufactured by Nippon Gosei Rubber (1), #1500) by the Pico method as a reference index of 100 (see Comparative Test Example 1). The larger the index, the better the wear resistance.

Reference Example 1 A dry autoclave with an internal volume of 51 cm equipped with a stirrer and a jacket was purged with nitrogen, and 2,500 g of previously purified and dried cyclohexane and 500 g of 1,3-butadiene were charged, then the autoclave was heated to 70°C and the contents shown in Table 1 The catalyst shown in was added to initiate polymerization. The polymerization reaction is
I went there as a subordinate.

When the polymerization addition rate reached approximately 95%, polymeric type diphenylmethane diisocyanate was added as a coupling agent to stop the polymerization.

Next, as an anti-aging agent, di-t-butyl-p-cresol was added to the rubber (solid content conversion > 0.7 per 100 g).
Polymer A was obtained by adding g and drying by dissolution according to a conventional method.

The microstructure of the poly-1,3-butadiene obtained by this reaction had cis-1,4 bonds <10%, 4% vinyl bonds, and 86% trans-1,4 bonds. The results are shown in Table 1.

Moreover, the GPC chart of this polymer is shown in FIG.

As is clear from Figure 1, the molecular weight distribution determined by a differential refractometer and the molecular weight distribution determined by ultraviolet (UV, 254 nm) appear in correspondence with the GPC counts, and the UV absorption spectrum shows that the lower molecular weight side It can be seen that the absorption intensity is large and corresponds to the number of polymer terminals.

Thus, it can be seen that even when 1,3-butadiene is polymerized alone using the specific catalyst system used in the present invention, a camping reaction with a specific compound occurs as in the present invention.

Reference Examples 2 to 10 In the same manner as Reference Example 1, using the catalyst system shown in Table 1, 1.
3-Butadiene (400 g) and styrene (100 g) were copolymerized, and a campling reaction was performed using the compounds shown in Table 1 to obtain Polymers B to J.

Examples 1 to 12 Natural rubber (NR) and commercially available styrene-butadiene copolymer (#
1500, made by Japan Synthetic Rubber, transformer-1,4 bond =
68%, bound styrene content = 23.5%, Mooney viscosity = 52), polybutadiene (JSRBROI, manufactured by Japan Synthetic Rubber C4ylJ, cis-1,4 bond = 96%, Mooney viscosity 44, hereinafter referred to as rBRJ), or Unmodified styrene-butadiene copolymer obtained with the catalyst system shown in Reference Example 1 in the table (HT-SBR, l-lance-1,4 bond = 83%, bound styrene content 1 = 15%, Mooney viscosity = 45 ) and according to the above formulation, 230
Table 2 shows the results of various measurements carried out using the vulcanizate, which was kneaded and blended using a CC plastic bender and a 6-inch roll, and then vulcanized at 145° C. for a predetermined period of time.

Comparative Examples 1 to 5 Polymer B, natural rubber (NR), commercially available styrene
Butadiene rubber (#1500) or unmodified styrene-butadiene copolymer (HT-3BR) was kneaded and blended in accordance with the above formulation using a 230 cc Brabender and a 6-inch roll, and then heated at 145°C. Table 2 shows the results of various measurements performed using the vulcanizate that was vulcanized for a predetermined period of time.

(Leaving space below) Table 2 Table 2 (Continued) [Effects of the invention] The present invention provides rubber compounded with a novel diene-based (co)polymer having a specific functional group by reacting a specific compound. It is a composition and when used as an industrial rubber product,
Repulsion, mechanical properties (especially modulus, tensile strength)
A vulcanizate can be obtained which has good exothermic properties and greatly improved wear resistance compared to known conjugated diene (co)polymers.

[Brief explanation of the drawing]

FIG. 1 is a GPC chart of Polymer A obtained in Reference Example 1. Patent applicant: Japan Synthetic Rubber Co., Ltd., Brideston Co., Ltd. Agent: Takashi Shirai, patent attorney Figure 1

Claims (3)

[Claims] (1) (a) Isocyanate compound and/or isothiocyanate compound, (b) Isocyanuric acid derivative and/or thiocarbonyl-containing compound corresponding to the derivative, (c) Urea compound, (d) Amide compound and/or imide compound, (e) N-alkyl substituted oxazolidinone compound, (f) pyridyl substituted ketone compound and/or pyridyl substituted vinyl compound, and (g) lactam compound modified with at least one compound selected from the group of compounds, and diene moiety To 100 parts by weight of a rubber raw material containing 20% by weight or more of a diene (co)polymer having a trans-bonding content of 70% to 90%, 20 to 100 parts by weight of carbon black and 0.0% of a vulcanizing agent are added. 1-5
A rubber composition for tires, characterized in that it contains parts by weight. (2) The rubber composition for tires according to claim 1, wherein the diene (co)polymer is a butadiene polymer or a styrene-butadiene copolymer. (3) The diene (co)polymer has a bound styrene content of 5 to
The rubber composition for tires according to claim 1 or 2, which is 45% by weight of a styrene-butadiene copolymer.