JPS62273267A - Carbon black and rubber composition containing same - Google Patents

Abstract

PURPOSE:To obtain a rubber composition improved in resilience, suitable for automobile tires, etc., by incorporating a rubbery polymer with carbon black on which a specific organic compound has been adsorbed. CONSTITUTION:The objective composition can be obtained by incorporating (A) a rubbery polymer with (B) carbon black on which an organic compound having in the molecule both -XH group (X is O or S) and unsubstituted amino group and/or substituted amino group (e.g. of formula I, formula II, etc.) has been adsorbed. The amount adsorbed on the carbon black of said organic compound is pref. >=50wt% of the saturated amount to be adsorbed.

Description

Detailed Description of the Invention 5. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to carbon black adsorbing a specific organic compound and a rubber composition containing the same with improved resilience. .

(Prior Art) Recently, from the viewpoint of low fuel consumption and safety of automobiles, there has been a strong demand for reduction in rolling resistance of tires and excellent braking performance on wet road surfaces, that is, improvement in wet skid resistance.

In general, these tire properties are considered to correspond to the dynamic viscoelastic properties of trend rubber materials, and are known to be contradictory properties [for example, Transacti
on of Engineering, R, 1,, Volume 40, Nos. 239-256.
Page, 1964] 0 In order to reduce the rolling resistance of tires, it is necessary for the trend rubber material to have a high recoil modulus, and considering the driving conditions of the car, this recoil modulus is 50°C. It is necessary to evaluate at temperatures ranging from 70°C to around 70°C. On the other hand, in order to improve braking performance on wet roads, which is an important performance in terms of vehicle safety, it is necessary to have a high wet skid resistance as measured by the Pretty Portable Skin Tester, and the tread rubber material Therefore, it is necessary that the energy loss in the form of frictional resistance that occurs when the tires are braked and caused to slide on the road surface is large.

Conventionally, in order to satisfy these two conflicting properties, styrene-butadiene copolymer rubber containing 20 to 25% by weight of bound styrene and high cis 1.4-copolymer rubber containing 80% or more of cis 1.4-bond units have been used. Combinations of polybutadiene rubber have been used, but have been unsatisfactory with respect to wet skid resistance (
Although attempts have been made to improve wet skid resistance by mixing resins and rubbers with high glass transition temperatures, it is inevitable that the rebound modulus will be low, and improvements are desired.

Against this background, the inventors of the present invention have made extensive studies and have found that the above requirements can be met by using a rubber composition in which a carbon blank adsorbed with a specific organic compound is blended with a rubber-like polymer. The present inventors have found that the present invention can be obtained by completing the present invention.

(Problems to be Solved by the Invention) Therefore, the object of the present invention is to provide a novel carbon blank that can improve anti-resilience by blending it into a rubber-like polymer, and a rubber composition containing the same with improved anti-resilience. According to the present invention, (1) -XH group (X represents 0 atom or S atom) and an unsubstituted amino group and A carbon blank characterized by adsorbing an organic compound having / or a substituted amino group, and (2) a rubbery polymer, in which -XH group (X represents an O atom or an S atom) in the molecule.
and a carbon blank adsorbed with an organic compound having an unsubstituted amino group and/or a substituted amino group.

In the present invention, the organic compound (hereinafter sometimes referred to as an adsorbent) includes monoethanolamine,
2-amino-1-butanol, 2-amino-2-methyl-1,3-propanediol, 1-dimethylamino-2
-propanethol, 2-(ethylamino)ethanol, 1,1-bis(diethylanilino)-1-pentanol, 1,1-bis(anilino)-1-pentanol, 1
-Phenyl-1-(4-pyridyl)-1-pentanol, 1,1-bis(1,1-dimethylamino)-1-pentanol, 1-phenyl-1-(N, N-dimethylamine)- 1-Pentanol, 1.1-bis(1-phenylniteramino)-1-pentanolnato amino alcohols and their corresponding aminothioflucols, dimethylaminophenol, p-(2-dimethylaminoethyl)phenol , p-(2-aminoethyl)phenol and their corresponding 7-minothiophenols, aminotriphenylmethanol, 4.4'
-diaminotriphenylmethanol, 4.4-bis(dimethylamino)triphenylmethanol, rosaaniline base, vararosaniline base, 4.4',4'-tris(dimethylamino)triphenylmethanol, 8-hydroxyquinoline, 2 -Methyl-8-hydroxyquinoline, 7-diethylamino-8-hydroxyquinoline, 7-
Cyptylaminomethylene-8-hydroxyquinoline and the like can be used.

In addition, -C-X group (X is ○
or S atom), an amino group and/or a substituted amino group, and an organic compound containing an alkali metal and/or alkaline earth gold, followed by hydrolysis. can also be used. Taking the reaction of 4-dimethylaminobenzaldehyde and alkyl lithium (R-Ll) as an example, the reaction is as follows.

(Reaction product) Examples of organic compounds used in the reaction are as follows.

The amino(thio)aldehyde and amino(thio)ketone include 3-dimethylaminoglobionaldehyde, 4-
Dimethylaminobenzaldehyde, 4-dimethylaminoacetophenone, a-7minobenzophenone, 4-dimethylaminobenzophenone, 4-dimethylamine-4'
-Methylbenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(dimethylaminobenzophenone, 4147-bis(ethylaminocobenzophenone, 5
．． 3'-dimethyl-4,47-bis(diethylamino)
Benzophenone, 3,3'-dimethoxy-4,47-bis(dimethylamino)benzophenone, 5.3', 5
．． 5'-f) laminobenzophenone, 2,416
-) IJ aminobenzophenone, 5.3', 5.5'
-Tetra(diethylamino)benzophenone, 1.5-
Bis(seal-propylamino)-3-pentanone, 3
, 5-bis(dioctylamino)-rouvaleraldehyde, 3-dicyclohexylamino 10 pionaldehyde, 6-cyphenylaminocagloaldehyde, 4-dicyclopentylaminobenzaldehyde, 1,3-bis(diethylamino)-2-globanone , 1,7-bis(methylethylamine)-4-heptanone, and the like, and their corresponding thioaldehydes and thioketones.

Other compounds include N,N-diethylformamide, N,N-diethylacetamide, globionamide,
Amides such as 4-pyridylamide, benzamide, p-aminobenzamide, N/, N/-(p-dimethylamino)benzamide, succiamide, nicotinamide, methyl carbamate, N-methylphthalimide, oxamide, and the like; Imides; urea, N, N'
- Ureas such as dimethylurea, N, N, N', N'-tetramethylurea, etc. Anilides such as 2N-methylacetanilide, p+p'-di(N,N-diethyl)aminobenzanilide; ε- Caglolactam, N-methyl-ε-caglolactam, 2-pyrrolidone,
N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-methyl-2-quinolone, N-methyl-2-
Lactams such as indolinone; isocyanuric acid,
N, N'.

Incyanuric acids such as N'-trimethyliso7anuric acid; and sulfur-containing compounds corresponding thereto.

Particularly preferred among the above compounds are those having an N,N-disubstituted amino group, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkaryl group.

Typical organic compounds containing alkali metals and/or alkaline earth metals to be reacted with the above-mentioned compounds are polymerization catalysts based on these metals. Alkali metals include sodium, potassium, lithium, cesium,
Examples of alkaline earth metal scraps include rubidium, barium, strontium, calcium, and the like.

As an alkali metal scrap-based catalyst, Japanese Patent Publication No. 43-2761
The compounds disclosed in JP-A-51-115590;
9090.17591.30543.48910.98
077; JP-A-56-112916; JP-A-57-1
Examples include compounds disclosed in publications such as No. 00146.

Particularly preferred in the present invention are lithium-based catalysts such as methyllithium, roofyllithium, phenyllithium, 1,4-dilithiobutane, and dilithionaphthalene.

The reaction between an organic compound having a C-O group or a C-8 group and the metal-containing organic compound is usually carried out in a solution. The metal is used in equimolar or excess amount relative to the number of moles of the group in the compound. The reaction takes place at a temperature of room temperature to 100° C. for several minutes to several hours. After the reaction is completed, the desired compound is obtained by adding water, alcohol, etc. to carry out hydrolysis.

The carbon blank of the present invention is made by adsorbing the above-mentioned adsorbed substances onto various grades of carbon black as a reinforcing agent, such as HAF, FRF, and 15AF, which are commonly used in the rubber industry. In the present invention, the adsorption method of the adsorbent is not particularly limited, but one method is to immerse the carbon blank in a bath liquid or suspension in which the adsorbent is dissolved or suspended.

In order to achieve the object of the present invention, the adsorption amount of the adsorbent on the carbon blank must be at least 10% of the saturated adsorption amount;
Preferably, it is required to be 50% or more.

The rubbery polymer with which the carbon blank of the present invention is blended is not particularly limited, and all rubbers commonly used in the rubber industry can be used. For example, natural rubber, polyisoprene rubber (high cis and low cis), polybutadiene rubber (high cis and low cis), styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber, acrylonitrile-butadiene copolymer rubber , polybentenamer, polyoctenamer, polychloroprene rubber, ethylene-globylene-diene monomer terpolymer rubber (EPDM)
, acrylic rubber, epichlorohydrin rubber, etc.

The carphone black (CD ellipsoid, CHAF, pxp, etc. grade) and blending amount of the rubber-like polymer of the present invention are appropriately selected and determined according to the purpose of use or required performance of the rubber composition to be used, and there are no particular restrictions.◇Blend amount is usually 5 to 100 parts by weight per 100 parts by weight of the rubbery polymer.

When used, the rubber composition of the present invention is sulfur-vulcanized with sulfur, zinc white, stearic acid, vulcanization accelerators (guanidine, thiazole, thiuram, dithioate, etc.) commonly used in the rubber industry. It is used as a compounded rubber composition further containing various compounding agents such as a vulcanization system, an organic peroxide vulcanization system, a process oil, a plasticizing agent, a processing aid, and an anti-aging agent.

Since the rubber composition of the present invention provides a vulcanizate with improved rebound elasticity, it is particularly suitable for automobile tires, automobile tires, and other trends and carcass, but is not limited to these uses.

The present invention will now be explained in more detail with reference to Examples. Unless otherwise specified, the number of parts and numbers used are based on weight.

4,4'-bis(diethylamino)benzophenone (120 tf) was dissolved in 500 d of benzene (120 tf) in the eggplant-shaped flask of Production Example 22 of Adsorbent Substance, and the atmosphere was replaced with nitrogen. Stirring was continued for 2 hours while cooling with added ice water. Thereafter, a large excess of methanol km relative to the molar amount of rubutyllithium was added to perform hydrolysis. After removing all precipitates from each house,
Solution F was mixed with large amounts of ether and water. After shaking thoroughly, the mixture was allowed to stand and the supernatant ether layer was separated. To the separated ether layer, powders of Na and S○4 anhydride were added and dehydrated, and then the precipitate N to SO4.2H20 was separated from each other. Ether and benzene are evaporated from the tear fluid using an evaporator according to a conventional method, and the target adsorbent substance if
) obtained.

In the same manner, the starting material benzophenone was replaced with the thiobenzophenone to synthesize adsorbent material (2).

Example 1 HAF carbon black (sheath manufactured by Tokai Carbon Co., Ltd.) 3) lj'(
After lightly grinding with a milk needle in advance, the mixture was dried under reduced pressure at a temperature of 110°C for 4 hours.After adding the powder and sealing it, it was stirred 200 times and left at 23°C for 24 hours.0 Pore size: 0.2
Separate the carbon blank with a μ Millipore filter,
The concentration of adsorbent substance (1) in each bath liquid was determined by FT-4H. Based on this result, the adsorption isotherm at was determined according to a conventional method.

As a result, the saturated adsorption amount of the adsorbent to the carbon blank was 3. I X 10-5 mol/f carbon black.

Carbon black on which adsorbent substance (2) was saturatedly adsorbed was also prepared in the same manner.

Based on these results, adsorbent material fi+ in the amount listed in Table 1
Alternatively, HAF carbon black adsorbed with adsorbent substance (2) was prepared in the same manner as above. The carbon blank separated from the carbon tetrachloride solution was air-dried for 3 hours at room temperature, and then
This is a hole needle dried under reduced pressure at 0℃ for 4 hours. 9 crushed Example 2
Example 2 SBR obtained by copolymerizing butadiene and styrene using rubyl lithium as a catalyst (combined styrene amount: 50
1.2-bond amount of butadiene unit 43 molt, cis 1
, 4-bonded gold amount 31 molt, trans 1.4-bonded gold amount 26 molt, weight average molecular weight by GPO 15Q, 00
0) 00 parts of I, 50 parts each of the carbon black listed in Table 1, and 1 part of dicumyl peroxide were added to a Prabender Plastograph (J3rabsnder Co., Ltd.) at 80°C.
manufactured by West Germany) to obtain a compounded rubber composition. After being left overnight, it was press-vulcanized at 150° C. for 30 minutes, and the anti-friction elasticity of the resulting vulcanized product was measured using a Dunlop trypsometer. The results are shown in Table 2.

Table 2 Example 3 EAF carbon black (Geast 3 manufactured by Tokai Carbon Co., Ltd.) in which the organic compounds listed in Table 4 were saturated and adsorbed at 23°C was used as the adsorbent, and high carbon black was used according to the formulation listed in Table 3. Suvobutadiene rubber (manufactured by Nippon Zeon Co., Ltd. N
1pol 1220) on a roll to obtain a compounded rubber composition.After standing overnight, press vulcanization was performed at 160"C for 15 minutes to obtain a vulcanized product.Strength characteristics were measured according to J.K. E3 6301. The rebound elasticity was measured at 53°C using a Dunlop trigometer.

The above results are shown in Table 4.

3rd notation combined prescription Table 4

Claims (2)

[Claims] (1) Carbon black characterized by adsorbing an organic compound having -XH group (X represents an O or S atom) and an unsubstituted amino group and/or a substituted amino group in the molecule. (2) A rubber-like polymer is blended with carbon black in which an organic compound having a -XH group (X represents an O atom or an S atom) and an unsubstituted amino group and/or a substituted amino group is adsorbed in the molecule. A rubber composition characterized by comprising: