JPS5891738A - Deodorized phosphorous additive for rubber - Google Patents

Abstract

PURPOSE:To provide the titled additive of which the odor is improved, obtained by incorporating an amine compound or a fine inorg. filler for a rubber compound in a specific phosphorous compound. CONSTITUTION:A rubber additive contains a phosphorus compound shown by the formula (wherein R1 and R2 are each alkyl, alkenyl, cycloalkyl or aryl, X is O or S) (A) (e.g., N,N',N''-trisisopropylthio-N,N',N''-triphenylphosphoric triamide) and an amine compound (e.g., triisopropanolamine) (B) or a fine inorg. filler for a rubber compound (e.g., CaCO3 with an average particle size of 0.1mu or less treated with an org. acid). By compounding component B with component A which has an excellent vulcanization retarding effect but is hardly used because of the peculiar odor thereof, the odor is improved to a large extent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to additives for rubber. More particularly, the present invention relates to deodorized rubber additives.

In recent years, in the rubber industry, with changes in the factory environment and increased awareness of safety (1) and hygiene, strict regulations have been put in place regarding the odor of compounding agents in rubber.

On the other hand, as rubber products such as tires and belts become larger and production efficiency improves, the unvulcanized rubber compound
Due to the harsher thermal history, there is a great social demand for better vulcanization retarders.

The inventors of the present invention have investigated the deodorization of phosphorus-based rubber additives, which have an excellent vulcanization retarding effect but are difficult to use due to their unique odor. The inventors have discovered that the odor can be greatly improved by incorporating an inorganic filler for blending, and have completed the present invention.

That is, the present invention provides (1) a phosphorus compound represented by the following formula (wherein R, , and R2 each represent an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group, or an oxygen or (represents a sulfur atom), and (2) is an additive for rubber containing an amine compound or a fine inorganic filler for rubber compounding.

In the above formula, examples of the alkyl group represented by k and 2 include methyl, ethyl, propyl, isopropyl,
Butyl, isobutyl, tert-butyl, hexyl,
n-octyl, tert-octyl, n-dodecyl,
Examples of the alkenyl group include tert-dodecyl and n-octadecyl, and examples of the alkenyl group include propenyl, n-budo-1-
Examples of the cycloalkyl group include enyl, isobutenyl, dodecenyl, and n-octadecenyl; examples of the cycloalkyl group include cyclopentyl and cyclohexyl; and examples of the aryl group include phenyl, 〇-1m- and p-tolyl, and naphthyl.

As the phosphorus compound represented by the above formula, N.

(3) Dartriphenylphosphoric acid triamide, N, N'.

Matris-n-butylthio-N,i,1''/-triphenylphosphoric triamide, N,N',N'-tris-cyclohexylthio-N,N',N'-triphenylphosphoric triamide N,N', N')!JsubenzylthioN,N',N'-)!Jphenylphosphoric triamide, N,N',N'-tris-n-ctadecylthio-N,N',N')listyl phosphoric triamide , N
, N', N'-tris-methylthio-N N' N
'-) listyl phosphate triamide, N.

N',N'-tris-isopropylthio-N,N'.

NI-tricyclohexylphosphoric triamide, N.

N', N')limethyl-N,N,N-tris(i,sopropylthio)phosphorthioic triamide, N,ma, Dartley n-butyl-N,ma.

Tartris(cyclohexylthio)phosphorthioic triamide, N,N',N'-tricyclohexyl-
N,N',N'-)lis(isopropylthio)phosphorthioic triamide, N,N'.

(4) N-trimethyl-N,O,#-tris(phenylthio)
Phosphorthioic triamide, N.

Go, zotriphenyl-N, Go, N') di-n-butyl-N, *, N'-) lis(cyclohexylthio)phosphorthioic triamide, N.

Co, two-tricyclohexyl-N,N',N') lis(isopropylthio)phosphorthioic)! J7E
)' , N , N' , N' -)
! J, l -F-/L/-N, N'.

N') lis(phenylthio)phosphorthioic triamide, N,N',N'-)riphenyl-N.

Examples include NI, NIF lis(isopropylthio)phosphorthioic triamide.

The amine compounds used in the present invention are aliphatic amines, alicyclic amines, aromatic amines, and alkanolamines. Specifically, the aliphatic amines include trimethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine, monobutylamine, dibutylamine, tributylamine, monooctylamine, dioc(5) tylamine, trioctylamine, Each isomer such as monostearylamine, distearylamine, and tristearinamine is used as an alicyclic amine, and each isomer such as monocyclohexylamine, dicyclohexylamine, and mono(dimethylcyclohexyl)amine is used as an aromatic amine. Each isomer of aniline, diphenylamine, toluidine, xylidine, etc., and alkanolamines such as trimethanolamine, monoethanolamine,
Examples include isomers such as jetanolamine, triethanolamine, monopropanolamine, dibrobanolamine, tripropanolamine, monobutanolamine, jetanolamine, and tributanolamine. Among these amine compounds, alkanolamines are preferably used.

In addition, examples of the fine inorganic filler for rubber compounding used in the present invention include silica, clay, calcium carbonate, titanium oxide, talc, diatomaceous earth, etc.
Calcium Carbonate (6) Particularly preferred is calcium carbonate having an average particle size of 0.001 microns or less and treated with an organic acid.

The amine compound is usually added in an amount of 0.1 to 20% by weight based on the phosphorus compound represented by the above formula. Addition amount is 00
If it is less than 1% by weight, the deodorizing effect will not be sufficient, and if it exceeds 20% by weight, it will tend to suppress the vulcanization retardation effect of the phosphorus compound, which is not preferable. Further, the fine inorganic filler for rubber compounding is added in an amount of 5 parts by weight or more, usually 5 to 200 parts by weight, per 10 parts by weight of the phosphorus compound.

The phosphorus compound and the amine compound or the fine inorganic filler for rubber compounding may be mixed by any conventional method, but for example, the phosphorus compound is dissolved in a suitable solvent and mixed uniformly, and then the solvent is distilled. This can be carried out by removing the particles by means of, for example, or mechanically mixing them uniformly by using a mixer or the like.

The additive of the present invention obtained in this manner is substantially deodorized without impairing the original (7) performance of the phosphorus compound represented by the above formula, and is suitable for use in rubber with no odor. Used to advantage without any problems.

The present invention will be explained in more detail below with reference to Examples.

Example 1 N, rJ, f-tris-isopropylthio-N, *, f-triphenylphosphoric acid triamide 10 as a phosphorus compound
After dissolving the solution in acetone 509, triisopropanolamine 12 was added and mixed uniformly, and the acetone was distilled under reduced pressure by a conventional method. The phosphorus compound was sealed before and after the addition of triisopropanolamine for 1ay each.
Pour into a 00 ml polyethylene bottle and heat at 40°C for 30 minutes.
Leave it for a minute.

Thereafter, the air in the bottle was put into a polyethylene bag with a zipper and diluted with clean air using a syringe. The odor index was the magnification up to the concentration at which no odor was felt. In a similar manner, the phosphorus compound rl1109/ and the amine compound shown in Table 1 were mixed (8
) The odor index is shown in Table 1.

(9) Example 2 N, N', N'-tris-isopropylthio-
N,N',N'-triphenylphosphoric acid triamide 1002
and Neolite S (fatty acid-treated calcium carbonate, average particle size 0.04 μm: Takehara Chemical Co., Ltd. trade name) 200 F were added and mixed by stirring at a rotational speed of 50 rpm for 10 minutes.

The above-mentioned phosphorus-based compound CVJ10g and the mixture 302 obtained above were each placed in a sealed 100 m/polyethylene bottle, and after being left at 40°C for 30 minutes, the air inside the bottle was removed with a syringe and a clean bottle was placed. It was diluted with air, and the dilution ratio at which no odor was sensed was defined as the odor index.

In the same manner, other phosphorus compounds shown in Table 1 were mixed with an inorganic filler for rubber compounding, and the same tests were conducted.

The odor test was conducted when the amount of phosphorus compounds in the bottle was constant (10
F).

(11) (10)

Claims (2)

[Claims] (1) A phosphorus compound represented by the following formula (in the formula, k□ and R2 each represent an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group, and X represents an oxygen or sulfur atom), and (2) Rubber additive containing an amine compound or a fine inorganic filler for rubber compounding