JPS6048544B2 - Crosslinkable chlorine-containing elastomer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to vulcanizable chlorinated elastomer compositions containing novel vulcanization accelerators.

The present inventors previously discovered the general formula R-Sx-R' (where RN
We have developed a chlorine-containing elastomer composition containing an accelerator (R' is a polyhydroxyaryl group having 6 to 18 carbon atoms, and X is an integer of 0 or 1 to 4).
When this composition is vulcanized using a metal oxide as a vulcanizing agent, there is a problem in that the vulcanized elastomer does not necessarily have sufficient aging resistance.

On the other hand, chloroprene rubber, sulfur as a vulcanizing agent, bis(1,3-dihydroxyphenyl)disulfide or poly(resorcinol disulfide), which is a type of R-Sx-R', and tetramethylthiuram disulfide Compositions consisting of sulfide and ZnO are also known, but according to research by the present inventors, the vulcanized product of this composition has a problem of considerably poor aging resistance due to the presence of sulfur.

Furthermore, the present inventors have determined that the above R-Sx-R in the absence of sulfur
', thiurams or other specific compounds, and a metal oxide vulcanizing agent when vulcanizing a chlorine-containing elastomer, the resulting vulcanizate has well-balanced physical properties and excellent properties. It was completed based on new knowledge that it has excellent aging resistance, and it contains a chlorine-containing elastomer, a metal oxide vulcanizing agent, viscatecol monosulfide, viscatecol polysulfide, and bishydroquinone monosulfide. , bishydroquinone polysulfide, and one or more compounds selected from the group consisting of derivatives of each of the above sulfides (
a), a compound (b) represented by the general formula B [wherein R'-R' is an alkyl group, an aryl group, or an aralkyl group, respectively, and y is an integer of 1 to 4], and guanidines (c)
, thioureas (d), thiazoles and their salts (
e), dithiocarbamates (f), sulfenamides (g), xanthate and its salts (h), aldehyde-amine condensates and aldehyde-ammonia condensates (j), and sulfur-providing compounds other than compound (b) Z consisting of one or more compounds selected from compound group (b) to (k) consisting of class (k), and per 1 part by weight of compound (a), compound group (b) to The vulcanization accelerator is characterized in that the total amount of the compounds selected from (k) is 0.05 to 20 parts by weight.

The chlorine-containing elastomer J-1 targeted in the present invention refers to polychloroprene, epichlorohydrin, chlorinated polyethylene rubber, chlorosulfonated polyethylene rubber, etc. Among these, polychloroprene is particularly preferable, and a more preferable chlorine-containing elastomer is a non-chlorine-containing elastomer. Sulfur-modified polychloroprene, that is, polychloroprene rubber in which sulfur is not added during the production of the polymer itself or in the raw comb state, such as polychloroprene rubber represented by DuPont's Neoprene W type, Neoprene T type, or equivalent products. ．． I can give you a mouthful.

The compound (a) used in the present invention is a hydroxyl group-containing aromatic compound (hereinafter simply referred to as a hydroxyl group-containing aromatic compound) having two hydroxyl groups located in the ortho or rose position relative to each other on the aromatic ring. Monosulfide (-S-) group or polysulfide group (-Sx-, where X is 2 to
4) has a structure in which they are bonded to each other, and the aromatic residue has a substituent other than the hydroxyl group, such as C, to C8
Alkyl group, alkoxy group, alkenyl group, C6-C
The aryl group, arylene group, carbonyl group, carbalkoxy group, amino group, etc. of l4 may be appropriately substituted.

In addition, sulfurs having the residue of a compound having two hydroxyl groups located in meta-position to each other on the aromatic ring,
Regarding manufacturing? Not very good in terms of product handling.

Compound (a) is the above-mentioned hydroxyl group-containing aromatic compound, such as dihydroxybenzenes such as catechol and hydroquinone, or derivatives thereof, 1/2-position, 1/4-position, 2/3-position, 3/4-position. Polyhydroxynaphthalenes or derivatives thereof having hydroxyl groups in the 1- and 2-positions, etc.
Obtained by reacting one or more polyhydroxyanthracenes or derivatives thereof having hydroxyl groups at the 1/4-position, 2/31-position, 3/4-position, etc. with sulfur monochloride or sulfur dichloride. .

Particularly preferred are those in which the hydroxyl group-containing aromatic compound is obtained by reacting catechol and/or hydroquinone with sulfur monochloride or sulfur dichloride, and in which the catechol residue and/or hydroquinone residue is monosulfite. (-S-) or disulfide (-S-S-). Although various methods for producing the compound (a) of the present invention can be considered, the compound (a) as a vulcanizing agent in the present invention
), the following method is particularly recommended. (a) For 1 mole of sulfur dichloride. A method of reacting 4.8 to 2.2 mol of the above hydroxyl group-containing aromatic compound in an organic solvent,
and (b) a method in which 1.8 to 3 moles of the hydroxyl group-containing aromatic compound is reacted with 1 mole of sulfur monochloride in an organic solvent. In addition, the reaction in an organic solvent in the above manufacturing methods (a) and (b) is completed by stirring the reaction at a predetermined temperature for 1 to 1 hour. The end point of the reaction can be determined by thin layer chromatography analysis or the like. The reaction may be carried out at the reflux temperature of the organic solvent, with cooling as necessary to control the reaction, or heating as necessary to promote the reaction. The end point of the reaction when the reaction is carried out by cooling or heating can also be determined in the same manner as above. In addition, as the organic solvent used in the present invention, organic solvents such as acetonitrile, dioxane, diethyl ether, ethyl acetate, η, methanol, ethanol, acetone, propanonol, carbon tetrachloride, chloroform, and K Tsukuda are used. The amount of the organic solvent used is not particularly limited, and is the amount used in ordinary solvent reactions, for example, 100 mL to 11 mL per mole of sulfur chloride.

After the completion of the above reaction, the residue after distilling off the organic solvent may be used as the reaction product of the compound (a) of the present invention, but the reaction product may also be used as it is as the compound (a). Alternatively, it may be further purified and used. Particularly preferred organic solvents are methanol,
Using ethanol, diethyl ether, ethyl acetate, tetrahydrofuran, etc., the reaction temperature is set to the above production method (a).
) at -10°C to room temperature, and at (b) at 0
Examples include reaction products obtained by reacting in a temperature range of 80°C to 80°C.

As the compound (b) of the present invention, those generally referred to as thiuram sulfides represented by the general formula (B) are used, and among them, in the general formula (B), R, to R. are each an alkyl group having 5 or less carbon atoms, or R, and R. and R. and R. are linked at their ends to form a carbocyclic ring, thus resulting in R, -N-R. forms a nitrogen-containing carbocycle and the number of carbon atoms constituting the carbocycle is 10 or less, or an aralkyl group having 8 or less carbon atoms,
Alternatively, an aryl group in which x is 1 to 4 is preferable. Tetramethylthiuram disulfide (TMT)
D), tetraethylthiuram disulfide (TETD)
), tetramethylthiuram monosulfide (TMT
M), tetrabutylthiuram disulfide (TBT)
D) Dipentamethylene lentithurum tetrasulfide (
DPMTT), N. N'-dimethyl-N. N'-diphenylthiuram disulfide (DMDPTD), tetrabutylthiuram monosulfide (TBTM), N
．． selected from the group consisting of N'-diethyl-N-N'-diphenylthiuram disulfide (DEDPTD), dipentamethylenethiuram disulfide (DPMTM), tetraethylthiuram monosulfide (TETM), dipentamethylenethiuram monosulfide (DPMTM) One or more types are suitable. Among them, TMTD)TMTM)TETD)TBT
D etc. are preferred.

In addition, the guanidines (c) used in the present invention can be expressed by the following general formula (C) [wherein R and R' are aromatic rings or -C (=
NH)-NHR'' (however, R
"represents a hydrogen atom or an aromatic ring)" are used, among which R) those in which R' is a phenyl group, tolyl group, or guanidino group, and their acetate, phthalate, or dicatechol borate salts. is preferred.

N. N'-diphenylguanidine (DPG), N-N'
-G-o-tril4. Guanidine (DTG), o-tolyl biguanide (BG), dicatechol borate
-Tolylguanidine salt (PR), diphenylguanidine phthalate (DPGP), triphenylguanidine (πG), phenyl tolyl xylyl guanidine (
PTXG), diphenylguanidine acetate (DP
One or more types of GA), especially DPGNDTG)
BG)PR is particularly preferred. In addition, the thioureas (d) used in the present invention are represented by the following general formula (D) [where R1 to
R4 represents an alkyl group, an aryl group, or a thiazolyl group having 20 or less carbon atoms], and among them, in the general formula (D), R'' to R' are alkyl groups having 20 or less carbon atoms. , preferred are aryl groups and thiazolyl groups having 10 or less carbon atoms.

Thiocarbanilide, 1,3-bis(2-benzothiazolylmercapto)urea, 1,3-diethyl thiourea (EUR), 1,3-dibutyl thiourea, dimethylethyl thiourea, trimethyl thiourea (TMU)
), di-o-tolylthiourea, tetramethyl thiourea, and dilauryl thiourea, and one or more of them are preferably used, and among them, EUR)TMU is preferable. Thiazole and its salts (e) may be represented by the following general formula (E) [wherein R is a divalent organic group having 20 or less carbon atoms, and X is a hydrogen atom, a metal, or -Sx-c? N'Υ group (provided that x is an integer of 1 to 4), and carbon number 20
Those represented by the following organic groups (excluding amino groups) and their amine salts are used, and among them, those in formula E in which R is an o-phenylene group are preferred.

2-(4'-morpholinodithio)benzothiazole (
MDB), 2-mercaptobenzothiazole (MB),
Dibenzothiazyl disulfide (DM), 2-(2
'・4'-dinitrophenylthio)benzothiazole, 2-mercaptobenzothiazole cyclohexylamine salt, 2-mercaptobenzothiazole zinc salt (■),
2-mercaptobenzothiazole copper salt (MCu), N.
N-diethylthiocarbamoyl-2-benzothiazolyl sulfide, 2-benzothiadylthiobenzoate,
2-(2 ・6-dimethyl-4-morpholinothio)
One or more of benzothiazole, 1,3-bis(2-benzothiazolylmercaptomethyl)urea, and 2-mercaptothiazoline are preferably used, and among them, MDB
、． MB, DM, , MZ are preferred.

The dithiocarbamates which are the compound (f) of the present invention have the following general formulas (F-1) and (F-2) [wherein R' to R' are an alkyl group having 20 or less carbon atoms, an aralkyl group, an aryl group] group, a cyclic alkyl group, or R゛ and R゜ or R゜ and R' may each be combined to form a cyclic alkyl group, M is a metal, and n is a number corresponding to the valence of the metal, from 1 to 5. ] indicating an integer is used,
Among these, those in which the organic group represented by R゛ to R゜ in formulas F-1 and F-2 have 10 or less carbon atoms are preferred, and in formula F-1, M is NaNKNZn)Pb)B
i) Cd) Te) Se, , FeNCu are preferred.

Copper salt (TTCu), iron salt (ΠFe) bismuth salt, zinc salt (PZ), selenium salt, potassium salt, and sodium salt of dimethyldithiocarbamate, nickel salt (NEC), tellurium salt (TEG) of diethyldithiocarbamate
), cadmium salts, zinc salts (EZ) and sodium salts,
Sodium, potassium, zinc (BZ), and nickel salts (NBC) of di-n-butyldithiocarbamate
, lead salt of ethyl phenyl dithiocarbamate (PE),
Zinc salt (PX), piperidine salt of pentamethylene dithiocarbamate, N-pentamethylene ammonium salt, sodium salt, and lead salt, pipecoline pipecolyl dithiocarbamate, zinc salt of dibenzyl dithiocarbamate, N-cyclohexylethyl ammonium cyclohexylethyl dithiocarbamate , N-pentamethylene ammonium pentamethylene dithiocarbamate (PPD) and the like are preferably used, and among them, PZ) ΠCu) TEG. ．． NBC and the like are particularly preferred. As the sulfenamide compound (g) of the present invention, N-substituted-2-
It is benzothiazyl sulfenamide. [In the formula R゛,
R' represents a hydrogen atom, an alkyl group having 15 or less carbon atoms, or a cycloalkyl group, or may be a -N (- p group. Among these, in the general formula (G), R" and R" are carbon Preferably, the number of alkyl groups is 10 or less, or one in which -N's form one NO group.

\ , / N-cyclohexy-2-benzothiazyl sulfenamide (CZ), N-oxydiethylene-2-benzothiazyl sulfenamide, N-N-dicyclohexy-2-benzothiazyl sulfenamide, N. N-diethyl-2-benzothiazylsulfenamide, N-t-butyl-2-benzothiazylsulfenamide (NS), N-t-octyl-2-benzothiazylsulfenamide, N-N-diisopropylene Ru-2-Benzithiazylsulfenamide (
PSA), 2-(2.6-dimethyl-4-morpholinothio)benzothiazole, etc. are preferably used.
Among them, CZNNSNNPSA is preferred.

Furthermore, as the xanthate and its salts (h) of the present invention, the following general formulas (H-1) and (H-2) [wherein R is an alkyl group having 10 or less carbon atoms, M is sodium or zinc, n represents an integer of 1 to 2.

For example, zinc dibutyl xanthate (π■), zinc isopropyl xanthate, sodium isopropyl xanthate, dibutylxanthogen disulfide (CPB), zinc diethyl xanthate, etc. are preferred, among which ZBX) C.P.
B is particularly preferred. Further, the compound (j) of the present invention is a condensate of one or more altehydes having 10 or less carbon atoms and amines having 10 or less carbon atoms, and preferred aldehydes include aliphatic aldehydes, and preferred amines include aliphatic aldehydes. Examples include ammonia primary aliphatic amines and anilines.

Examples of compound (j) include a condensate of butyraldehyde and aniline, a condensate of butyraldehyde and butylaniline, a condensate of butyraldehyde and butylideneaniline, a condensate of formaldehyde and paratoluidine (F
P), a condensate of heptaldehyde and aniline, a condensate of acetaldehyde and ammonia (AC), a condensate of ethylaldehyde, formaldehyde and ammonia,
Condensates of butyraldehyde, acetaldehyde, and aniline, hexamethylenetetramine, etc. are used.
Among these, FPNAC and the like are preferred. Also, the compound (k) of the present invention is a sulfur-donating compound (sulfur donor).
(excluding thiuram sulfides) decomposes above room temperature. It refers to a compound having the property of releasing sulfur, and in the present invention, R-S-S-R (R represents an alkyl, aryl, aralkyl acyl or morpholino group).

Preferably, the organic groups have 15 or fewer carbon atoms. )
are preferable, and morpholino disulfide, alkylphenol disulfide, dialkyl disulfide (n-amyl disulfide, γ-hydroxypropyl disulfide, α.α-dithiodipropionate, β・β-dithiodipropionate, ethyl-t-
butyl disulfide, etc.), diallyl disulfide (diphenyl disulfide, ditolyl disulfide, dixylyl disulfide, 4 4'-
Diaminodiphenyl disulfide, bis(2-aminophenyl) disulfide, di-o-benzamidophenyl disulfide, o-, m-, and p-nitrophenyl disulfide, etc.), benzoyl disulfide, etc. are used, among others, morpholino Disulfoids and diallyl disulfides are particularly preferred. The vulcanization accelerators used in this budding process are compound (a) and compound (
b) - ゛, at least one selected from (k); consisting of compounds (b) - (k) per 1 part by weight of compound (a);
Total amount of one or more selected from 0.05 to 20
It is used in an amount of 0.2 to 5 parts by weight, more preferably 0.2 to 5 parts by weight.

In addition, compounds (b) to (k) per 1 part by weight of component (a)
When the amount of at least one selected from the following is 0.5 parts by weight or more, especially 1 part by weight or more, the resulting mixture has the advantage of being easily powdered and easy to handle.

Furthermore, as the vulcanization accelerator, compound (a) and compound (a
) 0.05 to 2 parts by weight, preferably 0.05 to 2 parts by weight.
2 to 1 parts by weight of compound (b) and 0.05 to 20 parts by weight, more preferably 0.1 to 5 parts by weight of the above, per 1 part by weight of the mixture of compound (a) and compound (b). Compound group (
Particularly preferred is one consisting of at least one selected from c) to (k). In the present invention, the vulcanization accelerator used is mixed into the rubber base material that requires vulcanization, either all together or separately, using conventional means such as a roll mill or Panbury mixer. Then, add and mix.

Furthermore, when a reaction product of sulfur chloride and a hydroxyl group-containing aromatic compound is used as compound (a), a predetermined amount of compound (b) and /or compound groups (c) to (k
) may be used in combination with at least one selected from the following by appropriate means. The vulcanization accelerator used in the present invention is not necessarily a pure product, and even if it contains a relatively small amount of impurities, it still has suitable performance and does not pose any problem in achieving the purpose of the present invention. Therefore, for example, the following specific mixing method can be adopted.

(1) In the crude product (compound α) obtained by reacting sulfur chlorides and a hydroxyl group-containing aromatic compound in an organic solvent, the compound (b) and/or compound group (c) of the present invention is added. A predetermined amount of at least one species selected from ~(k) was added and mixed well. Well, under normal pressure or reduced pressure,
Allow the organic solvent to distill off. (2) The vulcanization accelerator obtained by distilling off the organic solvent in (1) is further washed several times with water, filtered, and then dried.

(3) The crude product obtained in (1) was once poured into water, left to stand, and then the upper supernatant water layer was removed, and the compound (b) and/or compound groups (c) to ( A predetermined amount of at least one of k) is added, mixed, and then dried under normal pressure or reduced pressure.

(4) If necessary, methanol is added to the crude product obtained by removing the upper supernatant water layer in (3) to form a solution, and then compound (b) and/or compound group (c The vulcanization accelerator obtained by adding and mixing a predetermined amount of at least one selected from () to (k) and then adding a large amount of water to settle the obtained vulcanization accelerator is separated from each other and dried.

An advantage of adopting the mixing methods (1) to (4) above is that the vulcanization accelerator thus obtained always works by closely bonding each component in the rubber base material under any usage conditions. The original synergistic effect is clearly exhibited, and poor dispersion during mixing into the rubber base material is greatly improved, and the mixture of each component can be easily made into a powder that is extremely easy to handle during use. It has many characteristics such as the heart.

Each of the compounds constituting the vulcanization accelerator used in the present invention may be composed of a single component as long as it is used as a mixture in the above-mentioned mixing ratio, or a combination of two or more kinds may be used. The total amount of each compound is about 0.1 to 30 parts by weight, preferably about 0.5 to 30 parts by weight, per 10 parts by weight of the chlorine-containing elastomer.

In the present invention, a metal oxide is used instead of the sulfur conventionally used as a vulcanizing agent, but the amount of sulfur is less than 1 part by weight, preferably less than 1 part by weight per 100 parts by weight of the chlorine-containing base lastomer. A small amount of less than 0.5 parts by weight may be allowed to coexist. However, it is preferable that they not coexist. In the present invention, anti-aging agent carbon black, mineral fillers, process oils, waxes, lubricants, anti-scorch agents, processing aids, pigments, and other additives commonly used in rubber may be used in combination. There is no problem, and these and the vulcanization accelerator may be mixed in advance and used in the form of powder or paste.

The amount of the metal oxide vulcanizing agent used in the present invention is 2 parts to 10 parts, preferably 5 parts to 25 parts, per 10 parts of the chlorine-containing elastomer. To obtain a chlorine-containing elastomer vulcanizate which is used as an elastomer vulcanization system and does not require the addition of scorch, has a moderately fast vulcanization rate, is tightly vulcanized, and exhibits excellent and well-balanced mechanical properties. be able to.

Examples of metal oxide vulcanizing agents used in the present invention include Group Ⅰ metal elements such as beryllium, magnesium, zinc, and calcium, Group Ⅰ metal elements such as titanium, tin, zirconium, and lead, antimony, vanadium, etc. Group V metal elements and group ■ such as chromium, molybdenum, tungsten, etc.
group metal elements, and group metal elements such as iron, nickel, and cobalt.
Examples include oxides of group metal elements, among which oxides of zinc, magnesium, calcium, titanium, antimony, and lead are preferred, and one or a mixture of two or more of these can be suitably used.

In order to vulcanize a chlorine-containing elastomer using the above-mentioned vulcanization accelerator and the metal oxide, these may be used separately or simultaneously, or after pre-mixing a predetermined amount of each, using a roll mill or a pan. Uniformly mixed into the chlorine-containing polymer using a conventional mixing method such as a bally mixer,
It is sufficient to maintain 5 to 12 powders at a temperature of 00 to 220°C.

Hereinafter, the present invention will be explained in more detail with reference to experimental examples and examples.

Experimental Example 1 165y of sulfur dichloride was added to a solution of 270 da of resorcin and 31 of anhydrous diethyl ether, and the mixture was reacted at 0 to 5°C.

After the reaction was completed, diethyl etherf was distilled off, and the contents were poured into ice water with stirring. The resulting white precipitate was dried door to door to obtain the target product in the form of a white powder. The product is M. p. l
It was 2,2',4,4'-tetrahydroxydiphenyl sulfide with a temperature of 6 l to 163°C, and the yield was 40%.

Experimental Example 2 The same reaction and post-treatment as in Experimental Example 1 were carried out, except that catechol 135da and hydroquinone 135f1 were used in place of resorcinol, and a pale yellow syrupy substance was obtained in a yield of 84%.
I got it.

Experimental Example 3 In a solution of 50 y of catechol and 100 ml of methanol, 4
24.5y of sulfur monoxide is added and reacted at a temperature below 5°C.

After the reaction was completed and left to stand for 12 hours, the methanol was distilled off under reduced pressure, the residue (syrup-like) was washed with the minimum amount of water (100 ml), and dried under reduced pressure at 50'C or less. A yellow caramel-like substance is obtained. (Yield 85.0%) Experimental example 450y
The reaction was carried out in the same manner and under the same conditions as in Experimental Example 3, except that 50y resorcinol was used instead of catechol, and a yellow carmela-like reaction product was obtained in a yield of 90%.

Experimental Example 50y of hydroquino instead of 50y of catechol. The reaction was carried out in the same manner and under the same conditions as in Experimental Example 3, except that a yellow carmela-like reaction product was obtained with a yield of 81%.

Experimental Example 6 The reaction was carried out in the same manner and under the same conditions as in Experimental Example 3, except that 56 Da pyrogallol was used in place of 50 Y catechol, and a light brown, viscous liquid reaction product was obtained with a yield of 73%.

Experimental Example 7 * *The reaction was carried out in the same manner and under the same conditions as in Experimental Example 3, except that 72y 2,3-dihydroxynaphthalene was used in place of 50y catechol, and a brown syrupy reaction product was obtained with a yield of 69%. obtain.

Experimental Example 8 25g of hydroquinone is dissolved in 50mt of methanol and reacted with 12.2y of sulfur monochloride at below 45°C.

Next, 25 Da of catechol in 50 ml of methanol solution was added, followed by 12.2 Da of i-sulfur monochloride, and the reaction was carried out at 45° C. or below. After the reaction was completed, it was left at room temperature for an hour. After distilling off the methanol, it is washed with water and dried to obtain a pale yellow fine powder product.

Yield: 47.1y Experimental Example 9 30y of the reaction product obtained in Experimental Example 3 was further dissolved in 300ml of methanol to form a solution, and then 15y of diphenylguanidine and 168y of tetramethylthiuram disulfide were added. After stirring vigorously, the resulting slurry mixture was distilled off with methanol under reduced pressure and dried to quantitatively obtain a pale yellowish white powder of a vulcanization accelerator used in the present invention.

Experimental Example 10 2e of water was added to the slurry mixture obtained in Experimental Example 9, and the precipitated pale yellow-white powder was separated and air-dried.

Similarly, vulcanization accelerators made of the compounds shown in Table 1 were obtained using the methods shown in Table 1.

Examples 1 to 40, Comparative Examples 1 to 6 Using W type chloroprene rubber as the resin base material, compounds (a) and compounds (b) to (k) shown in Table 2 were prepared in the following basic formulations.
and metal oxides.

Chloroprene rubber (Neoprene W) 10 parts (parts by weight) Stearic acid 1 part (parts by weight) Dixie clay Marked part (parts by weight) HAF carbon 25 parts (parts by weight) Process oil R-1000m parts (parts by weight) Micrololistalin wax 1 part (by weight) antioxidant DDAl part (by weight) Each compounding agent shown in Tables 2 and 3 is expressed in parts per 10 parts of chloroprene.

These formulations were kneaded by rolls, and then, in order to evaluate the crosslinking properties of each composition, the minimum value of Mooney viscosity and its viscosity increase characteristics were measured using a Mooney viscometer at 125°C, After 5 minutes using an oscillating disk rheometer at °C (T
. ), after 2 mins (T.O) and maximum torque reached (Tma
x) (K9-CwL) was measured. Furthermore, 1 of each formulation
Press vulcanization was performed at 50°C for 30 minutes to produce a vulcanized sheet with a thickness of about 27WL, and its mechanical properties were measured. Further, the elongation retention rate of the vulcanized rubber was measured after aging for 96 hours while the gear was open at 1200C. The results obtained are shown in Table 3.

Examples 41-45, Comparative Examples 7-8 As a resin base material, TW type black In the following basic formulation using The vulcanization accelerator of the present invention shown below was blended.

Neoprene TW Magnesia stearate SRF Black dexy clay*ZnO Microcrystalline wax Antioxidant DDA These blends were kneaded with a roll and heated at 150°C;
3. Mechanical properties of vulcanized rubber sheet obtained by press vulcanization,
And aging characteristics were measured in the same way as Examples 1-40.

Claims (1)

[Claims] 1. Chlorine-containing elastomer, metal oxide vulcanizing agent, biscatechol-mono-sulfide, biscatechol-
poly-sulfide, bishydroquinone-mono-sulfide, bishydroquinone-poly-sulfide,
and a compound (a) consisting of one or more types selected from the group consisting of the above-mentioned sulfide derivatives, and the general formula B ▲There are mathematical formulas, chemical formulas, tables, etc.▼...B [in the formula, R
_1 to R_4 are each an alkyl group, an aralkyl group,
or an aryl group, and y is a positive integer of 1 to 4] (b), guanidines (c), thioureas (d), thiazoles and their salts (e)
, dithiocarbamates (f), sulfenamides (g), xandate and its salts (h), aldehyde-amine condensates and aldehyde-ammonia condensates (
j), and one or more compounds selected from compound group (b) to (k) consisting of sulfur-providing compounds (k) excluding compound (b), and compound (a
) A crosslinkable chlorine-containing elastomer composition comprising a vulcanization accelerator in which the total amount of compounds selected from compound groups (b) to (k) is 0.05 to 20 parts by weight per part by weight. thing. 2. The composition of claim 1, wherein the chlorine-containing elastomer is polychloroprene. 3 As compound (a), 1 per mole of sulfur dichloride
．． Claim 1 uses a reaction product obtained by reacting a hydroxyl group-containing aromatic compound having at least two hydroxyl groups on an aromatic ring in an organic solution in the range of 8 to 2.2 moles. and the composition of item 2. 4 A reaction obtained by reacting a hydroxyl group-containing aromatic compound having at least two hydroxyl groups on an aromatic ring in an amount of 1.8 to 3 moles per mole of sulfur monochloride as compound (a) in an organic solvent. Compositions according to claims 1 and 2 using the products. 5. The composition according to claim 1, wherein compound (a) is a dihydric phenol or a monosulfide of a dihydric phenol derivative. 6. The composition of claim 1, wherein compound (a) is dihydroxynaphthalene monosulfide. 7 Compound (a) is added in an amount of 1.0% per mole of sulfur dichloride.
4. The composition according to claim 1, which is a reaction product obtained by reacting 8 to 2.2 moles of dihydric phenol or a dihydric phenol derivative in an organic solvent. 8 Compound (a) is 1.8 per mole of sulfur monochloride
The composition according to claims 1, 2, and 4, which is a reaction product obtained by reacting a dihydric phenol or a dihydric phenol derivative in an organic solvent in an amount of .about.3 moles. 9 Compound (a), compound (b) and compound group (c)
The composition according to claim 1, characterized in that it consists of one or two selected from (k). 10 1 mol of sulfur chloride and 1.8 to 1 mole of hydroxyl group-containing aromatic compound having at least two hydroxyl groups on the aromatic ring
3 moles in an organic solvent, and before isolating the reaction product produced by the reaction, 0% per 1 part by weight of the reaction product.
．． 5. The composition according to claim 4, wherein 05 to 20 parts by weight of at least one selected from compound groups (b) to (k) are added. 11 1 mole of sulfur dichloride and at least 2 moles of sulfur dichloride on the aromatic ring.
Hydroxyl group-containing aromatic compound having 1.8 to 2 hydroxyl groups
．． 2 mol in an organic solvent, and before isolating the reaction product produced by the reaction, 0.05 to 20 parts by weight of compounds ( b)
The composition according to claim 3, characterized in that at least one selected from ~(k) is added. 12. The composition according to claims 3, 4, 7, 8, 10 and 11, wherein the organic solvent is a low alcohol absorption or lower dialkyl ketone. 13 Compound (b) is R_1 to R_4 in general formula B
are each an alkyl group having 5 or less carbon atoms, or R_1
~R_2 and R_3 to R_4 are chain-bonded at their terminals to form a carbocycle, that is, R_1-N-R_2 forms a nitrogen-containing carbocycle, and the number of carbon atoms constituting the carbocycle is 10 or less or an aralkyl group or an aryl group having 8 or less carbon atoms, and y is 1 to 4.