JPS59129255A - Vulcanizable epichlorhydrin rubber composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having improved resistance to thermal aging, lubricating oil and fuel oil, consisting of an epichlorhydrin rubber and a carboxylic acid-contg. ethylene/acrylic rubber. CONSTITUTION:A vulcanizing agent such as ethylene-thiourea, 2-5pts.wt. acid acceptor selected from among arom. carboxylate salts, aliph. carboxylate salts, silicate salts, oxides and hydroxides of Groups IIa, IIb and IVa metals and, optionally, filler reinforcing agent, plasticizer, softening agent, antioxidant, etc. are blended with 100pts.wt. rubber component consisting of 50-97wt% epichlorhydrin and 50-3wt% carboxylic acid-contg. ethylene/acrylic rubber.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an epichlorohydrin rubber that improves heat aging resistance, lubricating oil resistance, and fuel oil resistance by adding carboxylic acid-containing edylene-acrylic rubber to epichlorohydrin rubber. The present invention relates to vulcanized compositions.

Conventionally, epichlorohydrin rubber has oil resistance, heat resistance,
Known as a rubber with excellent weather resistance, it is widely used mainly in rubber parts related to EJJ and other industries.

Recently, in the automobile industry, -C
Even more advanced performance is now required, and for example, f[ Rubber parts with high quality are in demand.

Conventionally, epichlorohydrin rubber and acrylic rubber have been used in such fields, but the epichlorohydrin rubber has problems with heat aging resistance and lubricant resistance in high-quality products, and acrylic rubber has poor flame resistance. Δ'81 Oiliness (I noticed this problem.

A report on the technique of adding polycarboxylic acids such as abilaic acid and zebacic acid to improve the heat aging resistance of the above epichlorohydrincomb (Percules Technical Coordination OR +
-(-, 19A), but this was sufficient to improve the heat aging resistance under the above-mentioned high temperature conditions (') was 4T.

As a result of intensive studies to obtain a rubber composition that meets the above-mentioned high performance requirements, the present inventors have developed a composition in which a carboxylic acid-containing ethylene-acrylic rubber is blended with an epichlorohydrin rubber. However, it has been found that a vulcanizate with a good balance of the above properties can be obtained.However, even if the polymer also contains carboxylic acid, in the case of carboxylated acrylonitrile-butadiene rubber, , (2) It was found that the heat aging resistance of the dichloromethane-based rubber composition was hardly improved.

A (The invention is an ethylene acrylic rubber containing 50 to 97% epichlorohydrin rubber and carboxylic acid)
The present invention provides a J-pichlorohythrin-based rubber-added Mi composition with well-balanced physical properties as described above, which is characterized by containing a rubber component of ~3w%.

As a bichlorohydrin rubber used in the present invention (Y, epichlorohydrin homopolymer rubber, J Biku []
] Ruhydrin-ethylene A-X-→noid copolymer rubber, shrimp chlorohydrin-allyl glycidyl dec-ral copolymer rubber, shrimp "I-ruhydrin-ethylene oxide allyl glycidyl ether copolymer rubber, etc. alone or Mixtures may be mentioned.

The carboxylic acid-containing ethylene-acrylic rubber used in the present invention is mainly composed of nytylene and lower alkyl acrylic esters such as methyl acrylate and acrylic A'2-c del. Refers to at least three-component copolymer rubber containing several percent of carboxylic acid such as acrylic acid or methacrylic acid as a rubber vulcanizing component.

As such a carbibonic acid-containing ethylene-acrylic rubber (l' V AMAC
B-12'4. l, IVAMACN-123",
These materials are commercially available as elastomer master bunches containing some fillers. Incidentally, C in the above-mentioned carboxylic acid-containing ethylene-acrylic rubber is described in detail in JP-A-54-127947.

In the composition of the present invention,
1. Epichlorohydrin rubber j) 0 to 97 @ suspension %, special (,'l good sl: L < c 6 () to 95 small volume carboxylic acid-containing 1-Runula'cri r) Tsuku-based rubber 50
to 3% by weight, especially in the range of 40 to 41%.

] Biku [1 Rujidolin rubber is less than 50 hands 1i% 41
In addition, if the amount of carboxylic acid-containing ethylene-acrylic rubber is less than 3% by weight, the fuel oil resistance will gradually deteriorate. I can't seem to improve my sexuality enough.

As the vulcanizing agent for this component, those commonly used in epichlorohydrin-based rubbers may be used, such as diuretic derivatives such as Edilene A-urea and Trimédiluti A-urea; BoI noamines such as Kizamethi 1 nondiamino J-bamei 1; 1 to S'f-Δcyanuric acid, 2
, 3-Dimerkab 1 to quinocyryline; thiurams such as Te 1 helame 1 ruthiium disulfide; Examples include vulcanizing agents using polycarboxylic acids that use strong bases such as ammonium salts.In particular, vulcanizing agents using polyamines and polycarboxylic acids that co-vulcanize the two types of rubber of the composition of the present invention. (additional) φ1
It is possible to further improve the heat aging resistance of objects.

The composition of the present invention preferably contains an acid acceptor such as those commonly used in phosphorus-based additive compositions. Moreover, as an acid acceptor, E
Jl, for example, period I'' (Table group ■ al disease, 1st [bh\
, and an apricot group carboxylate of group 17a,
Examples include aliphatic) J-notate salts, silicates, hydroxides, oxides, and the like. In particular, it is preferable to use a Group 1 VA lead compound.The effective amount of the adsorbent used is 2 to 5 parts by weight based on 100 parts by weight of the rubber component.

The composition of the present invention may further contain compounding agents commonly used in the field of art 14.j, such as fillers, reinforcing agents, plasticizers, softeners, anti-oxidants, antioxidants, and processing aids. Agents and the like may be added as appropriate.

Mixing and molding of the composition of the present invention are generally carried out in the field of rubber additives (
The method used in J-3 is applied.

Although the invention will be explained with reference to examples, the present invention is not limited to the following examples.

Example 1 - 1] Comparative Examples 1 to 4 Each compounding agent in Table 1 was added to the following common compound, mixed in a finch roll at 60 to 70°C for 15 to 20 minutes, and then mixed at 160' C180kg/cn? After pressing for 30 minutes at 150°C, the mixture was further post-vulcanized at 150°C for 5 hours.

Physical property tests according to JISK-6301 were conducted on each of the 44 vulcanized samples, and the results are shown in Table 2.

4, Comparative Example 1, 21J: This is an example in which the rubber component is only epichlorohydrin rubber, and Comparative Example 3 is an example in which polycarboxylic acid is added to -L-Pic 1-ruhydrin rubber. Comparative Example 1 is a polymer doji-
This is an example in which carboxyltadiene rubber was used instead of the carboxylic acid-containing ethylene-acrylic rubber of the present invention.

Rubber 1oO small part SR
F Carbon 60 Il Dibutylene Tin Sdeare - 1-in Nickel Dibutyl Tin Sdeere 17.

Table 1 Compound Niyama Ti
Part: 11 (1)i±Bitter]n-1"j Daiso shrimp chlorano\one1 made (2) IVΔ[\4△C B-12/IJte"-
The products listed in 1. Rubber 100 include S Todo Carbon 24 East Early Part, but Go compound i1 in Table 1 is shown as pure rubber.

3) 1-Flynac 2 2 1 j Manufactured by Borisar (
/l)1. Scarcity (-shibu7su- bisik D (5,4
．． 0) "Syn-i" t-7 (1 BU) and (11,5)'Ele salt of levacic acid (i 1-4 m9)-: (-1-2 From Table 2 I wonder if it's okay (K-hoi I! I
] σ) 11116A product (Rad copper 1 aging resistance, especially at high temperatures) σ) 141 Y/]

Implementation IyJ6-10 Comparative Examples 2 and 5 to 8 Using the rubbers shown in Table 3, the following formulations were vulcanized in the same manner as Examples 1 to 5, and physical property tests were conducted. The results are shown in Table 4. Ta. By the way, Comparative Example 2 uses the compound of Comparative Example 2 as is, and Comparative Example 5 is an example outside the range of the rubber compounding ratio of the present invention.
Comparative Example 6 is an example C' using only bichlorohydrin-based binary copolymer rubber, Comparative Example 7 is an example using only ordinary acrylic rubber, and Comparative Example 8 is an example using only carboxylic acid-containing ethylene-acrylic rubber. It is.

Compound rubber 1oo8i2 part S RF force-1'60j! i
! fllI5 n 1 to 111 1 to 111 1 to 111 1 to 111 1 to 111 1 to 111 1 to 111
u total〈1) 1-Ebikroma = HJ Inuso Ebiku ``1-Tuber observation (2) ru Nibiku 0? -C-1 person W J-e Ril
-, U Ra/<, - manufactured by Co., Ltd. (3) [Epichrome 1mer CG j Jiso Ebiku [] manufactured by Rubber Co., Ltd. (4) rVAMΔCB-'12/ll Teyubonn 1 (,
5) ItAc[]]n△R-740j Manufactured by Toa Pain Co., Ltd. 63 45 0 (-17 51 → -7 -+-45 18 7 '' = 18 82 76 30 +88 As is clear from Table 4 above, It can be seen that the vulcanizate of the present invention has a well-balanced 1Q quality in heat aging resistance at high temperatures, lubricating oil resistance, and flame resistance.In contrast, C, epichlorohydrin-based rubber The vulcanizates of Comparative Examples 2 and 6 alone have excellent heat aging resistance and 614 lubricating oil IV.
J has a defect. Furthermore, Comparative Examples 7 and 8, which contained only epichlorohydrin rubber and only goacrylic rubber, were significantly inferior in fuel oil resistance.

As long as the applicant is l,i)! Agent Co., Ltd. Buwo Tanukishi Toru Monta

Claims (1)

[Claims] An epichlorohydrin-based comb vulcanization composition comprising a rubber component consisting of 50-97% by weight of Epic 1-1 lehydrin-based rubber and 50-3% by weight of a carboxylic acid-containing ethylene-acrylic rubber.