WO2022071279A1 - Rubber composition - Google Patents

Abstract

There is a need for a material that uses a polyether polymer to have better heat resistance, and also a need for said material to simultaneously have better oil resistance. The present invention addresses the problem of providing a rubber composition and a cross-linked product thereof for these needs. The present invention provides: a rubber composition containing (a) a polyether polymer as a rubber component and (b) calcium silicate which has a wollastonite-type crystal system; and a cross-linked product of the rubber composition.

Description

Rubber composition

It is an object of the present invention to provide a rubber composition and a crosslinked product for a material having excellent heat resistance and oil resistance.

Generally, a polyether polymer such as an epichlorohydrin-based polymer is widely used as a material having excellent various physical properties by being crosslinked, and is used as a fuel hose, an air-based hose, and a tube material in automobile applications. ing.

Various anti-aging agents have been studied in order to improve heat resistance, and it is widely known that excellent heat resistance can be obtained by applying an organic nickel-based anti-aging agent such as nickel dibutyldithiocarbamate to rubber. (See Patent Document 1).

Japanese Unexamined Patent Publication No. 2013-147582

However, as a material using a polyether-based polymer, further excellent heat resistance may be required, and at the same time, excellent oil resistance is also required, and a rubber composition for that purpose and a crosslinked product thereof. The challenge is to provide.

The present inventors have (a) a rubber composition containing a polyether-based polymer as a rubber component, and (b) a rubber composition containing calcium silicate having a wollastonite-type crystalline system, and a crosslinked product thereof. , The present invention has been completed by finding a solution to the above-mentioned problems.

That is, the present invention relates to the following.
Item 1 (a) A rubber composition containing a polyether polymer and (b) calcium silicate having a wollastonite crystal system.
Item 2 The rubber composition according to Item 1, wherein the (a) polyether-based polymer contains at least one unit selected from ethylene oxide, propylene oxide, epichlorohydrin, and allyl glycidyl ether as a constituent unit.
Item 3 The rubber according to Item 1 or 2, wherein the content of calcium silicate in which the crystal system is a wollastonite type is 10 parts by mass or more with respect to 100 parts by mass of the (a) polyether polymer. Composition.
Item 4 A crosslinked product obtained by cross-linking the rubber composition according to any one of Items 1 to 3.

The crosslinked product obtained by cross-linking the rubber composition of the present invention has excellent heat resistance and oil resistance, and is therefore useful as a tube material for fuel hoses, air hoses, etc., and rubber packing, especially in automobile applications.

The present invention will be described in detail below.

The rubber composition of the present invention contains (a) a polyether polymer as a rubber component, and (b) calcium silicate whose crystal system is a wollastonite type. As a result, it is excellent in heat resistance and oil resistance.

Although the above-mentioned effect can be obtained from the rubber composition, the reason why such an action and effect can be obtained is not always clear, but it is presumed as follows.
(B) Calcium silicate having a wollastonite-type crystal system is needle-like (fibrous), and therefore has good dispersion in a rubber composition containing (a) a polyether-based polymer as a rubber component. Has sex. Therefore, in a rubber composition containing (a) a polyether-based polymer as a rubber component, (b) calcium silicate whose crystal system is a wollastonite type is appropriately dispersed, resulting in heat resistance and oil resistance. Excellent for.

Examples of the polyether polymer (rubber) used in the present invention include alkylene oxides such as ethylene oxide, propylene oxide and n-butylene oxide, methyl glycidyl ether, ethyl glycidyl ether, n-glycidyl ether and allyl glycidyl ether. , A homopolymer or a copolymer of a compound selected from glycidyls such as phenylglycidyl ether, epihalohydrins such as epichlorohydrin and epibromhydrin, and styrene oxide. (A) The polyether-based polymer may be used alone or in combination of two or more.

The polyether-based polymer preferably contains at least one unit selected from ethylene oxide, propylene oxide, epichlorohydrin, and allylglycidyl ether as a constituent unit, and the epichlorohydrin unit as a constituent unit. It is more preferable to include at least one unit selected from propylene oxide, ethylene oxide, and allylglycidyl ether and epichlorohydrin as a unit constituent unit, and the epichlorohydrin and ethylene oxide units are more preferably contained. Most preferably, it is included in the structural unit.

As the polyether-based polymer, the constituent unit based on epichlorohydrin is preferably 10 to 100 mol%, more preferably 20 to 75 mol%, and 25 to 65 with respect to the total polymerization unit. It is particularly preferably mol%.

As the polyether-based polymer, the composition unit based on ethylene oxide is preferably 0 to 90 mol%, more preferably 25 to 80 mol%, and 35 to 75 mol% with respect to the total polymerization units. Is particularly preferable.

As the polyether-based polymer, the structural unit based on propylene oxide and the structural unit based on allyl glycidyl ether are preferably 0 to 15 mol%, preferably 0 to 12 mol%, based on the total polymerization units. More preferably, it is particularly preferably 0 to 10 mol%.

The rubber composition of the present invention may contain only (a) a polyether-based polymer as a rubber component, or may further contain a rubber type other than the above-mentioned polyether-based polymer. Examples of rubber other than the polyether polymer obtained by polymerizing an oxylan compound include natural rubber and synthetic rubber, and examples of the synthetic rubber include isoprene rubber (IR), 1,2-polybutadiene (VBR), and styrene butadiene rubber. (SBR), Butyl Rubber (IIR), Ethylene Propropylene Rubber (EPM), Ethylene Propropylene Diene Rubber (EPDM), Chloroprene Rubber (CR), Chlorosulfonated Polyethylene (CSM), Chlorinated Polyethylene (CPE), Acrylic Rubber (ACM) , Acrylonitrile butadiene rubber (NBR), hydrided acrylonitrile butadiene rubber (H-NBR), and at least one selected from ethylene propylene rubber (EPDM), chloroprene rubber (CR), and acrylonitrile butadiene rubber (NBR). Is preferable.

When the rubber component of the rubber composition of the present invention contains a rubber type other than the polyether polymer, the polyether polymer is 10 to 90% by mass in the rubber component, and the polyether polymer is used. It is preferable to contain 90 to 10% by mass of a rubber type other than the material, and more preferably to contain 30 to 90% by mass of the polyether polymer and 70 to 10% by mass of a rubber type other than the polyether polymer. It is particularly preferable to contain 70 to 90% by mass of the polyether polymer and 30 to 10% by mass of a rubber species other than the polyether polymer.

The content of the (a) polyether polymer in 100% by mass of the rubber component is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass. May be.

In the present invention, as a specific example of (b) calcium silicate in which the crystal system is a wollastonite type, wollastonite such as zono (to) light, cataite, okenite, finbrandite, and foschagit (b) Calcium silicate, which is a type (including both α-type and β-type), can be exemplified, and at least one selected from these is preferable. (B) Calcium silicate whose crystal system is a wollastonite type may be used alone or in combination of two or more.

(B) The average length of calcium silicate having a wollastonite type crystal system is 10 μm or more, preferably 12 μm or more, more preferably 20 μm or more, 1000 μm or less, preferably 200 μm or less, and more preferably 50 μm or less. Is.

(B) The aspect ratio (average length / average width) of calcium silicate having a wollastonite type crystal system is preferably 1.6 or more, more preferably 2.0 or more, still more preferably 2.5 or more. It is particularly preferably 2.8 or more, preferably 10 or less, more preferably 5.0 or less, and further preferably 3.5 or less.

In the present specification, the average width of calcium silicate is an average value of the width of calcium silicate measured by a transmission electron microscope (for example, an average value calculated by measuring the width of 100 calcium silicates). Is. Further, in the present specification, the average length of calcium silicate is calculated by measuring the average value of the lengths of calcium silicate measured by a transmission electron microscope (for example, the lengths of 100 calcium silicates). Average value).
Here, the width of calcium silicate is the length of the short side of the main surface (the surface having the largest area when viewed in a plan view), and the length of calcium silicate is the length of the long side of the main surface. That's right.

In the present invention, (b) calcium silicate having a wollastonite type crystal system is preferably contained in an amount of 10 parts by mass or more, preferably 15 parts by mass or more, based on 100 parts by mass of the (a) polyether polymer. It is more preferably 20 parts by mass or more, 25 parts by mass or more, 60 parts by mass or less, more preferably 50 parts by mass or less, and 45 parts by mass. It is particularly preferable to contain a portion or less.

For the rubber composition of the present invention, in addition to the above, various antioxidants, reinforcing agents, plasticizers, processing aids, flame retardants, etc. used in the art, as long as the effects of the present invention are not impaired. A pigment, a cross-linking accelerator, a cross-linking agent and the like can be optionally blended. Further, as long as the characteristics of the present invention are not lost, it is possible to perform blending of a resin or the like, which is usually performed in the art. Each of these combination agents may be used alone or in combination of two or more.

Specific examples of anti-aging agents include benzimidazole-based anti-aging agents, dithiocarbamate-based anti-aging agents, amine-based anti-aging agents, phenol-based anti-aging agents, thiourea-based anti-aging agents, organic thioacids, and phosphite. Acids are mentioned, and at least one selected from these is preferable, benzimidazole-based anti-aging agent, dithiocarbamate-based anti-aging agent is more preferable, and dithiocarbamate-based anti-aging agent is preferable. More preferred.

Examples of the benzimidazole-based antiaging agent include zinc salts of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and 2-mercaptobenzimidazole.

Specific examples of the dithiocarbamate-based antiaging agent are nickel diethyldithiocarbamate, nickel dimethyldithiocarbamate, nickel dibutyldithiocarbamate, nickel diisobutyldithiocarbamate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate, N. Examples thereof include copper ethyl-N-phenyldithiocarbamate, copper N-pentamethylene dithiocarbamate, and copper dibenzyldithiocarbamate.

Examples of the amine-based antiaging agent include phenyl-α-naphthylamine, phenyl-β-naphthylamine, p- (p-toluenesulfonylamide) -diphenylamine, 4,4'-(α, α'-dimethylbenzyl) diphenylamine, 4 , 4'-Dioctyl diphenylamine, high temperature reaction product of diphenylamine and acetone, low temperature reaction product of diphenylamine and acetone and low temperature reaction product, low temperature reaction product of diphenylamine, aniline, acetone, reaction product of diphenylamine and diisobutylene, octylated diphenylamine, Dioctylated diphenylamine, p, p'-dioctyl-diphenylamine, octylated diphenylamine mixture, substituted diphenylamine, alkylated diphenylamine, alkylated diphenylamine mixture, aralkylated diphenylamine-based alkyl and aralkyl-substituted phenol mixture, diphenylamine derivative, N, N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N, N'-di-2-naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl -P-Phenylenideamine, N-Phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl) -p-Phenylenideamine, N, N'-bis (1-methylheptyl) -p-Phenylenideamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) There are a mixture of -N'-phenyl-p-phenylenediamine, diallyl-p-phenylenediamine, phenyl, hexyl-p-phenylenediamine, phenyl, octyl-p-phenylenediamine, etc., and aromatic amines as other amines. Condensed product of and aliphatic ketone, butylaldehyde-aniline condensate, polymer of 2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-2,2,4-trimethyl-1,2-dihydro Examples thereof include quinoline, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 4,4'-bis (a, a-dimethylbenzyl) diphenylamine, N, N'-di-2-naphthyl-. It is preferably at least one selected from p-phenylenediamine.

Examples of the phenolic antiaging agent include 2,5-di- (t-amyl) -hydroquinone, 2,5-di-t-butylhydroquinone, and hydroquinone monomethyl ether, and the monophenolic agent is 1-oxy-3-. Methyl-4-isopropylbenzene, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6 -Di-t-butyl-4-sec-butylphenol, butyl hydroxyanisole, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-t-butyl-α-dimethylamino-p -Cresol, alkylated phenol, aralkyl substituted phenol, phenol derivative, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2 , 2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2-methylenebis (6-α-methyl-benzyl-p) -Cresol), 4,4'-butylidenebis (3-methyl-6-tert-butyl cresol), 2,2'-etylidenebis (4,6-di-tert-butylphenol), 1,1'-bis (4) -Hydroxyphenyl) -cyclohexane, 2,2'-dihydroxy-3,3'-di- (α-methylcyclohexyl) -5,5-dimethyldiphenylmethane, alkylated bisphenol, butylation of p-cresol and dicyclopentadiene Reaction product, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (4-tert-butyl) -3-Hydroxy-2,6-dimethylbenzyl) isocyanurate, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2- [1- (2-Hydroxy-3,5-di-tert-pentylphenyl) -ethyl] -4,6-di-tert-pentylphenyl acrylate, 3,9-bis [2- {3 (3- (3-) tert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] un Decane, butylic acid 3,3-bis (3-tert-butyl-4-hydroxyphenyl) ethylene ester, 1,3,5-tri (2-hydroxyethyl) -s-triazine-2,4,6- (1H) , 3H, 5H) Trione 3,5-di-tert-butyl-4-hydroxyhydrolauric acid triester, modified polyalkyl subphosphate polyvalent phenol, 4,4'-thiobis (6-tert-butyl-) 3-Methylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-thiobis- (6-tert-butyl-o-cresol), 4,4'-di and Tri-thiobis- (6-tert-butyl-o-cresol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 1,1,3-tris- (2-methyl-4-) Hydroxy-5-tert-butylphenyl) butane, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2-thiobis (4-methyl-6-tert-butylphenol), n-octadecyl- 3- (4'-Hydroxy-3', 5'-di-tert-butyl-phenyl) propionate, tetrakis- [methylene-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) Propionate] methane, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4) -Hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-Hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 2,2- Thio-diethylenebis [3- (3,5-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethirebis (3,5-tert-butyl-4-hydroxy-hydrocinnamamide), 2 , 4-Bis [(octylthio) methyl] -o-cresol, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate-diethyl ester, tetrakis [methylene (3,5-di-t) ert-butyl-4-hydroxyhydrocinnamate)] methane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ester, hindered phenol, hindered bisphenol, 2-hydroxynaphthalene -3-Carboil-2'-methoxyanilide, 2-hydroxynaphthalene-3-carboyl-2'-methylanilide, 2-hydroxynaphthalen-3-carboyl-4'-methoxyanilide, 4,4'-bis (N, Examples thereof include N'-dimethylamino) -triphenylmethane, 2-hydroxynaphthalene-3-carboylanilide, 1,1'-bis (4,4'-N, N'-dimethylaminophenyl) -cyclohexane, and the like. 2,2'-Methylenebis (4-ethyl-6-tert-butylphenol), 2'2-Methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert- Butylphenol), preferably at least one selected from 4,4'-thiobis (3-methyl-6-tert-butylphenol).

Examples of the thiourea-based antiaging agent include 1,3-bis (dimethyl-aminopropyl) -2-thiourea and tributylthiourea. It was

Dilauryl thiodipropionate, disstearyl thiodipropionate, dimyristyl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, pentaerythritol-tetrakis- (β) as organic thioacids -Lauryl-thiopropionate), dilauryl-thiodipropionate and the like are exemplified.

Examples of phosphites include tris (nonyl-phenyl) phosphite, tris (mixed mono- and di-nonylphenyl) phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monotridecyl phosphite, and diphenyl isodecyl. -Phosphite, Diphenyl-Isooctyl-Phosphite, Diphenyl-Nonylphenyl-Phosphite, Triphenylphosphite, Tris (Tridecyl) Phosfite, Triisodecylphosfite, Tris (2-ethylhexyl) Phosfite, Tris (2, 4-Di-tert-butylphenyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, 1,1,3-tris (2-methyl-4-di-) Tridecylphosfite-5-tert-butylphenyl) butane, 4,4'-butylidenebis (3-methyl-6-tert-butyl-di-tridecylphosfite), 2,2'-ethylidenebis (4,6) -Di-tert-butylphenol) fluorophosphite, 4,4'- _isopropidene -diphenolalkyl ₍ C12-C15) phosphite, cyclic neopentanetetraylbis (2,4-di-tert-butylphenylphoss) Fight), Cyclic Neopentantetraylbis (2,6-di-tert-butyl-4-phenylphosphite), Cyclic Neopentantetraylbis (Nonylphenylphosphite), Bis (Nonylphenyl) Pentaerythritol diphosphite , Dibutylhydrogenphosphite, distearyl / pentaerythritol / diphosfite, hydrogenated bisphenol A / pentaerythritol phosphite / polymer and the like are exemplified.

As for the amount of the antiaging agent added, the lower limit is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and 0.1 part by mass with respect to 100 parts by mass of the rubber component. The above is particularly preferable, and it may be 0.3 parts by mass or more, the upper limit is preferably 3.5 parts by mass or less, and particularly preferably 3.0 parts by mass or less.

In the rubber composition of the present invention, a known acid receiving agent may be used, but it may not be used when a known cross-linking agent utilizing the reactivity of the side chain double bond is used. Preferred acid receiving agents are metal compounds and / or inorganic microporous crystals. Examples of the metal compound include oxides of Group II (Groups 2 and 12) metals in the periodic table, hydroxides, carbonates, carboxylates, silicates, borates, phosphites, and Group III of the periodic table. (Groups 3 and 13) Metal oxides, hydroxides, carboxylates, silicates, sulfates, nitrates, phosphates, periodic table Group IV (Groups 4 and 14) metal oxides, Examples thereof include metal compounds such as a basic carbonate, a basic carboxylate, a basic subphosphate, a basic sulfite, and a tribasic sulfate. These may be used alone or in combination of two or more.

Specific examples of the metal compound include magnesia, magnesium hydroxide, aluminum hydroxide, barium hydroxide, sodium carbonate, magnesium carbonate, barium carbonate, fresh lime, slaked lime, calcium carbonate, calcium stearate, zinc stearate, calcium phthalate, and the like. Calcium phosphite, zinc flower, tin oxide, litharge, lead tan, lead white, basic lead phthalate, basic lead carbonate, tin stearate, basic lead phosphite, basic tin phosphite, basic Examples thereof include lead sulfite and tribasic lead sulfate, and examples thereof include sodium carbonate, magnesia, magnesium hydroxide, fresh lime, slaked lime, and zinc flower.

The inorganic microporous crystal means a crystalline porous body, and can be clearly distinguished from an atypical porous body such as silica gel and alumina. Examples of such inorganic microporous crystals include zeolites, aluminophosphate-type molecular sieves, layered silicates, synthetic hydrotalcites, alkali metal titanates and the like. Particularly preferred acid receiving agents include synthetic hydrotalcite.

The zeolites are, in addition to natural zeolites, various zeolites such as A-type, X-type, and Y-type synthetic zeolites, sodalites, natural or synthetic mordenites, and ZSM-5, and metal substituents thereof. It may be used in combination of two or more kinds. The metal of the metal substituent is often sodium. As the zeolites, those having a large acid receptivity are preferable, and type A zeolites are preferable.

The synthetic hydrotalcite is represented by the following general formula (1).
Mg _X Zn _Y Al _Z (OH) _{(2 (X + Y) + 3Z-2)} CO ₃・ wH ₂ O (1)
[In the equation, x and y are real numbers of 0 to 10 having a relationship of x + y = 1 to 10, z is a real number of 1 to 5, and w is a real number of 0 to 10, respectively. ]

As an example of the hydrotalcites represented by the general formula (1), Mg _4.5 Al ₂ (OH) ₁₃ CO 3.3.5H ₂ O, Mg _4.5 Al ₂ (OH) ₁₃ CO _{3 ,} Mg ₄ Al ₂ (OH) ₁₂ CO ₃・ 3.5H ₂ O, Mg ₆ Al ₂ (OH) ₁₆ CO ₃・ 4H ₂ O, Mg ₅ Al ₂ (OH) ₁₄ CO ₃・ 4H ₂ O, Mg ₃ Al ₂ (OH) ₁₀ CO 3.1.7H ₂ O, Mg ₃ ZnAl ₂ (OH) ₁₂ CO _{3.3.5H 2} O, Mg ₃ ZnAl _{2 (} OH) ₁₂ CO ₃ and the like can be mentioned.

As for the blending amount of the acid receiving agent, the lower limit is preferably 0.01 part by mass or more, and more preferably 0.05 part by mass or more with respect to 100 parts by mass of (a) the polyether polymer. , 0.1 part by mass or more, preferably 0.5 part by mass or more, and the upper limit is preferably 5 parts by mass or less, and particularly preferably 3.5 parts by mass or less.

The cross-linking agent includes known cross-linking agents that utilize the reactivity of halogen (for example, chlorine) atoms, that is, polyamines, thioureas, thiadiasols, triazines, quinoxalins, bisphenols, and the like, as well as side chain double bonds. Examples of known cross-linking agents that utilize the reactivity of the above, for example, organic peroxides, sulfur, morpholine polysulfides, thiuram polysulfides, etc., are triazines, quinoxalins, organic peroxides, sulfur. Is preferable, and quinoxalins are more preferable.

Examples of polyamines include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, p-phenylenediamine, cumenediamine, N, N'-dicinnamilyden-1,6-hexanediamine, ethylenediamine carbamate, and hexamethylenediamine carbamate. And so on.
Examples of thioureas include 2-mercaptoimidazoline, 1,3-diethylthiourea, 1,3-dibutylthiourea, and trimethylthiourea.
Examples of thiadiazoles include 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-thiadiazole-5-thiobenzoate and the like.
Examples of triazines include 2,4,6-trimercapto-1,3,5-triazine, 2-hexylamino-4,6-dimercaptotriazine, 2-diethylamino-4,6-dimercaptotriazine and 2-cyclohexyl. Amino-4,6-dimercaptotriazine, 2-dibutylamino-4,6-dimercaptotriazine, 2-anilino-4,6-dimercaptotriazine, 2-phenylamino-4,6-dimercaptotriazine and the like. Will be.
Examples of quinoxalines include 2,3-dimercaptoquinoxaline, quinoxaline-2,3-dithiocarbonate, 6-methylquinoxaline-2,3-dithiocarbonate (quinomethionate), and 5,8-dimethylquinoxaline-2,3-dithiocarbonate. And so on.
Examples of bisphenols include bisphenol AF and bisphenol S.
Examples of the organic peroxide include tert-butylhydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, diisopropylbenzenehydroperoxide, di-tert-butyl peroxide, and dik. Milperoxide, tert-butylcummilperoxide, 1,1-tert-butylperoxycyclohexane, 2,5-dimethyl-2,5-ditert-butylperoxyhexane, 2,5-dimethyl-2,5-ditert Dibutylperoxyhexin-3,1,3-bistert-butylperoxyisopropylbenzene, 2,5-dimethyl-2,5-dibenzoylperoxyhexane, 1,1-bistert-butylperoxy-3,3,5- Trimethylcyclohexane, n-butyl-4,4-bistert-butylperoxyvalerate, benzoyl peroxide, tert-butyl peroxide isobutyrate, tert-butylperoxy2-ethylhexanoate, tert-butylperoxybenzoate, tert -Butylperoxyisopropylcarbonate, tert-butylperoxyallyl monocarbonate, p-methylbenzoyl peroxide and the like can be mentioned.
Examples of morpholine polysulfides include morpholine disulfides.
Examples of thiuram polysulfides include tetramethylthium disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylene thiuram tetrasulfide, dipentamethylene thiuram hexasulfide and the like.

The lower limit of the blending amount of the cross-linking agent is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, and the upper limit is preferably 0.1 part by mass or more with respect to 100 parts by mass of the (a) polyether polymer. Is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less.

As the reinforcing agent, a known reinforcing agent can be used, specifically, calcium carbonate, talc, silica, clay, carbon fiber, glass fiber, carbon black, titanium oxide, magnesium oxide, hydrotalcite, and hydroxylation. Examples thereof include magnesium, antimony oxide, zinc oxide and the like, and carbon black and silica are preferable.

Examples of carbon black include furnace black, acetylene black, thermal black, channel black, graphite, and the like, and specifically, SAF, ISAF, HAF, EPC, XCF, FEF, GPF, HMF, SRF, FT, and MT. It can be exemplified. These carbon blacks may be used alone or in combination of two or more.

The type of silica is not particularly limited, and is, for example, wet silica (hydrous silicic acid), dry silica (silicic anhydride), aluminum silicate, and the like. As the silica to be used, wet method silica is preferable. Wet method silica is a fine particle of hydrous silicic acid produced by acid decomposition of an aqueous sodium silicate solution or an alkaline earth metal silicate, and is a filler for rubber mainly composed of silicon dioxide.

The blending amount of the reinforcing agent is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the (a) polyether-based polymer.

When carbon black and silica are used in combination as a reinforcing agent, it is preferable that the blending ratio of carbon black and silica is 4: 1 to 1: 1 (the former is carbon black and the latter is silica).

Specific examples of the processing aid include paraffin waxes such as paraffin waxes and hydrocarbon waxes and hydrocarbon resins; fatty acids such as stearic acid and palmitic acid; fatty acid amides such as stearoamide and oleylamide; n-. Fatty acid esters such as butyl stearate; sorbitan fatty acid esters such as sorbitan stearate; fatty alcohols; etc. may be mentioned, and these may be used alone or in combination of two or more.

The blending amount of the processing aid may be 0 to 20 parts by mass, 0.1 to 20 parts by mass, and 0.3 to 10 parts by mass with respect to 100 parts by mass of the (a) polyether polymer. It may be a mass part.

Examples of the plasticizer include phthalic acid derivatives such as dioctyl phthalate (bis phthalate (2-ethylhexyl)) and diallyl ester phthalate, adipic acid derivatives such as dibutyl diglycol-adipate and di (butoxyethoxy) ethyl adipate, and sebacic acid. Examples thereof include sebacic acid derivatives such as dioctyl and trimellitic acid derivatives such as trioctyl remeritate, and these may be used alone or in combination of two or more.

The blending amount of the plasticizer may be 0 to 50 parts by mass, 0.1 to 50 parts by mass, or 3 to 35 parts by mass with respect to 100 parts by mass of the (a) polyether polymer. It may be there.

As a method for blending the rubber composition of the present invention, any means conventionally used in the field of polymer processing can be used, and for example, a mixing roll, a Banbury mixer, various kneaders and the like can be used. For example, first knead only rubber, then prepare an A kneading compound containing a compounding agent other than a cross-linking agent and a cross-linking accelerator, and then perform B-kneading by adding a cross-linking agent and a cross-linking accelerator. be able to.

The crosslinked product using the rubber composition of the present invention is obtained by cross-linking the rubber composition of the present invention. Specifically, it is usually obtained by heating to 100 to 200 ° C., and the crosslinking time varies depending on the temperature, but is usually carried out between 0.5 and 300 minutes. In the cross-linking treatment, heating may be performed in one or two steps. In cross-linking molding, in addition to the case where cross-linking and molding are performed integrally, the case where the rubber-containing composition previously molded is heated again to form a cross-linked product, and the case where the cross-linked product is heated first and processed for molding. It may be applied in any case. As a specific method of cross-linking molding, any method such as compression molding by a mold, injection molding, steam can, air bath, infrared rays, or heating by microwave can be used.

The following will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to this.

First, each compounding agent shown in Table 1 was kneaded with a pressurized kneader at 120 ° C. to prepare an A kneading compound. This A kneading compound was kneaded with an open roll to prepare a B kneading compound. In the table, A is a raw material of the A kneading compound, and B is a raw material to be blended in the A kneading compound when the B kneading compound is prepared. The unit in the table is the mass part.

Specifically, the compounding agents shown in Table 1 were kneaded with a pressurized kneader at 120 ° C. to prepare an A kneading compound, which was molded into a sheet using an open roll to obtain an A kneading sheet. To 100 parts by mass of the polyether polymer, 1.7 parts by mass of quinomethionate was added to the obtained A kneaded sheet, and the sheet was formed into a sheet by an open roll. Then, it was press-crosslinked at 170 ° C. for 15 minutes to obtain a crosslinked sheet. Further, this was heated in an air oven at 150 ° C. for 2 hours to obtain a secondary crosslinked product. Using the obtained secondary crosslinked product, a tensile test was carried out according to JIS K6251 and a hardness test was carried out according to JIS K6253. A heat resistance test was carried out according to the JIS K6257 accelerated aging test A-2 method, a tensile test was carried out according to JIS K6251 after the heat resistance test (125 ° C. × 70 hours), and a hardness test was carried out according to K6253. An oil resistance test was carried out according to JIS K6258, a tensile test was carried out according to JIS K6251 after the oil resistance test (No. 3 oil 125 ° C. × 70 hours), and a hardness test was carried out according to K6253.

The compounding agents used in the implementation and comparative examples are shown below.
* 1 Epichlorohydrin-ethylene oxide binary copolymer "Epichromer D" manufactured by Osaka Soda Co., Ltd.
* 2 "Splendor R-300V" manufactured by Kao Corporation
* 3 "Nocrack NBC" manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
* 4 "Noxeller MB" manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
* 5 "Noxeller TTCU" manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
* 6 "Seast 3" manufactured by Tokai Carbon Co., Ltd.
* 7 "Carplex # 1120" made by Evonik Japan
* 8 "ADEKA SIZER RS-107" manufactured by ADEKA CORPORATION
* 9 "STABIACE HT-1" manufactured by Sakai Chemical Industry Co., Ltd.
* 10 Wollastonite-type calcium silicate "NYAD 400" manufactured by Tomoe Kogyo Co., Ltd. (needle-shaped crystals, aspect ratio (average length / average width): 3.0, average length: 24 μm)
* 11 Tobamorite powder (tobamorite type calcium silicate) manufactured by Japan Insulation Co., Ltd. "Tobamorite powder TK" (strip-shaped crystal, aspect ratio (average length / average width): 1.0, average length: 24 μm)
* 12 "Disonet XL-21S" manufactured by Osaka Soda Co., Ltd.

Table 2 shows the test results obtained from each test method. In the table, Tb means the tensile strength specified in the tensile test, Eb means the elongation specified in the tensile test, and Hs means the hardness. In addition, ΔEb, Hsch. Indicates the rate of change in elongation and the difference in hardness before and after the heat aging test and the oil resistance test (standards are before the heat aging test and before the oil resistance test).

In Table 2, the crosslinked products obtained by cross-linking the rubber compositions of Examples 1 and 2 are compared with the cross-linked products obtained by cross-linking the rubber compositions of Comparative Examples 1 and 2 before and after the heat aging test and oil resistance. It was shown that ΔEb (rate of change in elongation specified in the tensile test) before and after the test was small, and that it was excellent in heat resistance and oil resistance.

Since the crosslinked product obtained by cross-linking the rubber composition of the present invention has excellent heat resistance and oil resistance, tube materials such as fuel hoses and air hoses and rubber packings (particularly, have not been widely used so far) are particularly used in automobile applications. It is useful as a rubber packing that did not exist.

Claims (4)

1. A rubber composition containing (a) a polyether polymer and (b) calcium silicate having a wollastonite crystal system.
2. The rubber composition according to claim 1, wherein the (a) polyether-based polymer contains at least one unit selected from ethylene oxide, propylene oxide, epichlorohydrin, and allyl glycidyl ether as a constituent unit.
3. The rubber composition according to claim 1 or 2, wherein the content of calcium silicate in which (b) the crystal system is a wollastonite type is 10 parts by mass or more with respect to 100 parts by mass of (a) the polyether-based polymer. thing.
4. A crosslinked product obtained by cross-linking the rubber composition according to any one of claims 1 to 3.