Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
  • C08L71/03—Polyepihalohydrins

Definitions

• epihalohydrin-based polymers are widely used as materials having excellent various physical characteristics by being crosslinked, and are used as fuel hoses, air-based hoses, and tube materials in automobile applications.
• the present inventors include (a) an epihalohydrin-based polymer, (b) calcium silicate whose crystal system is a tovamolite type, (c) a cross-linking agent utilizing the reactivity of a halogen atom, and (a) an epihalohydrin-based polymer.
• Item 1 (a) Epihalohydrin-based polymer, (b) Calcium silicate whose crystal system is tovamorite type, (c) Cross-linking agent utilizing the reactivity of halogen atom, (a) Epihalohydrin-based polymer 100 mass (B) A rubber composition containing 10 parts by weight or more of calcium silicate having a tovamorite type crystal system.
• Item 2 The weight of the (a) epihalohydrin-based polymer containing at least one unit selected from an epihalohydrin homopolymer or a structural unit based on epihalohydrin and ethylene oxide, propylene oxide, and allyl glycidyl ether as a structural unit.
• Item 2. The rubber composition according to Item 1, which is a coalescence.
• Item 3 A crosslinked product obtained by cross-linking the rubber composition according to Item 1 or Item 2.
• the crosslinked product obtained by cross-linking the rubber composition of the present invention is excellent in water resistance and acid resistance, and is therefore useful as a rubber packing or the like that requires water resistance and acid resistance.
• the rubber composition of the present invention contains (a) an epihalohydrin-based polymer as a rubber component, and (b) a cross-linking agent that utilizes the reactivity of calcium silicate having a tovamorite-type crystal system and (c) halogen atoms.
• the epihalohydrin-based polymer (epihalohydrin rubber) used in the present invention is obtained by ring-opening polymerization of epihalohydrin such as epichlorohydrin and epibromhydrin, has a structural unit based on epihalohydrin, and is an epihalohydrin.
• epihalohydrin such as epichlorohydrin and epibromhydrin
• alkylene oxides such as ethylene oxide, propylene oxide and n-butylene oxide
• glycidyls such as methyl glycidyl ether, ethyl glycidyl ether, n-glycidyl ether, allyl glycidyl ether and phenyl glycidyl ether.
• the epihalohydrin-based polymer can be used alone or in combination of two or more.
• the epichlorohydrin-based polymer at least a compound selected from ethylene oxide, propylene oxide, and allylglycidyl ether other than the epichlorohydrin-based structural unit having only the epihalohydrin-based structural unit as a structural unit (epichlorohydrin homopolymer) or at least the epihalohydrin-based structural unit. It is preferable to include a structural unit based on one, and further preferably to contain a structural unit based on at least one selected from propylene oxide, ethylene oxide, and allylglycidyl ether and a structural unit based on epichlorohydrin. Most preferably, the constituent units include units of chlorohydrin and ethylene oxide.
• the constitutional unit based on epihalohydrin is preferably 10 to 100 mol%, more preferably 15 to 75 mol%, and 20 to 65 mol% with respect to the total polymerization units. Is particularly preferred.
• the epichlorohydrin-based structural unit is preferably an epichlorohydrin-based structural unit.
• the ethylene oxide-based constituent unit is preferably 0 to 90 mol%, more preferably 25 to 85 mol%, and 35 to 80 mol% with respect to the total polymerization unit. It is particularly preferable to have.
• the structural unit based on propylene oxide and the structural unit based on allyl glycidyl ether are preferably 0 to 15 mol%, more preferably 0 to 12 mol%, based on the total polymerization units. It is preferably 0 to 10 mol%, and particularly preferably 0 to 10 mol%.
• the rubber composition of the present invention may contain only (a) an epihalohydrin-based polymer as a rubber component, or may further contain a rubber type other than the epihalohydrin-based polymer.
• the rubber other than the epihalohydrin-based polymer include natural rubber and synthetic rubber, and examples of the synthetic rubber include isoprene rubber (IR), 1,2-polybutadiene (VBR), styrene butadiene rubber (SBR), and butyl rubber (IIR).
• EPM Ethylene propylene rubber
• EPDM ethylene propylene diene rubber
• CSM chlorosulfonated polyethylene
• CPE chlorinated polyethylene
• ACM acrylic rubber
• NBR acrylonitrile butadiene rubber
• H-NBR hydrided acrylonitrile butadiene rubber
• the epihalohydrin-based polymer is 10 to 90% by mass in the rubber component, other than the epihalohydrin-based polymer. It is preferable to contain 90 to 10% by mass of the rubber type, more preferably 30 to 90% by mass of the epihalohydrin-based polymer, and more preferably 70 to 10% by mass of the rubber type other than the epihalohydrin-based polymer. It is particularly preferable to contain 70 to 90% by mass of the polymer and 30 to 10% by mass of the rubber species other than the epihalohydrin-based polymer.
• the content of (a) epihalohydrin-based 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 good.
• (b) calcium silicate in which the crystal system is a tovamolite type 14 ⁇ tovamolite, 11 ⁇ tovamolite, 9 ⁇ tovamolite, CSH (I), CSH (II).
• (B) Calcium silicate whose crystal system is a tovamorite type may be used alone or in combination of two or more.
• the average length of calcium silicate having a tovamorite type crystal system is 10 ⁇ m or more, preferably 15 ⁇ m or more, more preferably 20 ⁇ m or more, 200 ⁇ m or less, preferably 45 ⁇ m or less, and more preferably 30 ⁇ m or less. ..
• the aspect ratio (average length / average width) of calcium silicate having a tovamorite type crystal system is preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.8 or more. It is preferably 1.4 or less, more preferably 1.3 or less, still more preferably 1.2 or less.
• 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).
• 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).
• 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.
• (b) calcium silicate having a tovamorite type crystal system is preferably contained in an amount of 10 parts by mass or more, preferably 12 parts by mass or more, based on 100 parts by mass of the (a) epihalohydrin-based polymer. Is more preferable, 15 parts by mass or more is particularly preferable, 20 parts by mass or more is most preferable, 25 parts by mass or more is more preferable, and 30 parts by mass or more is even more preferable.
• the upper limit is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less.
• cross-linking agent utilizing the reactivity of the halogen atom examples include polyamines, thioureas, thiadiazoles, triazines, quinoxalines, bisphenols and the like.
• the cross-linking agent utilizing the reactivity of the halogen atom may be used alone or in combination of two or more. Of these, quinoxalines are preferable.
• polyamines examples include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, p-phenylenediamine, cumenediamine, N, N'-dicinnamilyden-1,6-hexanediamine, ethylenediamine carbamate, and hexamethylenediamine carbamate.
• thioureas examples 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.
• quinoxalines include 2,3-dimercaptoquinoxaline, quinoxaline-2,3-dithiocarbonate, 6-methylquinoxaline-2,3-dithiocarbonate (quinomethionate), and 5,8-dimethylquinoxaline-2,3-dithiocarbonate.
• bisphenols include bisphenol AF and bisphenol S.
• the blending amount of the cross-linking agent utilizing the reactivity of the halogen atom is preferably 0.1 part by mass or more, preferably 0.3 part by mass or more, with respect to 100 parts by mass of the (a) epihalohydrin-based polymer.
• the amount is more preferably 10 parts by mass or less, the upper limit 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.
• 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 vulcanizing 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.
• 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 thioic acids, and subphosphorus. Acids are mentioned, and at least one selected from these is preferable, benzimidazole-based anti-aging agents and dithiocarbamate-based anti-aging agents are more preferable, and benzimidazole-based anti-aging agents and dithiocarbamate-based agents are more preferable. It is more preferable to use an anti-aging agent in combination.
• Examples of the benzimidazole-based antiaging agent include zinc salts of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and 2-mercaptobenzimidazole.
• dithiocarbamate-based antiaging agent examples include 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.
• amine-based antiaging agent examples include phenyl- ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, p- (p-toluenesulfonylamide) -diphenylamine, 4,4'-( ⁇ , ⁇ '-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
• 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.
• phenolic antiaging agent examples 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- ⁇ -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
• 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).
• thiourea-based antiaging agent examples 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- ( ⁇ ) as organic thioacids -Lauryl-thiopropionate), dilauryl-thiodipropionate and the like are exemplified.
• phosphites examples include tris (nonyl-phenyl) phosphite, tris (mixed mono- and di-nonylphenyl) phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monotridecyl phosphite, and diphenyl isodecyl.
• the lower limit is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more with respect to 100 parts by mass of (a) epihalohydrin-based polymer. It is particularly preferably 0.1 part by mass or more, it may be 0.3 part 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. ..
• a known acid receiving agent may be used.
• Preferred acid receiving agents are metal compounds and / or inorganic microporous crystals.
• 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.
• 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.
• the metal compound examples 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.
• 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).
• z is a real number of 1 to 5
• w is a real number of 0 to 10, respectively.
• the lower limit is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more with respect to 100 parts by mass of (a) epihalohydrin-based polymer. It is particularly preferably 0.1 part by mass or more, preferably 0.3 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.
• 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.
• carbon black examples 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.
• silica is not particularly limited, and is, for example, wet silica (hydrous silicic acid), dry silica (silicic anhydride), aluminum silicate, and the like.
• 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) epihalohydrin-based polymer.
• the blending ratio of carbon black and silica is 4: 1 to 1: 1 (the former is carbon black and the latter is silica).
• processing aid examples 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) epihalohydrin-based polymer. It may be a department.
• plasticizer examples 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.
• 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
• sebacic acid examples 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) epihalohydrin-based polymer. It's okay.
• 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.
• a mixing roll a Banbury mixer, various kneaders and the like can be used.
• 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.
• 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.
• any method such as compression molding by a mold, injection molding, steam can, air bath, infrared rays, or heating by microwave can be used.
• 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.
• A is a raw material of the A kneading compound
• B is a raw material to be blended in the A kneading compound when the B kneading compound is prepared.
• the units of Tables 1 to 3 are parts by mass.
• 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.
• the vulcanizing agent shown in the table 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.
• Tobamorite powder TK strip-shaped crystal, aspect ratio (average length / average width): 1.0, average length: 24 ⁇ m) * 12 "Disonet XL-21S” manufactured by Osaka Soda Co., Ltd. * 13 "Perbutyl P” manufactured by NOF CORPORATION
• Tables 4 to 6 show the test results obtained from the water resistance test method and the acid resistance test method.
• the water resistance test was carried out in accordance with JIS K6258 by immersing the above-mentioned secondary crosslinked product in distilled water at a temperature of 100 ° C. for 70 hours, and a dipping test was performed to calculate the water absorption rate from the volume change before and after the dipping ( ⁇ (after the test). Volume of crosslinked product-Volume of crosslinked product before test) / Volume of crosslinked product before test ⁇ x 100 (%)).
• the acid resistance test was based on JIS K6258, and 4 g of formic acid was added to 1000 g of water to prepare a 4000 ppm formic acid aqueous solution. 100 ml of the prepared aqueous solution of formic acid was placed in the autoclave, the secondary crosslinked product cut into approximately 1 cm squares was immersed, stored at 80 ° C. for 72 hours, and then the water absorption rate was calculated from the volume change before and after immersion ( ⁇ (after the test). Volume of crosslinked product-Volume of crosslinked product before test) / Volume of crosslinked product before test ⁇ ⁇ 100 (%)).
• the crosslinked product obtained by cross-linking the rubber composition of the present invention is excellent in water resistance and acid resistance, it is useful as a rubber packing or the like that requires water resistance and acid resistance.

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• 2021
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