WO2006129705A1 - Composition de caoutchouc acrylique et produit reticule - Google Patents

Composition de caoutchouc acrylique et produit reticule Download PDF

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Publication number
WO2006129705A1
WO2006129705A1 PCT/JP2006/310870 JP2006310870W WO2006129705A1 WO 2006129705 A1 WO2006129705 A1 WO 2006129705A1 JP 2006310870 W JP2006310870 W JP 2006310870W WO 2006129705 A1 WO2006129705 A1 WO 2006129705A1
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acrylic rubber
carboxyl group
rubber composition
acid
acrylic
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PCT/JP2006/310870
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English (en)
Japanese (ja)
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Takeshi Ooishi
Yuki Ishii
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Zeon Corporation
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Publication of WO2006129705A1 publication Critical patent/WO2006129705A1/fr

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    • 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
    • C08K5/16—Nitrogen-containing compounds

Definitions

  • the present invention relates to an acrylic rubber composition and a crosslinked product thereof, and more specifically, an acrylic rubber composition having excellent scorch stability and high crosslinking speed during processing, and the crosslinked acrylic rubber composition. It is related to the bridge
  • Acrylic rubber is excellent in heat resistance, oil resistance, and the like, and therefore is used for a wide range of rubber parts in automobile-related fields. Recently, however, there has been a growing demand for improved durability such as automotive sealing materials, hose materials, anti-vibration materials, tube materials, belt materials or boot materials, and acrylic rubber with better heat resistance and lower compression set has been developed. There is a strong demand.
  • Patent Document 1 in order to improve heat resistance and reduce compression set, an acrylic rubber having a carboxyl group-containing ethylenically unsaturated monomer unit is bonded to a monoramine compound and a diamine crosslinking.
  • a composition containing an agent has been proposed.
  • a cross-linked product meeting the requirements for heat resistance and compression set was obtained, and the scorch stability was improved.
  • demands for resource saving, energy saving and productivity improvement at the time of molding are increasing, and if the product is made thinner or the molding time is shortened, even if this composition is used, the molded product Since there is a tendency for deformation to occur during the removal, further improvement of the crosslinking rate is desired.
  • Patent Document 2 a carboxyl group-containing acrylic rubber, a primary amine acetate, a diamine cross-linking agent, and a guanidine compound are used to improve the balance of processability, vulcanization characteristics, and compression set.
  • a custom composition has been proposed. However, this composition is insufficient in terms of the crosslinking rate even for thin and short-time molding trends.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-265737
  • Patent Document 2 JP 2004-269873 A
  • the object of the present invention is to provide a cross-linked product having excellent scorch stability, high cross-linking speed during processing, low compression set, and high heat resistance in view of the above-described actual situation.
  • Another object of the present invention is to provide an acrylic rubber composition that can be used.
  • the present inventors have achieved the above object with an acrylic rubber composition containing a carboxyl group-containing acryl rubber, an aliphatic diamine carboxylate and a crosslinking agent. Based on this finding, the present inventors have completed the present invention.
  • an acrylic rubber composition comprising a carboxyl group-containing acrylic rubber, an aliphatic diamine carbonate and a crosslinking agent.
  • the aliphatic diamine carboxylate is preferably an aliphatic diamine dicarboxylate.
  • the crosslinking agent is preferably at least one compound selected from aliphatic diamine, aromatic diamine and dihydrazide compound strength.
  • crosslinking one of the said acrylic rubber compositions is provided.
  • the acrylic rubber composition of the present invention has a long scorch time and excellent scorch stability, but has a high crosslinking rate during processing. Furthermore, by crosslinking this acrylic rubber composition, a crosslinked product having a small compression set and excellent heat resistance can be provided. Therefore, taking advantage of these characteristics, it can be suitably used in a wide range as a material for rubber parts such as seals, hoses, anti-vibration materials, tubes, belts and boots.
  • the acrylic rubber composition of the present invention comprises a carboxyl group-containing acrylic rubber, an aliphatic diamine carboxylate and a crosslinking agent.
  • the carboxyl group-containing acrylic rubber is an acrylic rubber having a carboxyl group that forms a crosslinking point.
  • This cross-linked product of carboxyl group-containing acrylic rubber has excellent heat resistance compared to conventional cross-linked products of chlorine group-containing acrylic rubber and epoxy group-containing acrylic rubber having a chlorine atom or epoxy group at the cross-linking point, and after heat load In particular, the change in hardness of the steel is small, and the permanent compression strain is reduced.
  • the carboxyl group-containing acrylic rubber used in the present invention includes (a) a carboxyl group-containing acrylic rubber having a carboxyl group-containing monomer unit as a copolymerizable monomer unit, and (b) having no carboxyl group.
  • Carboxyl group-containing acrylic rubber obtained by graft-modifying a carbon-carbon unsaturated bond-containing compound having a carboxyl group in the presence of a radical initiator in the presence of a radical initiator, or (c) a carboxylic acid ester group, an acid amide group
  • the carboxylic acid-containing acrylic rubber obtained by converting a part of the carboxylic acid-derived group in the acrylic rubber molecule having a rubonic acid-derived group into a carboxyl group by hydrolysis, Moyo! /
  • the carboxyl group-containing acrylic rubber used in the present invention has (meth) acrylic acid ester monomer [meaning acrylic acid ester monomer and Z or methacrylic acid ester monomer] in the molecule.
  • (meth) acrylic acid ester monomer meaning acrylic acid ester monomer and Z or methacrylic acid ester monomer
  • methyl (meth) acrylate is a polymer containing preferably 70% by weight or more, more preferably 80% by weight or more with respect to 100% by weight of all monomer units.
  • Examples of the (meth) acrylic acid ester monomer that is the main raw material of the monomer unit constituting the carboxyl group-containing acrylic rubber include (meth) acrylic acid alkyl ester monomers, (meth) Examples include acrylic acid alkoxyalkyl ester monomers.
  • an ester of (1) to C8 alkenol and (meth) acrylic acid is preferred! /.
  • the (meth) acrylic acid alkoxyalkyl ester monomer is preferably an ester of an alkoxyalkyl alcohol having 2 to 8 carbon atoms and (meth) acrylic acid! /.
  • (meth) acrylic acid 2-ethoxyethyl and (meth) acrylic acid 2-methoxyethyl are particularly preferred, and acrylic acid 2-ethoxyethyl and acrylic acid 2-methoxyethyl are preferred.
  • the force lpoxyl group-containing monomer used as a raw material for the monomer unit constituting the carboxyl group-containing acrylic rubber of type (a) can be copolymerized with the above (meth) acrylate monomer.
  • Any carboxyl group-containing monomer is not particularly limited. Examples of such carboxyl group-containing monomers include ⁇ , ⁇ ethylenically unsaturated monocarboxylic acids having 3 to 12 carbon atoms, ⁇ , ⁇ ethylenically unsaturated dicarboxylic acids having 4 to 12 carbon atoms, and carbon. Examples thereof include monoesters of ⁇ , ⁇ ethylenically unsaturated dicarboxylic acid having 4 to 11 carbon atoms and alkenol having 1 to 8 carbon atoms.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms include acrylic acid, methacrylic acid, ethylacrylic acid, crotonic acid, and cinnamic acid.
  • Examples of the ⁇ , ⁇ unsaturated dicarboxylic acid having 4 to 12 carbon atoms include butenedionic acid such as fumaric acid and maleic acid, itaconic acid and citraconic acid.
  • Monoesters of L 1, ⁇ -unsaturated dicarboxylic acid and C 1-8 alkanol are monomethyl fumarate, monoethyl fumarate, mono-fumarate ⁇ -butyl, malein Butenedionic acid mono-chain alkyl esters such as monomethyl acid, monoethyl maleate and mono- ⁇ butyl maleate; monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclohexyl fumarate, monocyclopentyl maleate, maleic acid Butenedionic acid monoesters having an alicyclic structure such as monocyclohexyl and monocyclohexyl maleate; itaconic acid monoesters such as monomethyl itaconate, monoethyl itaconate and monobutyl itaconate; mono 2-hydro fumarate Qichetil; and the like.
  • butenedionic acid mono-chain alkyl esters and butenedionic acid monoesters having an alicyclic structure are preferred, particularly mono-n-butyl fumarate, mono-n-butyl maleate, and monocyclofumarate.
  • Hexyl and monocyclohexyl maleate are preferred. These can be used alone or in combination of two or more.
  • the content of the carboxyl group-containing monomer unit is 0.5% by weight or more with respect to 100% by weight of the carboxyl group-containing acrylic rubber, preferably 0.7 to 15% by weight, more preferably 1 to 12% by weight. If the number of carboxyl group-containing monomer units is too small, the cross-linked density of the cross-linked product will be insufficient, and good mechanical properties may not be obtained, and the surface skin of the molded product may not be smooth. On the other hand, when there are too many carboxyl group-containing monomer units, there is a possibility that the elongation of the cross-linked product will decrease or the hardness will become too high.
  • the carboxyl group content in the carboxyl group-containing acrylic rubber is preferably 4 X 10 _4 to 4 X 10 _1 ephr. It is preferably 8 X 10 — 4 to 2 X 10 — 1 ephr, particularly preferably 1 X 10 — 3 to 1 X 10 ephr.
  • dicarboxylic acid when used for copolymerization, it may be copolymerized as an anhydride.
  • a crosslinking point is formed by hydrolyzing to form a carboxyl group during crosslinking.
  • carboxyl group-containing acrylic rubber is copolymerized with an epoxy group-containing monomer, a hydroxyl group-containing monomer, a gen monomer, or the like as a monomer having a crosslinking point other than a carboxyl group. It may be.
  • the epoxy group-containing monomer is not particularly limited, and examples thereof include epoxy group-containing (meth) acrylic acid esters and epoxy group-containing (meth) aryl ethers. Specific examples of the epoxy group-containing (meth) acrylic acid ester include glycidyl (meth) acrylate.
  • epoxy group-containing (meth) aryl ether examples include (meth) aryl glycidyl ether.
  • the hydroxyl group-containing monomer is not particularly limited, and examples thereof include a hydroxyl group-containing (meth) acrylate ester and a hydroxyl group-containing (meth) acrylamide.
  • hydroxyl-containing (meth) acrylic acid esters include (meth) acrylic acid 2-hydroxychetyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2 -Hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
  • hydroxyl group-containing (meth) acrylamide examples include N-methylol (meth) acrylamide.
  • Examples of the gen monomer include a conjugated gen monomer and a non-conjugated gen monomer.
  • Examples of the conjugated gen monomer include 1,3-butadiene, isoprene, and piperylene.
  • Non-conjugated gen monomers include ethylidene norbornene, dicyclopentagen, (meth) acrylic acid dicyclopentagel, (meth) acrylic acid 2-dicyclopentagel-rutile, and the like. .
  • an epoxy group-containing monomer is preferable.
  • Monomers having a crosslinking point other than a carboxyl group can be used alone or in combination of two or more.
  • the content of the monomer unit having a crosslinking point other than the carboxyl group in the acrylic rubber is preferably 0 to 5% by weight, more preferably 0 to 3% by weight with respect to 100% by weight of the total monomer units. It is.
  • the carboxyl group-containing acrylic rubber is an object of the present invention. If necessary, it may contain a monomer unit that can be copolymerized with each of these monomers.
  • Such copolymerizable monomers include aromatic vinyl monomers, ⁇ , ⁇ -ethylene. Unsaturated-tolyl monomer, a monomer having two or more acryloyloxy groups (polyfunctional acryl monomer), and other olefin-based monomers.
  • Examples of the aromatic bur monomer include styrene, at-methyl styrene, and dibulene benzene.
  • Examples of the a, ⁇ -ethylenically unsaturated-tolyl monomer include acrylonitrile and meta-tallow-tolyl.
  • polyfunctional acrylic monomer examples include (meth) acrylic acid diester of ethylene glycol and (meth) acrylic acid diester of propylene glycol.
  • olefin-based monomers include ethylene, propylene, butyl acetate, ethyl butyl ether, butyl butyl ether, and the like.
  • acrylonitrile and meta-tallow-tolyl are preferred.
  • the content of such copolymerizable monomer units is preferably 0 to 49.9 weights 0/0, more preferably 0 to 20 weights, based on 100 weight percent of all monomer units. 0/0.
  • a chlorine group-containing monomer may be further contained in addition to the above-described compounds.
  • the content of the chlorine group-containing monomer is preferably 0 to 0.1% by weight, more preferably 0 to 0.07% by weight, and still more preferably 0 to 100% by weight of all monomer units. It is particularly preferred that the content is ⁇ 0.05% by weight and substantially free of chlorine group-containing monomers.
  • the chlorine group-containing monomer includes, for example, chloromaleic acid which is an a, ⁇ unsaturated dicarboxylic acid having 4 to 12 carbon atoms, and other compounds capable of forming a crosslinking point, such as halogen.
  • Unsaturated alcohol ester of saturated carboxylic acid (meth) acrylic acid haloalkyl ester, (meth) acrylic acid haloacyloxyalkyl ester, (meth) acrylic acid (noroacetylcarbamoyloxy) alkyl ester, halogen-containing unsaturated ether
  • examples include halogen-containing unsaturated ketones, halomethyl group-containing aromatic vinyl compounds, halogen-containing unsaturated amides, and haloacetyl group-containing unsaturated monomers.
  • Mu-one viscosity (ML, 100 ° C) of the acrylic rubber containing carboxyl group is preferably 1 It is 0 to 90, more preferably 15 to 80, particularly preferably 20 to 70. If the mu-1 viscosity is too small, the shape-retaining property of the acrylic rubber composition is lowered, which may reduce the molding processability and the mechanical strength of the crosslinked product. On the other hand, if it is too large, there is a possibility that the moldability is lowered due to a decrease in fluidity.
  • the carboxyl group-containing acrylic rubber is a (meth) acrylic acid ester monomer, a carboxyl group-containing monomer, a monomer having a crosslinking point other than the carboxyl group used as necessary, and a copolymer thereof. It can be produced by copolymerizing monomer mixtures such as possible monomers.
  • a deviation from the known emulsion polymerization method, suspension polymerization method, bulk polymerization method and solution polymerization method can be used. However, in view of ease of control of the polymerization reaction, the emulsion polymerization under normal pressure can be used. Legal is preferred.
  • the carbon-carbon unsaturated bond-containing compound having a carboxyl group for graft-modifying the acrylic rubber includes a, j8-ethylenic group.
  • Examples of the a, ⁇ -ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, a-ethylacrylic acid, 2-hydroxyethyl (meth) acrylic acid, and the like.
  • ethylenically unsaturated dicarboxylic acid examples include maleic acid, fumaric acid, and itaconic acid.
  • Examples of the a, ⁇ -ethylenically unsaturated dicarboxylic acid anhydride include maleic anhydride, butyl succinic anhydride, tetrahydrophthalic anhydride, and citraconic anhydride.
  • Examples of the ⁇ , ⁇ ethylenically unsaturated dicarboxylic acid monoester include monomethyl maleate and monoethyl itaconate.
  • the carboxyl group-containing acrylic rubber of the type (b) is obtained by adding a carbon-carbon unsaturated bond-containing compound having the carboxyl group in the presence of a radical initiator to an talyl rubber dissolved in an organic solvent. It is obtained by reacting.
  • the rubonic acid-derived group include a carboxylic acid ester group possessed by a (meth) acrylic acid ester monomer unit.
  • a carboxyl group-containing acrylic rubber can be obtained by hydrolyzing a part of the rubonic acid ester group of acrylic rubber dissolved in an organic solvent in the presence of hydrochloric acid, sulfuric acid, sodium hydroxide or the like.
  • carboxyl group-containing acrylic rubber of the type (b) and the type (c) ! the carboxyl group content in terms of carboxyl group-containing monomer units, and 100 g of acrylic rubber
  • the number of moles of carboxyl groups per unit is the same as that in the type (a).
  • the chlorine group content in terms of chlorine group-containing monomer units is also the same as that of the above type (a).
  • the aliphatic diamine carboxylate used in the present invention is an aliphatic diamine monocarboxylate represented by the following general formula (1) or an aliphatic diamine dicarboxylate represented by the following chemical formula (2). Of these, the aliphatic diaminedicarboxylate represented by the chemical formula (2) is preferable.
  • R 1 is an alkyl group having 6 to 24 carbon atoms.
  • R 2 and R 3 are hydrogen or an alkyl group having 1 to 24 carbon atoms or a alkenyl group having 2 to 24 carbon atoms which may have one carboxy group.
  • X is an integer of 1-6.
  • Examples of the aliphatic diamine monocarboxylate represented by the general formula (1) include beef tallow alkyl diamine monoformate, beef tallow alkyl diamine monoacetate, tallow alkyl diamine monopropion Acid salt, beef tallow alkyldiamine monobutyrate, beef tallow alkyldiamine monolaurate, beef tallow alkyldiamine monostearate, beef tallow alkyl diamine monooleate, tallow alkyl diamine monolinoleate, Tallow Alkyl Diamine Monolactate, Tallow Alkyl Diamine Mono-Quenate, Tallow Alkyl Diamine Mono-Adipate, Coco Alkyl Diamine Monoformate, Coco Alkyl Diamine Monoacetate, Coco Alkyl Di Amine monopropionate, cocoalkyl diamine monobutyrate, coco alkyl diamine monolaur Phosphate, cocoalkyl diamine monostearate, cocoalkyl diamine monooleate,
  • Examples of the aliphatic diamine dicarboxylate represented by the general formula (2) include beef tallow alkyl diamine diformate, tallow alkyl diamine diacetate, tallow alkyl diamine dipropionate, tallow alkyl diamine dibutyric acid.
  • beef tallow alkyl diamine dioleate beef tallow alkyl diamine diadipate, coco alkyl diamine dioleate, and coco alkyl diamine diadipate are preferable.
  • the content of the aliphatic diamine carboxylate in the acrylic rubber composition of the present invention is preferably 0.1 to 7 parts by weight, more preferably 0.15 parts per 100 parts by weight of the ruboxyl group-containing acrylic rubber. -5 parts by weight, particularly preferably 0.2-3 parts by weight. If the content of the aliphatic diamine carboxylate is too small, scorching may occur quickly and burn may occur during molding. Conversely, if the content is too large, compression set may be reduced.
  • the acrylic rubber composition of the present invention preferably contains carbon black.
  • the carbon black used in the present invention is not particularly limited and is used for rubber compounding.
  • furnace black, acetylene black, thermal black, channel black, graphite and the like can be used.
  • furnace black is particularly preferred as SAF, IS AF, ISAF—HS, ISAF—LS, IISAF—HS, HAF, HAF—HS, HAF—LS, M AF ⁇ .
  • Various grades such as FEF-FEF-LS, GPF-GPF-HS-GPF-LS, SRF, SRF-HS, SRF-LM are listed.
  • the particle size, specific surface area and oil absorption are not particularly limited.
  • the particle size is preferably 15 to 200 m, more preferably 18 to: LOOm, the specific surface area is preferably 10 to 260 m 2 Zg, more preferably 20 to 240 m 2 Zg, and the oil absorption is preferably 50 to 200 ml ZlOOg Preferably it is 70-180mlZl00g.
  • Carbon black has an effect of reinforcing a cross-linked product obtained by cross-linking.
  • the carbon black content of the acrylic rubber composition of the present invention is a carboxyl group-containing acrylic rubber.
  • the amount is preferably 20 to 200 parts by weight, more preferably 30 to 150 parts by weight, particularly preferably 40 to: LOO parts by weight with respect to 100 parts by weight. If the carbon black content is too low, the strength of the resulting crosslinked product may be reduced, while if too high, the elongation of the crosslinked product may be reduced.
  • the crosslinking agent used in the acrylic rubber composition of the present invention is not limited as long as it is a compound capable of crosslinking with the carboxyl group of the carboxyl group-containing acrylic rubber.
  • crosslinking agents include polyvalent amines, polyvalent hydrazide compounds, polyvalent epoxy compounds, polyvalent isocyanate compounds, aziridine compounds, basic metal oxides, and organometallic halides.
  • the polyvalent amine is a covalently bonded compound having two or more amine structures, and preferably has 4 to 30 carbon atoms.
  • Examples of such polyvalent amines include aliphatic polyvalent amines and aromatic polyvalent amines, and those having non-conjugated nitrogen-carbon double bonds such as guanidine compounds are not included. .
  • aliphatic polyamine examples include aliphatic diamines such as hexamethylene diamine, hexamethylene diamine carbamate, N, N, -dicinnamylidene 1,6 hexane diamine.
  • the aromatic polyvalent amine is preferably 4,4, -methylenedialine, m-phenylene.
  • Diamine 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4,1 (m-phenol-diisopropylidene) dialine, 4, 4,1 (p-phenol) -Range sopropylidene) diline, 2,2,1bis [4- (4-aminophenoxy) phenol] propane, 4,4,1 diaminobenzaldehyde, 4,4,1bis (4-aminophenoxy) biphenol
  • Aromatic diamines such as -le, m-xylylenediamine, p-xylylenediamine, 1,3,5-benzenetriamine.
  • One or more polyamines can be used in combination.
  • the polyhydric hydrazide compound is a compound having at least two hydrazide groups.
  • polyhydric hydrazide compound examples are preferably oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide , Dodecanedioic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide, naphthalic acid dihydrazide, acetone dicarboxylic acid dihydrazide, fumaric acid dihydrazide, maleic acid dihydrazide, ditaconic acid dihydrazide
  • trimellitic acid dihydrazide 1, 3, 5-benzenetricar
  • Examples of the polyvalent epoxy compound include phenol novolac epoxy compounds, cresol novolac epoxy compounds, talesol epoxy compounds, bisphenol A epoxy compounds, bisphenol F epoxy compounds, and brominated bisphenols.
  • Glycidyl ether type epoxy compounds such as A type epoxy compounds, brominated bisphenol F type epoxy compounds, hydrogenated bisphenol A type epoxy compounds; alicyclic epoxy compounds, glycidyl ester type epoxy compounds, glycidylamine type epoxies
  • Compounds, other polyvalent epoxy compounds such as isocyanurate-type epoxy compounds; compounds having two or more epoxy groups in the molecule, and the like can be used alone or in combination of two or more. .
  • Preferred examples of the polyvalent isocyanate compound are diisocyanates having 6 to 24 carbon atoms and triisocyanates! /.
  • Specific examples of diisocyanates include 2, 4 tolylene diisocyanate (2, 4-TDI), 2, 6 tolylene diisocyanate (2, 6-TDI), 4, 4 'diphenyl- Methane diisocyanate (HMDI), hexamethylene diisocyanate, p-phenolic diisocyanate, m-phenolic diisocyanate, 1,5 naphthylene diisocyanate.
  • triisocyanates include 1, 3, 6 hexamethylene triisocyanate, 1, 6, 11-undecane triisocyanate, and bicycloheptane triisocyanate.
  • aziridine compound examples include tris-2,4,6- (1 aziridyl) -1,3,5 triazine, tris [1- (2-methyl) aziridyl] phosphinoxide, hexa [1 — (2-Methyl) aziridinyl] triphosphatriazine and the like, and these can be used alone or in combination of two or more.
  • Examples of the basic metal oxide include zinc oxide, lead oxide, calcium oxide, and magnesium oxide. These may be used alone or in combination of two or more.
  • organometallic halides examples include dicyclopentagenyl metal dihalides.
  • metals that are preferably used in this case include titanium, zirconium, and hafnium.
  • aliphatic polyamines, aromatic polyamines and polyhydric hydrazide compounds are preferred, and aliphatic diamines, aromatic diamines and dihydrazide compounds are more preferred. preferable.
  • aliphatic diamines hexamethylene diamine carnomate is particularly preferred.
  • aromatic diamines 2,2,1bis [4 (4-aminophenoxy) phenol] propane is particularly preferred.
  • dihydrazide compounds adipic acid dihydrazide and isophthalic acid dihydrazide are particularly preferred.
  • the content of the crosslinking agent in the acrylic rubber composition of the present invention is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the carboxyl group-containing acryl rubber. Particularly preferred is 0.2 to 7 parts by weight. If the content of the crosslinking agent is too small, crosslinking may be insufficient, and it may be difficult to maintain the shape of the crosslinked product. On the other hand, if the amount is too large, the bridge will be too hard and the elasticity as a crosslinked rubber may be impaired.
  • the acrylic rubber composition of the present invention may include a crosslinking accelerator, a reinforcing agent, a processing aid, an anti-aging agent, a light stabilizer, a plasticizer, a lubricant, an adhesive, a lubricant, a flame retardant, as necessary.
  • You may contain additives, such as an antifungal agent, an antistatic agent, a coloring agent, and a filler.
  • the cross-linking accelerator is not particularly limited. Particularly when a polyvalent amine is used as the cross-linking agent, the cross-linking accelerator used in combination with the polyvalent amine is a base at 25 ° C in water. Those having a dissociation constant of 10 1 12 to 10 6 are preferred. Examples of such crosslinking accelerators include aliphatic monovalent secondary amine compounds, aliphatic monovalent tertiary amine compounds, guanidine compounds, imidazole compounds, quaternary onium salts, tertiary salts. Grade phosphine compounds, alkali metal salts of weak acids, and the like.
  • the aliphatic monovalent secondary amine compound is a compound in which two hydrogen atoms of ammonia are substituted with an aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group substituted for the hydrogen atom is preferably one having 1 to 30 carbon atoms, more preferably one having 8 to 20 carbon atoms.
  • dioctylamine dioctylamine, didecylamine, didodecylamine, ditetradecylamine, dicetylamine, dioctadecylamine, dicis-9-octadecylamine, dinonadecylamine, dicyclohexylamine and the like are preferable.
  • the aliphatic monovalent tertiary amine compound is a compound in which all three hydrogen atoms of ammonia are substituted with an aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group that substitutes for a hydrogen atom preferably has 1 to 30 carbon atoms, and more preferably has 1 to 22 carbon atoms.
  • N, N-dimethyldodecylamine, N, N-dimethyltetradecylamine, N, N-dimethylcetylamine, N, N-dimethyloctadecylamine, N, N-dimethylbe- Luamine and the like are preferable.
  • Examples of the guanidine compound include 1,3-di-o-tolylguanidine, 1,3-diphenylguanidine, and the like.
  • imidazole compound examples include 2-methylimidazole and 2-phenolimidazole.
  • Examples of the quaternary o-um salt include tetra n-butyl ammo-um bromide, octadecyl chloride n-butyl ammo-um bromide, and the like.
  • tertiary phosphine compound examples include triphenylphosphine and tri-p-tolylphosphine.
  • alkali metal salts of weak acids include inorganic weak acid salts such as sodium or potassium phosphates and carbonates, or organic weak acid salts such as stearates and laurates.
  • the amount of the crosslinking accelerator used is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight, and particularly preferably 0.3 to 100 parts by weight of the carboxyl group-containing acrylic rubber. ⁇ 10 parts by weight. If the amount of the crosslinking accelerator is too large, the crosslinking speed may be too high during crosslinking, the crosslinking accelerator may bloom on the surface of the bridge, or the crosslinked product may become too hard. If the amount of the crosslinking accelerator is too small, the tensile strength of the crosslinked product may be remarkably lowered, and the elongation and the change in tensile strength after heat load may be too large.
  • the acrylic rubber composition of the present invention may be blended with a polymer such as rubber other than the above-mentioned acrylic rubber, elastomer, and resin if necessary.
  • a polymer such as rubber other than the above-mentioned acrylic rubber, elastomer, and resin if necessary.
  • rubbers that can be blended include natural rubber, acrylic rubber not containing a carboxyl group, polybutadiene rubber, polyisoprene rubber, styrene butadiene rubber, and alitrononitrile butadiene rubber.
  • elastomers that can be blended include olefin-based elastomers, styrene-based elastomers, polyester-based elastomers, polyamide-based elastomers, polyurethane-based elastomers, polysiloxane-based elastomers, and the like.
  • Examples of the resin that can be blended include olefin-based resin, styrene-based resin, acrylic resin, polyphenylene ether, polyester, polycarbonate, and polyamide.
  • an appropriate mixing method such as roll mixing, Banbury mixing, screw mixing, or solution mixing can be employed.
  • the order of blending is not particularly limited, but after sufficiently mixing components that are not likely to react or decompose with heat, components that are easily reacted with heat or components that are easily decomposed, such as crosslinking agents and crosslinking accelerators, are reacted or decomposed. Don't happen! / Mix at a short temperature for a short time.
  • the acrylic rubber composition of the present invention has excellent scorch stability and has a high crosslinking rate during processing. Therefore, it is excellent in productivity with a short molding cycle.
  • the crosslinked product of the present invention can be crosslinked by heating while molding the above-described acrylic rubber composition of the present invention by a molding method such as extrusion molding, injection molding, transfer molding, compression molding, etc. It is obtained from this.
  • a general rubber processing procedure can be employed for the extrusion.
  • the acrylic rubber composition prepared by roll mixing is supplied to the feed port of the extruder and softened by heating the barrel force in the process of sending it to the head with a screw.
  • a long extruded product plate, bar, pipe, hose, deformed product, etc.
  • the temperature of the barrel, head and die is controlled by heating using electricity, steam or the like as a heat source.
  • the barrel temperature is preferably 50 to 120 ° C, more preferably 60 to 100.
  • the head temperature is preferably 60 to 130, more preferably 60 to 110.
  • the die temperature is preferably 70 to 130 ° C, more preferably 80 to 100 ° C.
  • the shaped article is preferably cross-linked (primary cross-linked) by heating to 130 ° C.
  • cross-linked product (primary cross-linked product).
  • the cross-linked product is heated to 130 ° C to 220 ° C, more preferably 140 ° C to 200 ° C in an oven using electricity, steam or the like as a heat source for secondary cross-linking.
  • secondary cross-linked product is heated to 130 ° C to 220 ° C, more preferably 140 ° C to 200 ° C in an oven using electricity, steam or the like as a heat source for secondary cross-linking.
  • a mold cavity having a shape corresponding to one or several products is filled with the acrylic rubber composition of the present invention, and the mold is molded.
  • it is crosslinked (primary crosslinked) by heating to 130 to 220 ° C, more preferably 140 to 200 ° C to obtain a crosslinked product (primary crosslinked product).
  • the crosslinked product is heated at 130 ° C to 220 ° C, more preferably 140 ° C to 200 ° C for 1 to 48 hours in an oven using electricity, hot air, steam or the like as a heat source.
  • a cross-linked product secondary cross-linked product.
  • the mu-one viscosity ML of the carboxyl group-containing acrylic rubber at a measurement temperature of 100 ° C. was measured according to the mu-one viscosity test of the uncrosslinked rubber physical test method of JIS K6300.
  • the Mooney scorch of the acrylic rubber composition was measured using an L-shaped rotor at a temperature of 125 ° C according to JIS K 6300-1. From this measurement result, the Moony scorch time t 5 (min) of the acrylic rubber composition was determined. The higher the value of t5, the better the scorch stability.
  • the cross-linking properties of acrylic rubber composition are in accordance with JIS K 6300-2. It measured using. Using a rotorless rheometer type tester as the cross-linking tester, the torque after 10 minutes at a temperature of 170 ° C was determined to evaluate the cross-linking characteristics. The larger the torque value, the higher the degree of crosslinking and the faster the crosslinking speed!
  • Acrylic rubber composition is molded and crosslinked by compression molding at 170 ° C for 20 minutes.
  • a sheet having a length of 5 cm, a width of 15 cm, and a thickness of 2 mm was prepared, and further left standing in an electric oven at 170 ° C. for 4 hours for secondary crosslinking to obtain a sheet-like crosslinked product.
  • this sheet-like cross-linked product was prepared, and further left standing in an electric oven at 170 ° C. for 4 hours for secondary crosslinking to obtain a sheet-like crosslinked product.
  • a specimen was obtained by punching with No. 3 dumbbell.
  • the tensile strength at break, tensile elongation at break, and 100% tensile stress were determined by the change rate (percentage) of the measured value after heating with respect to the measured value of the normal physical properties.
  • the hardness was evaluated by determining the difference (change) between the measured value of normal physical properties and the measured value after heating. The closer to 0, the better the heat resistance.
  • a cylindrical cross-linked product was prepared in the same manner as the cross-linked product for measuring the physical properties, except that the cross-linked product was a cylindrical type with a diameter of 29 mm and a height of 12.5 mm. .
  • the obtained test piece was placed in an environment of 150 ° C or 175 ° C for 72 hours in a state of being compressed by 25% according to JIS K 6262, and then the compression was released and the compression set was measured.
  • the compression permanent strain rate is better as the numerical value is smaller and the material is more difficult to deform.
  • the composition of the obtained carboxyl group-containing acrylic rubber A was composed of 40% ethyl acrylate monomer unit, 40% n-butyl acrylate monomer unit, and 18% 2-methoxyethyl acrylate monomer unit. And 2% mono-n-butyl fumarate monomer unit (carboxyl group content 1.08 X 10 _2 ephr), and mu-one viscosity (ML
  • Acrylic rubber A 100 parts, FEF carbon black (SEAST SO, manufactured by Tokai Carbon Co., Ltd., reinforcing agent): 65 parts, stearic acid (strengthening agent): 2, 4, 4, bis, a-dimethyl benzil) Diphenylamine (NOCRACK CD, manufactured by Ouchi Shinsei Engineering Co., Ltd., anti-aging agent): 2 parts and cocoalkyl diamine diadipate (duomine CDA, Lionaxo), an aliphatic diamine dicarboxylate : 0.5 part in a Banbury mixer and kneaded at 50 ° C, then transferred to an open roll, hexamethylenediamine carnomate (crosslinking agent): 0.5 part and 1, 3— Di-o-tolylguazine (Noxeller DT, manufactured by Ouchi Shinsei Chemical Co., Ltd., crosslinking accelerator): 2 parts were added and kneaded at 40 ° C. to prepare an acrylic rubber composition.
  • Scorch stability and crosslinking characteristics of the resulting acrylic rubber composition and normal properties (breaking strength, breaking elongation, 100% tensile stress, hardness) of the crosslinked product obtained by crosslinking the acrylic rubber composition And heat resistance, and compression set (150 ° C and 175 ° C) were tested. The results are shown in Table 1.
  • Example 1 an acrylic rubber composition was prepared in the same manner as in Example 1 except that the cocoalkyldiamine diadipate was changed to beef tallow alkyldiamine dioleate (Duomin TDO, manufactured by Lionaxo). The test was conducted in the same manner as in Example 1. The results are shown in Table 1. [0090] (Comparative Examples 1 and 2)
  • Example 1 an acrylic rubber composition was prepared in the same manner as in Example 1 except that the cocoalkyldiaminediadipineate was changed to stearylamine and cocoalkylamine acetate, respectively. Evaluation was performed in the same manner as above. The results are shown in Table 1.
  • the Mooney scorch t5 is at a practical level that is sufficiently long in about 5 minutes, and the torque is high. It can be confirmed that the cross-linking speed is high and the strength is high.
  • the crosslinked products of Examples 1 and 2 have sufficient normal physical properties and high heat resistance as acrylic rubber, and have a low compression set.
  • Acrylic rubber A 100 parts, FEF carbon black (SEAST SO, manufactured by Tokai Carbon Co., Ltd., reinforcing agent): 65 parts, stearic acid (strengthening agent): 2, 4, 4, bis, a-dimethyl benzil) Diphenylamine (Nocrack CD, manufactured by Ouchi Shinsei Gakken Kogyo Co., Ltd., anti-aging agent) and cocoalkyldiamine diadipate (Duomin CDA, manufactured by Lionaxo) have the number of parts listed in Table 2 as one Banbury mixer.
  • Examples 3 to 6 instead of cocoalkyl diamine diadipate, stearylamine (Farmin 80, manufactured by Kao Corporation) was used in the same manner as in Examples 3 to 6 except that the number of parts shown in Table 2 was used. A rubber composition was prepared and tested in the same manner as in Examples 3-6. The results are shown in Table 2.
  • the cross-linked product (primary cross-linked product or secondary cross-linked product) of the present invention is excellent in heat resistance while maintaining the basic properties of rubber such as tensile strength, elongation, and hardness, and has a compression set. Is small.
  • the cross-linked product of the present invention is used in a wide range of fields such as transportation equipment such as automobiles, general equipment, and electrical equipment, for example, sealing materials such as O-rings, gaskets, oil seals, and bearing seals; Wire covering materials; industrial belts; tubes and hoses; sheets;
  • sealing materials such as O-rings, gaskets, oil seals, and bearing seals
  • Wire covering materials industrial belts; tubes and hoses; sheets;

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L’invention décrit une composition de caoutchouc acrylique contenant un caoutchouc acrylique contenant un groupe carboxyle, un diaminecarboxylate aliphatique et un agent de réticulation. Il est préférable pour la composition de caoutchouc acrylique que le diaminecarboxylate aliphatique soit un diaminedicarboxylate aliphatique et que l'agent de réticulation soit une amine polyvalente choisie parmi des diamines aliphatiques, des diamines aromatiques et des composés de type dihydrazide. Cette composition de caoutchouc acrylique a une stabilité de grillage élevée et un taux de réticulation élevé lorsqu’elle est travaillée, et permet d'obtenir un produit réticulé ayant une faible compression rémanente et une résistance thermique élevée.
PCT/JP2006/310870 2005-05-31 2006-05-31 Composition de caoutchouc acrylique et produit reticule WO2006129705A1 (fr)

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JP2009084514A (ja) * 2007-10-02 2009-04-23 Nippon Zeon Co Ltd 架橋性アクリルゴム組成物およびその架橋物
JP2010065147A (ja) * 2008-09-11 2010-03-25 Nakanishi Metal Works Co Ltd アクリル系ゴム組成物及びアクリル系ゴム成形体
JP2010090351A (ja) * 2008-10-11 2010-04-22 Nok Corp アクリルゴム組成物及びそれを用いて加硫成形されたシール部品
JP2010100777A (ja) * 2008-10-27 2010-05-06 Kokoku Intech Co Ltd 耐熱性アクリルゴム組成物
CN111918883A (zh) * 2018-03-30 2020-11-10 日本瑞翁株式会社 丙烯酸橡胶的制造方法、丙烯酸橡胶组合物的制造方法以及丙烯酸橡胶用双轴挤出干燥机

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WO2021067693A1 (fr) * 2019-10-04 2021-04-08 Ecovia Renewables, Inc. Acide polycarboxylique polymère réticulé absorbant l'eau et ses procédés de fabrication

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JPH069904A (ja) * 1991-11-01 1994-01-18 Katayama Chem Works Co Ltd 持続性水中防汚組成物
JP2002220505A (ja) * 2001-01-29 2002-08-09 Tokai Rubber Ind Ltd ゴム組成物及び耐熱ホース
JP2002302576A (ja) * 2001-04-05 2002-10-18 Du Pont Mitsui Polychem Co Ltd エチレン・アクリルゴム組成物
JP2003342437A (ja) * 2002-05-27 2003-12-03 Nippon Zeon Co Ltd アクリルゴム組成物及び架橋物

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JPH069904A (ja) * 1991-11-01 1994-01-18 Katayama Chem Works Co Ltd 持続性水中防汚組成物
JP2002220505A (ja) * 2001-01-29 2002-08-09 Tokai Rubber Ind Ltd ゴム組成物及び耐熱ホース
JP2002302576A (ja) * 2001-04-05 2002-10-18 Du Pont Mitsui Polychem Co Ltd エチレン・アクリルゴム組成物
JP2003342437A (ja) * 2002-05-27 2003-12-03 Nippon Zeon Co Ltd アクリルゴム組成物及び架橋物

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009084514A (ja) * 2007-10-02 2009-04-23 Nippon Zeon Co Ltd 架橋性アクリルゴム組成物およびその架橋物
JP2010065147A (ja) * 2008-09-11 2010-03-25 Nakanishi Metal Works Co Ltd アクリル系ゴム組成物及びアクリル系ゴム成形体
JP2010090351A (ja) * 2008-10-11 2010-04-22 Nok Corp アクリルゴム組成物及びそれを用いて加硫成形されたシール部品
JP2010100777A (ja) * 2008-10-27 2010-05-06 Kokoku Intech Co Ltd 耐熱性アクリルゴム組成物
CN111918883A (zh) * 2018-03-30 2020-11-10 日本瑞翁株式会社 丙烯酸橡胶的制造方法、丙烯酸橡胶组合物的制造方法以及丙烯酸橡胶用双轴挤出干燥机
CN111918883B (zh) * 2018-03-30 2023-05-16 日本瑞翁株式会社 丙烯酸橡胶的制造方法、丙烯酸橡胶组合物的制造方法以及丙烯酸橡胶用双轴挤出干燥机

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