WO2021014791A1 - 保存安定性と加工性に優れるアクリルゴムシート - Google Patents

保存安定性と加工性に優れるアクリルゴムシート Download PDF

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Publication number
WO2021014791A1
WO2021014791A1 PCT/JP2020/022314 JP2020022314W WO2021014791A1 WO 2021014791 A1 WO2021014791 A1 WO 2021014791A1 JP 2020022314 W JP2020022314 W JP 2020022314W WO 2021014791 A1 WO2021014791 A1 WO 2021014791A1
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Prior art keywords
acrylic rubber
weight
rubber sheet
acrylic
sheet according
Prior art date
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Ceased
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PCT/JP2020/022314
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English (en)
French (fr)
Japanese (ja)
Inventor
増田　浩文
川中　孝文
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Zeon Corp
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Zeon Corp
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Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Priority to US17/626,439 priority Critical patent/US20220235190A1/en
Priority to JP2021534584A priority patent/JP7567792B2/ja
Priority to EP20843788.9A priority patent/EP4001323A4/en
Priority to CN202080048274.1A priority patent/CN114072460A/zh
Priority to KR1020217042248A priority patent/KR102851307B1/ko
Publication of WO2021014791A1 publication Critical patent/WO2021014791A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Definitions

  • the present invention relates to an acrylic rubber sheet having excellent storage stability and processability and a method for producing the same, an acrylic rubber bale formed by laminating the acrylic rubber sheet, a rubber mixture obtained by mixing the acrylic rubber sheet or the acrylic rubber bale, and the like.
  • the present invention relates to a manufacturing method and a rubber crosslinked product obtained by bridging it.
  • Acrylic rubber is a polymer containing acrylic acid ester as a main component, and is generally known as rubber having excellent heat resistance, oil resistance, and ozone resistance. It is widely used in automobile-related fields and is aged as needed. It is used with the addition of an inhibitor.
  • Patent Document 1 International Publication No. 2018/139466 pamphlet
  • Patent Document 1 contains pure water, sodium lauryl sulfate, and polyoxy as monomer components containing ethyl acrylate, n-butyl acrylate, monobutyl fumarate, and the like.
  • the resulting hydrous crumb was washed with industrial water four times, acid washed once with pH 3, and then washed with pure water once.
  • a method for producing a crumb-shaped acrylic rubber which can suppress stains on the polymerization apparatus during polymerization and has excellent initial mechanical strength by drying in a hot air dryer at 160 ° C. for 10 minutes. Further, it is described that the hydrous crumb washed with a screw type extruder can be dried at 150 ° C. or higher according to this method.
  • workability and storage stability in a harsh environment have been required.
  • Patent Document 2 Japanese Patent No. 3599962 contains two radically reactive unsaturated groups having different reactivity with 95 to 99.9% by weight of alkyl acrylate or alkoxyalkyl acrylate.
  • Acrylate rubber having a gel content of 5% by weight or less of an acetone-insoluble matter obtained by copolymerizing 0.1 to 5% by weight of the above-mentioned polymerizable monomer in the presence of a radical polymerization initiator, reinforcing property
  • An acrylic rubber composition composed of a filler and an organic peroxide-based vulcanizer and having excellent extrusion processability such as extrusion rate, die well, and surface surface is disclosed.
  • the acrylic rubber used here having a very small gel fraction is higher than the acrylic rubber having a high gel fraction (60%) obtained when the polymerization solution is in a normal acidic region (pH 4 before polymerization, pH 3.4 after polymerization).
  • the polymerization solution is obtained by adjusting the pH to 6 to 8 with sodium hydrogen carbonate or the like.
  • acrylic rubber containing (meth) acrylic acid ester as the main component has problems in handling such as decomposition in the neutral to alkaline region and inferior storage stability, and emulsion polymerization is carried out by changing the pH from neutral to alkaline.
  • the acrylic rubber used had a problem of inferior mechanical strength due to the loss of reactive groups (crosslink points) such as carboxyl group, epoxy group and chlorine atom.
  • Patent Document 3 International Publication No. 2018/143101 pamphlet
  • a (meth) acrylic acid ester and an ion-crosslinkable monomer are emulsion-polymerized and have a complex viscosity at 100 ° C. ([ ⁇ ] 100 ° C.). Is 3,500 Pa ⁇ s or less, and the ratio of the complex viscosity at 60 ° C. ([ ⁇ ] 60 ° C.) to the complex viscosity at 100 ° C.
  • a technique for improving the extrusion moldability, particularly the discharge amount, the discharge length, and the surface texture of a rubber composition containing a reinforcing agent and a cross-linking agent by using an acrylic rubber having a ° C.) of 0.8 or less is disclosed.
  • the gel amount of the tetrahydrofuran insoluble component of the acrylic rubber used in the same technique is 80% by weight or less, preferably 5 to 80% by weight, and preferably exists as much as possible in the range of 70% or less, and the gel. It is stated that extrudability deteriorates when the amount is less than 5%.
  • the weight average molecular weight (Mw) of the acrylic rubber used is 200,000 to 1,000,000, and when the weight average molecular weight (Mw) exceeds 1,000,000, the viscoelasticity of the acrylic rubber is high. It is stated that it is too much to be preferable. However, there has been a demand for high strength and workability at the time of kneading such as Banbury, which are highly balanced, and improvement of storage stability is also required.
  • the present invention has been made in view of such an actual situation, and is an acrylic rubber sheet having excellent storage stability and workability, a method for producing the same, an acrylic rubber bale formed by laminating the acrylic rubber sheet, and the acrylic rubber sheet.
  • the acrylic rubber sheet that contains a specific anti-aging agent and is made into a sheet with a specific gel amount is highly excellent in storage stability and workability without impairing the strength characteristics. I found.
  • the present inventors can further enhance the effect of the present invention by specifying the sheet type, the shape of the specific anti-aging agent, the melting point, the molecular weight and the content, the complex viscosity at a specific temperature, the pH and the specific gravity. I found.
  • the present inventors also have difficulty in uniformly dispersing the anti-aging agent in an emulsion polymerization solution obtained by emulsion-polymerizing a monomer component containing (meth) acrylic acid ester as a main component to improve the storage stability of acrylic rubber.
  • an emulsion-containing crumb after cleaning was melted with a phenolic anti-aging agent and acrylic rubber in a state where it was substantially free of water (specific water content) using a specific screw type extruder. It has been found that an acrylic rubber sheet having highly excellent storage stability and workability can be produced by kneading and extruding into a sheet.
  • the present inventors also, when the polymerization conversion rate of emulsion polymerization is increased in order to improve the strength characteristics of acrylic rubber, the amount of gel rapidly increases and the processability of acrylic rubber deteriorates, but the water-containing crumb after washing is used.
  • Acrylic rubber with excellent workability because the amount of gel that rapidly increased due to emulsion polymerization disappears by melt-kneading and extruding into a sheet in a state where it does not contain substantially water (specific water content) using a specific screw type extruder. We found that sheets can be manufactured.
  • the present inventors also emulsify a specific antioxidant to be added to an emulsion polymerization solution, specify its production temperature and emulsifier concentration, and specify the water-containing crumb temperature to be charged into a screw extruder. It has been found that the storage stability and workability of the obtained acrylic rubber sheet can be significantly improved.
  • the present inventors have completed the present invention based on these findings.
  • the weight average molecular weight (Mw) containing the (meth) acrylic acid ester as a main component is 100,000 to 5,000,000
  • the z average molecular weight (Mz) and the weight average molecular weight (Mw) are Provided is an acrylic rubber sheet comprising acrylic rubber having a ratio (Mz / Mw) of 1.3 or more, containing a phenolic antioxidant, and having a gel amount of 50% by weight or less.
  • the acrylic rubber sheet of the present invention it is preferable that the acrylic rubber sheet is a melt-kneaded sheet.
  • the amount of gel is preferably 15% by weight or less.
  • the proportion of acrylic rubber in the acrylic rubber sheet is preferably 85% by weight or more.
  • the amount of ash in the acrylic rubber sheet is preferably 0.8% by weight or less.
  • the content of at least one element selected from the group consisting of sodium, sulfur, calcium, magnesium and phosphorus in the ash is preferably 60% by weight or more.
  • the phenolic antioxidant is preferably a hindered phenolic antioxidant.
  • the melting point of the phenolic anti-aging agent is preferably 150 ° C. or lower.
  • the molecular weight of the phenolic anti-aging agent is preferably in the range of 100 to 1,000.
  • the content of the phenolic anti-aging agent is preferably 0.001 to 15% by weight.
  • the weight average molecular weight (Mw) is preferably in the range of 1,000,000 to 5,000,000.
  • the complex viscosity at 60 ° C. ([ ⁇ ] 60 ° C.) is preferably 15,000 Pa ⁇ s or less.
  • the ratio of the complex viscosity at 100 ° C. ([ ⁇ ] 100 ° C.) to the complex viscosity at 60 ° C. ([ ⁇ ] 60 ° C.) ([ ⁇ ] 100 ° C./[ ⁇ ] 60 ° C. ) is preferably 0.5 or more.
  • the pH is preferably 6 or less.
  • the acrylic rubber sheet of the present invention preferably has a specific gravity of 0.7 or more.
  • the specific gravity is more preferably in the range of 0.8 to 1.4.
  • the Mooney viscosity (ML1 + 4,100 ° C.) of the acrylic rubber sheet is preferably in the range of 10 to 150.
  • a monomer component containing (meth) acrylic acid ester as a main component is emulsified with water and an emulsifier, and in the presence of a polymerization initiator, emulsion polymerization is carried out to a polymerization conversion rate of 90% by weight or more to emulsify.
  • a screw type consisting of a coagulation step for producing a solidification step, a cleaning step for cleaning the produced water-containing crumb, a dehydration barrel having a dehydration slit, a drying barrel for drying the washed water-containing crumb under reduced pressure, and a die at the tip.
  • a method for producing an acrylic rubber sheet which comprises a dehydration / drying / molding step of extruding a sheet-shaped dry rubber having a water content of less than 1% by weight using an extruder.
  • the temperature of the hydrous crumb charged into the screw type extruder is preferably 40 ° C. or higher.
  • the phenol-based anti-aging agent to be added is a phenol-based anti-aging agent-containing emulsion emulsified with warm water and an emulsifier.
  • the temperature of hot water is preferably 40 ° C. or higher.
  • the temperature of hot water is equal to or higher than the melting point of the phenolic antiaging agent used.
  • the emulsifier concentration of the phenol-based antiaging agent-containing emulsion is preferably 1% by weight or more.
  • an acrylic rubber veil formed by laminating the above acrylic rubber sheets.
  • a rubber mixture obtained by mixing a filler and a cross-linking agent with the acrylic rubber sheet or acrylic rubber veil.
  • a method for producing a rubber mixture which comprises mixing a filler and a cross-linking agent with the acrylic rubber sheet or the acrylic rubber bale using a mixer.
  • a method for producing a rubber mixture in which the above acrylic rubber sheet or acrylic rubber bale and a filler are mixed and then a cross-linking agent is mixed.
  • a rubber crosslinked product obtained by cross-linking the above rubber mixture is further provided.
  • an acrylic rubber sheet having excellent storage stability and processability and a method for producing the same an acrylic rubber bale formed by laminating the acrylic rubber sheet, and a rubber mixture obtained by mixing the acrylic rubber sheet or the acrylic rubber bale. And a method for producing the same, and a rubber crosslinked product obtained by cross-linking the same.
  • the acrylic rubber sheet of the present invention has a weight average molecular weight (Mw) of 100,000 to 5,000,000 containing (meth) acrylic acid ester as a main component, and has a z average molecular weight (Mz) and a weight average molecular weight (Mw). It is characterized by being composed of acrylic rubber having a ratio (Mz / Mw) of 1.3 or more, containing a phenolic antioxidant, and having a gel amount of 50% by weight or less.
  • the acrylic rubber constituting the acrylic rubber sheet of the present invention contains (meth) acrylic acid ester as a main component.
  • the ratio of the (meth) acrylic acid ester in the acrylic rubber is appropriately selected depending on the intended use, but is usually 50% by weight or more, preferably 70% by weight or more, and more preferably 80% by weight or more.
  • "(meth) acrylic acid ester” is used as a general term for esters of acrylic acid and / or methacrylic acid.
  • the acrylic rubber constituting the acrylic rubber sheet of the present invention is a bonding unit derived from at least one (meth) acrylic acid ester selected from the group consisting of (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester. It is preferable that the material containing the above can highly improve the cross-linking characteristics of the acrylic rubber sheet.
  • acrylic rubber constituting the acrylic rubber sheet of the present invention those containing a reactive group-containing monomer in the bonding unit are suitable because heat resistance, compression set resistance, and the like can be highly improved. ..
  • At least one (meth) acrylic acid ester selected from the group consisting of (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester. , Reactive group-containing monomers, and, if necessary, other monomers copolymerizable.
  • the (meth) acrylic acid alkyl ester is not particularly limited, but usually has a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms (preferably having an alkyl group having 1 to 8 carbon atoms).
  • a meta) acrylic acid alkyl ester more preferably a (meth) acrylic acid alkyl ester having an alkyl group having 2 to 6 carbon atoms.
  • (meth) acrylic acid alkyl ester examples include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n- (meth) acrylic acid.
  • the (meth) acrylic acid alkoxyalkyl ester is not particularly limited, but usually has a (meth) acrylic acid alkoxyalkyl ester having 2 to 12 alkoxyalkyl groups, preferably having 2 to 8 alkoxyalkyl groups (meth). ) Acrylic acid alkoxyalkyl ester, more preferably a (meth) acrylic acid alkoxy ester having an alkoxyalkyl group having 2 to 6 carbon atoms.
  • (meth) acrylic acid alkoxyalkyl ester examples include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, methoxybutyl (meth) acrylate, and (meth) acrylic.
  • examples thereof include ethoxymethyl acid, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, and butoxyethyl (meth) acrylate.
  • methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and the like are preferable, and methoxyethyl acrylate and ethoxyethyl acrylate are more preferable.
  • At least one (meth) acrylic acid ester selected from the group consisting of these (meth) acrylic acid alkyl esters and (meth) acrylic acid alkoxyalkyl esters may be used alone or in combination of two or more, and acrylic.
  • the proportion in the rubber is usually 50 to 99.99% by weight, preferably 70 to 99.9% by weight, more preferably 80 to 99.5% by weight, and most preferably 87 to 99% by weight. If the amount of (meth) acrylic acid ester in the monomer component is excessively small, the weather resistance, heat resistance, and oil resistance of the obtained acrylic rubber may decrease, which is not preferable.
  • the reactive group-containing monomer is appropriately selected depending on the intended use without any particular limitation, but usually has at least one functional group selected from the group consisting of a carboxyl group, an epoxy group and a halogen group.
  • a monomer having at least one functional group selected from the group consisting of a monomer, a carboxyl group, an epoxy group and a chlorine atom is preferable, and a monomer having an ionic reactive group such as a carboxyl group and an epoxy group is more preferable.
  • a monomer having a carboxyl group is particularly preferable.
  • the monomer having a carboxyl group is not particularly limited, but an ethylenically unsaturated carboxylic acid can be preferably used.
  • the ethylenically unsaturated carboxylic acid include ethylenically unsaturated monocarboxylic acid, ethylenically unsaturated dicarboxylic acid, and ethylenically unsaturated dicarboxylic acid monoester, and among these, ethylenically unsaturated dicarboxylic acid monoester. It is preferable that the ester can further enhance the compression resistance permanent strain property when the acrylic rubber is used as a rubber crosslinked product.
  • the ethylenically unsaturated monocarboxylic acid is not particularly limited, but an ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms is preferable, for example, acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, crotonic acid, and the like. Examples thereof include crotonic acid.
  • the ethylenically unsaturated dicarboxylic acid is not particularly limited, but an ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms is preferable, and for example, butenedioic acid such as fumaric acid and maleic acid, itaconic acid, and citraconic acid are used. Can be mentioned.
  • the ethylenically unsaturated dicarboxylic acid includes those existing as an anhydride.
  • the ethylenically unsaturated dicarboxylic acid monoester is not particularly limited, but usually, an ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms and an alkyl monoester having 1 to 12 carbon atoms, preferably 4 to 6 carbon atoms.
  • ethylenically unsaturated dicarboxylic acid monoester examples include monomethyl fumarate, monoethyl fumarate, mono n-butyl fumarate, monomethyl maleate, monoethyl maleate, mono n-butyl maleate, monocyclopentyl fumarate, and fumarate.
  • Butendionic acid monoalkyl esters such as monocyclohexyl acid, monocyclohexenyl fumarate, monocyclopentyl maleate, and monocyclohexyl maleate; Examples thereof include monoalkyl esters; among these, mono n-butyl fumarate and mono n-butyl maleate are preferable, and mono n-butyl fumarate is particularly preferable.
  • Examples of the monomer having an epoxy group include an epoxy group-containing (meth) acrylic acid ester such as glycidyl (meth) acrylate; and an epoxy group-containing vinyl ether such as allyl glycidyl ether and vinyl glycidyl ether.
  • Examples of the monomer having a halogen group include unsaturated alcohol esters of halogen-containing saturated carboxylic acids, (meth) acrylic acid haloalkyl esters, (meth) acrylic acid haloacyloxyalkyl esters, and (meth) acrylic acids (haloacetylcarbamoyl).
  • Oxy) alkyl esters, halogen-containing unsaturated ethers, halogen-containing unsaturated ketones, halomethyl group-containing aromatic vinyl compounds, halogen-containing unsaturated amides, haloacetyl group-containing unsaturated monomers and the like can be mentioned.
  • Examples of the unsaturated alcohol ester of the halogen-containing saturated carboxylic acid include vinyl chloroacetate, vinyl 2-chloropropionate, and allyl chloroacetate.
  • Examples of the (meth) acrylic acid haloalkyl ester include chloromethyl (meth) acrylic acid, 1-chloroethyl (meth) acrylic acid, 2-chloroethyl (meth) acrylic acid, and 1,2-dichloroethyl (meth) acrylic acid. Examples thereof include 2-chloropropyl (meth) acrylic acid, 3-chloropropyl (meth) acrylic acid, and 2,3-dichloropropyl (meth) acrylic acid.
  • Examples of the (meth) acrylic acid haloacyloxyalkyl ester include (meth) acrylic acid 2- (chloroacetoxy) ethyl, (meth) acrylic acid 2- (chloroacetoxy) propyl, and (meth) acrylic acid 3- (chloroacetoxy). ) Propyl, 3- (hydroxychloroacetoxy) propyl (meth) acrylate and the like.
  • Examples of the (meth) acrylic acid (haloacetylcarbamoyloxy) alkyl ester include (meth) acrylic acid 2- (chloroacetylcarbamoyloxy) ethyl and (meth) acrylic acid 3- (chloroacetylcarbamoyloxy) propyl. Be done.
  • Examples of the halogen-containing unsaturated ether include chloromethyl vinyl ether, 2-chloroethyl vinyl ether, 3-chloropropyl vinyl ether, 2-chloroethyl allyl ether, 3-chloropropyl allyl ether and the like.
  • halogen-containing unsaturated ketone examples include 2-chloroethyl vinyl ketone, 3-chloropropyl vinyl ketone, 2-chloroethyl allyl ketone and the like.
  • halomethyl group-containing aromatic vinyl compound examples include p-chloromethylstyrene, m-chloromethylstyrene, o-chloromethylstyrene, and p-chloromethyl- ⁇ -methylstyrene.
  • halogen-containing unsaturated amide examples include N-chloromethyl (meth) acrylamide.
  • haloacetyl group-containing unsaturated monomer examples include 3- (hydroxychloroacetoxy) propylallyl ether and p-vinylbenzylchloroacetic acid ester.
  • Each of these reactive group-containing monomers is used alone or in combination of two or more, and the proportion in the acrylic rubber is usually 0.01 to 20% by weight, preferably 0.1 to 10% by weight. , More preferably 0.5 to 5% by weight, and most preferably 1 to 3% by weight.
  • the other monomer used as needed is not particularly limited as long as it can be copolymerized with the above-mentioned monomer.
  • aromatic vinyl ethylenically unsaturated nitrile, acrylamide-based monomer, and the like.
  • Olefin-based monomers and the like examples of the aromatic vinyl include styrene, ⁇ -methylstyrene, divinylbenzene and the like.
  • the ethylenically unsaturated nitrile include acrylonitrile and methacrylonitrile.
  • the acrylamide-based monomer include acrylamide and methacrylamide.
  • other olefin-based monomers include ethylene, propylene, vinyl acetate, ethyl vinyl ether, and butyl vinyl ether.
  • the proportion in the acrylic rubber is usually 0 to 30% by weight, preferably 0 to 20% by weight, and more preferably 0. It is in the range of ⁇ 15% by weight, most preferably 0-10% by weight.
  • the acrylic rubber constituting the acrylic rubber sheet of the present invention is composed of the above-mentioned monomer components and preferably has a reactive group.
  • the reactive group is appropriately selected depending on the intended use without any particular limitation, but preferably at least one functional group selected from the group consisting of a carboxyl group, an epoxy group and a halogen group, more preferably a carboxyl group. At least one functional group selected from the group consisting of a group, an epoxy group and a chlorine atom, particularly preferably a carboxyl group, an epoxy group, and most preferably a carboxyl group, can highly improve the crosslinked properties of the acrylic rubber sheet. Suitable. Further, as the reactive group, when it is an ionic reactive group such as a carboxyl group or an epoxy group, the water resistance can be particularly improved, which is preferable. As the acrylic rubber having such a reactive group, a reactive group may be imparted to the acrylic rubber by a post-reaction, but a copolymer of a reactive group-containing monomer is preferable.
  • the content of the reactive group may be appropriately selected according to the purpose of use, but is usually 0.001% by weight or more, preferably 0.001 to 5% by weight, more preferably the weight ratio of the reactive group itself. Is in the range of 0.01 to 3% by weight, particularly preferably 0.05 to 1% by weight, most preferably 0.1 to 0.5% by weight, and has workability, strength characteristics, compressive permanent strain resistance, and oil resistance. Properties such as properties, cold resistance, and water resistance are highly balanced and suitable.
  • the acrylic rubber constituting the acrylic rubber sheet of the present invention include at least one (meth) acrylic acid ester selected from the group consisting of (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester. It consists of a reactive group-containing monomer and, if necessary, other copolymerizable monomers, and the proportions in each acrylic rubber are (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester.
  • the binding unit derived from at least one (meth) acrylic acid ester selected from the group consisting of is usually 50 to 99.99% by weight, preferably 70 to 99.9% by weight, and more preferably 80 to 99.5% by weight.
  • the binding unit derived from the reactive-containing monomer is usually 0.01 to 20% by weight, preferably 0.1 to 10% by weight, and more preferably 0. It is in the range of 5 to 5% by weight, particularly preferably 1 to 3% by weight, and the binding unit derived from other monomers is usually 0 to 30% by weight, preferably 0 to 20% by weight, and more preferably 0. It is in the range of ⁇ 15% by weight, particularly preferably 0 to 10% by weight.
  • the weight average molecular weight (Mw) of the acrylic rubber constituting the acrylic rubber sheet of the present invention is an absolute molecular weight measured by GPC-MALS, which is 100,000 to 5,000,000, preferably 500,000 to 5,000. In the range of 000, more preferably 1,000,000 to 5,000,000, particularly preferably 1,100,000 to 3,500,000, most preferably 1,200,000 to 2,500,000. At one point, the processability, strength characteristics, and compression-resistant permanent strain characteristics of the acrylic rubber sheet when mixed are highly balanced and suitable.
  • the ratio (Mz / Mw) of the z average molecular weight (Mz) and the weight average molecular weight (Mw) of the acrylic rubber constituting the acrylic rubber sheet of the present invention is absolute focusing on the polymer region measured by GPC-MALS.
  • the molecular weight distribution is 1.3 or more, preferably 1.4 to 5, more preferably 1.5 to 2, the processability and strength characteristics of the acrylic rubber bale are highly balanced and the physical properties at the time of storage. It is suitable because it can mitigate changes.
  • the glass transition temperature (Tg) of the acrylic rubber constituting the acrylic rubber sheet of the present invention is not particularly limited, but is usually 20 ° C. or lower, preferably 10 ° C. or lower, and more preferably 0 ° C. or lower.
  • the lower limit of the glass transition temperature (Tg) is not particularly limited, but is usually ⁇ 80 ° C. or higher, preferably ⁇ 60 ° C. or higher, and more preferably ⁇ 40 ° C. or higher.
  • the content of acrylic rubber in the acrylic rubber sheet of the present invention is appropriately selected depending on the intended use, but is usually 85% by weight or more, preferably 90% by weight or more, more preferably 95% by weight or more, and particularly preferably 95% by weight or more. It is 97% by weight or more, most preferably 98% by weight or more.
  • the content of acrylic rubber in the acrylic rubber sheet of the present invention is the amount of ash that could not be completely removed from the emulsifier and coagulant used from the total amount of the acrylic rubber sheet, and the phenolic aging that was added and dispersed in the acrylic rubber sheet. It is almost the same as the one minus the amount of inhibitor.
  • the acrylic rubber sheet of the present invention is characterized by containing a phenolic anti-aging agent.
  • the phenolic anti-aging agent used is not particularly limited as long as it is usually used as an anti-aging agent for rubber, but preferably when it is a hindered phenol-based anti-aging agent, it has storage stability. It is suitable because the effect of heat resistance can be highly achieved.
  • the hindered phenolic antioxidant is a phenolic antioxidant having a hindered structure, and the hindered structure is a structure having bulky substituents on both sides of the phenol group, and bulky substitutions on both sides.
  • the group is a substituent having 3 or more carbon atoms, preferably 4 groups, and specific examples thereof include an isobutyl group and a t-butyl group, and a t-butyl group is preferable.
  • the melting point of the phenolic antiaging agent is not particularly limited, but is usually 150 ° C. or lower, preferably 100 ° C. or lower, more preferably 90 ° C. or lower, particularly preferably 80 ° C. or lower, and most preferably 70 ° C. or lower. It is suitable because it has excellent uniform fine dispersibility with acrylic rubber during melt-kneading and can highly improve the storage stability and heat resistance of the acrylic rubber sheet.
  • the molecular weight of the phenolic antiaging agent is not particularly limited, but is excellent in uniform fine dispersibility with acrylic rubber when it is usually 250 to 1,000, preferably 300 to 800, and more preferably 350 to 600. It is suitable because it can highly improve the heat resistance and storage stability of the acrylic rubber sheet.
  • hindered phenolic anti-aging agent examples include 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, and 2,6-di-t-butyl- ⁇ -dimethyl.
  • octyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate
  • decyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate
  • phenol-based anti-aging agents other than hindered phenol-based anti-aging agents include styrenated phenols such as butylhydroxyanisole and mono (or di or tri) ( ⁇ -methylbenzyl) pheonol.
  • phenolic anti-aging agents can be used alone or in combination of two or more.
  • the content of the phenolic antioxidant in the acrylic rubber sheet is not particularly limited, but is usually 0.001 to 15% by weight, preferably 0.01 to 10% by weight, and more preferably 0.1 to 5% by weight. , Particularly preferably in the range of 0.3 to 3% by weight, most preferably in the range of 0.5 to 2% by weight.
  • the acrylic rubber sheet of the present invention can contain other anti-aging agents other than the phenol-based anti-aging agent as long as the object of the present invention is not impaired.
  • the acrylic rubber sheet of the present invention is characterized by being made of the acrylic rubber, containing the anti-aging agent, and having a specific gel amount.
  • the thickness of the acrylic rubber sheet of the present invention is not particularly limited, but is usually in the range of 1 to 40 mm, preferably 2 to 35 mm, more preferably 3 to 30 mm, and most preferably 5 to 25 mm.
  • Storage stability and productivity are highly balanced and suitable.
  • the thickness of an inexpensive acrylic rubber sheet with significantly improved productivity is usually in the range of 1 to 30 mm, preferably 2 to 25 mm, more preferably 3 to 15 mm, and particularly preferably 4 to 12 mm.
  • the width of the acrylic rubber sheet of the present invention is appropriately selected depending on the intended use, but is particularly handled when it is usually in the range of 300 to 1,200 mm, preferably 400 to 1,000 mm, and more preferably 500 to 800 mm. It has excellent properties and is suitable.
  • the length of the acrylic rubber sheet of the present invention is not particularly limited, but is particularly handleable when it is usually in the range of 300 to 1,200 mm, preferably 400 to 1,000 mm, and more preferably 500 to 800 mm. Excellent and suitable.
  • the gel amount of the acrylic rubber sheet of the present invention is the insoluble content of methyl ethyl ketone, which is 50% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less, still more preferably 15% by weight or less, and particularly preferably 10. When it is not more than% by weight, most preferably 5% by weight or less, the workability is highly improved and is preferable.
  • the amount of gel which is the insoluble matter of methyl ethyl ketone in the acrylic rubber veil, is related to the processability at the time of kneading such as Banbury, but the characteristics of the amount of gel differ depending on the solvent used, and in particular, THF (tetrahydrofuran) is insoluble. It did not correlate with the amount of gel in.
  • the ash content of the acrylic rubber sheet of the present invention is. Although not particularly limited, it is usually 0.8% by weight or less, preferably 0.5% by weight or less, more preferably 0.3% by weight or less, particularly preferably 0.2% by weight or less, and most preferably 0.15% by weight. When the following, it is excellent in storage stability and water resistance and is suitable.
  • the lower limit of the ash content of the acrylic rubber sheet of the present invention is not particularly limited, but is usually 0.0001% by weight or more, preferably 0.0005% by weight or more, and more preferably 0.001% by weight or more. Particularly preferably, when it is 0.005% by weight or more, and most preferably 0.01% by weight or more, metal adhesion is suppressed and workability is excellent.
  • the amount of ash in which the storage stability, water resistance and workability of the acrylic rubber sheet of the present invention are highly balanced is usually 0.0001 to 0.8% by weight, preferably 0.0005 to 0.5% by weight, and more. It is preferably in the range of 0.001 to 0.3% by weight, particularly preferably 0.005 to 0.2% by weight, and most preferably 0.01 to 0.15% by weight.
  • the content (total amount) of at least one element selected from the group consisting of sodium, sulfur, calcium, magnesium and phosphorus in the ash content of the acrylic rubber sheet of the present invention is not particularly limited, but is based on the total ash content.
  • Storage stability and water resistance are usually at least 30% by weight, preferably 50% by weight or more, more preferably 60% by weight or more, particularly preferably 70% by weight or more, and most preferably 80% by weight or more. Highly excellent and suitable.
  • the total amount of sodium and sulfur in the ash content of the acrylic rubber sheet of the present invention is not particularly limited, but is usually 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight, as a ratio to the total ash content. % Or more, particularly preferably 80% by weight or more, the storage stability and water resistance are highly excellent and suitable.
  • the ratio of sodium to sulfur ([Na] / [S]) in the ash content of the acrylic rubber sheet of the present invention is a weight ratio and is not particularly limited, but is usually 0.4 to 2.5, preferably 0. When it is in the range of .6 to 2, preferably 0.8 to 1.7, and more preferably 1 to 1.5, the water resistance is highly excellent and suitable.
  • the total amount of magnesium and phosphorus in the ash content of the acrylic rubber sheet of the present invention is not particularly limited, but is usually 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight, as a ratio to the total ash content. % Or more, particularly preferably 80% by weight or more, the storage stability and water resistance are highly excellent and suitable.
  • the ratio of magnesium to phosphorus ([Mg] / [P]) in the ash content of the acrylic rubber sheet of the present invention is a weight ratio and is not particularly limited, but is usually 0.4 to 2.5, preferably 0.
  • Storage stability and water resistance are in the range of .4 to 1.3, more preferably 0.4 to 1, particularly preferably 0.45 to 0.75, and most preferably 0.5 to 0.7. Highly excellent and suitable.
  • the specific gravity of the acrylic rubber sheet of the present invention is not particularly limited, but is usually 0.7 or more, preferably 0.8 to 1.4, more preferably 0.9 to 1.3, and particularly preferably 0.95 to. When it is 1.25, most preferably in the range of 1.0 to 1.2, the storage stability is highly excellent and suitable.
  • the pH of the acrylic rubber sheet of the present invention is not particularly limited, but is usually 6 or less, preferably 2 to 6, more preferably 2.5 to 5.5, and particularly preferably 3 to 5.
  • the storage stability is highly improved and is suitable.
  • the complex viscosity ([ ⁇ ] 60 ° C.) of the acrylic rubber sheet of the present invention at 60 ° C. is not particularly limited, but is usually 15,000 Pa ⁇ s or less, preferably 2,000 to 10,000 Pa ⁇ s. , More preferably in the range of 2,500 to 7,000 Pa ⁇ s, and most preferably in the range of 2,700 to 5,500 Pa ⁇ s, it is excellent in processability, oil resistance and shape retention.
  • the complex viscosity ([ ⁇ ] 100 ° C.) of the acrylic rubber sheet of the present invention at 100 ° C. is not particularly limited, but is usually 1,500 to 6,000 Pa ⁇ s, preferably 2,000 to 5, When it is in the range of 000 Pa ⁇ s, more preferably 2,500 to 4,000 Pa ⁇ s, and most preferably 2,500 to 3,500 Pa ⁇ s, it is excellent in processability, oil resistance, and shape retention. ..
  • the ratio of the complex viscosity at 100 ° C. ([ ⁇ ] 100 ° C.) of the acrylic rubber sheet of the present invention to the complex viscosity ([ ⁇ ] 60 ° C.) at 60 ° C. ([ ⁇ ] 100 ° C./[ ⁇ ] 60 ° C.) Is not particularly limited, but is usually 0.5 or more, preferably 0.6 or more, more preferably 0.7 or more, particularly preferably 0.8 or more, and most preferably 0.83 or more. Further, the ratio ([ ⁇ ] 100 ° C./[ ⁇ ] 60 of the complex viscosity ([ ⁇ ] 100 ° C.) of the acrylic rubber sheet of the present invention at 100 ° C.
  • the complex viscosity ([ ⁇ ] 60 ° C.) at 60 ° C. ° C.) is usually 0.5 to 0.99, preferably 0.6 to 0.98, more preferably 0.75 to 0.95, particularly preferably 0.8 to 0.94, and most preferably 0.
  • the range is in the range of 83 to 0.93, workability, oil resistance, and shape retention are highly balanced and suitable.
  • the water content of the acrylic rubber sheet of the present invention is not particularly limited, but the cross-linking characteristics are optimized when it is usually less than 1% by weight, preferably 0.8% by weight or less, and more preferably 0.6% by weight or less. It is suitable because it has excellent properties such as heat resistance and water resistance.
  • the Mooney viscosity (ML1 + 4,100 ° C.) of the acrylic rubber sheet of the present invention is not particularly limited, but is usually processed when it is in the range of 10 to 150, preferably 20 to 100, and more preferably 25 to 70. It is suitable because its properties and strength characteristics are highly balanced.
  • the type of the acrylic rubber sheet of the present invention is not particularly limited, and examples thereof include a blow sheet by a hollow molding method, a cast sheet by a solution casting method, and a melt kneading sheet by a melt extrusion method.
  • the melt-kneaded sheet is preferable because the storage stability effect of the phenol-based antiaging agent can be maximized.
  • the method for producing the acrylic rubber sheet of the present invention is not particularly limited, but for example, a monomer component containing (meth) acrylic acid ester as a main component is emulsified with water and an emulsifier in the presence of a polymerization initiator.
  • An emulsion polymerization step of obtaining an emulsion polymerization solution by emulsion polymerization to a polymerization conversion rate of 90% by weight or more, an antiaging agent addition step of adding a phenolic antiaging agent to the obtained emulsion polymerization solution, and an antiaging agent are added.
  • a monomer component containing (meth) acrylic acid ester as a main component is emulsified with water and an emulsifier, and the polymerization conversion rate is 90% by weight or more in the presence of a polymerization initiator. It is characterized in that an emulsion polymerization solution is obtained by emulsion polymerization.
  • the monomer component used is the same as that exemplified in the monomer component and those described in the preferred range, and the amount used is the monomer of the acrylic rubber constituting the acrylic rubber sheet. It may be appropriately selected so as to have a composition.
  • the emulsifier used for emulsion polymerization is not particularly limited, and examples thereof include an anionic emulsifier, a cationic emulsifier, and a nonionic emulsifier, and preferably include an anionic emulsifier.
  • the anionic emulsifier is not particularly limited, for example, salts of fatty acids such as myristic acid, palmitic acid, oleic acid and linolenic acid; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; sulfate esters such as sodium lauryl sulfate. Phosphate esters such as salts, polyoxyalkylene alkyl ether phosphate salts; alkyl sulfosuccinates and the like can be mentioned. Among these anionic emulsifiers, phosphate ester salts and sulfate ester salts are preferable, and phosphate ester salts are particularly preferable.
  • Suitable phosphate salts include, for example, sodium lauryl phosphate, potassium lauryl phosphate, sodium polyoxyalkylene alkyl ether phosphate and the like.
  • suitable sulfate ester salts include sodium lauryl sulfate, ammonium lauryl sulfate, sodium myristyl sulfate, sodium laureth sulfate, sodium polyoxyethylene alkyl sulfate, sodium polyoxyethylene alkylaryl sulfate, and the like.
  • Sodium lauryl sulfate is particularly suitable.
  • These anionic emulsifiers can be used alone or in combination of two or more.
  • Examples of the cationic emulsifier include alkyltrimethylammonium chloride, dialkylammonium chloride, and benzylammonium chloride.
  • the nonionic emulsifier is not particularly limited, but for example, a polyoxyalkylene fatty acid ester such as polyoxyethylene stearate ester; a polyoxyalkylene alkyl ether such as polyoxyethylene dodecyl ether; and a polyoxy such as polyoxyethylene nonylphenyl ether.
  • a polyoxyalkylene fatty acid ester such as polyoxyethylene stearate ester
  • a polyoxyalkylene alkyl ether such as polyoxyethylene dodecyl ether
  • a polyoxy such as polyoxyethylene nonylphenyl ether.
  • Alkylene alkylphenol ether; polyoxyethylene sorbitan alkyl ester and the like can be mentioned, and polyoxyalkylene alkyl ether and polyoxyalkylene alkyl phenol ether are preferable, and polyoxyethylene alkyl ether and polyoxyethylene alkyl phenol ether are more preferable.
  • Each of these emulsifiers can be used alone or in combination of two or more, and the amount used is usually 0.01 to 10 parts by weight, preferably 0, with respect to 100 parts by weight of the monomer component. It is in the range of 1 to 5 parts by weight, more preferably 1 to 3 parts by weight.
  • a conventional method may be followed, and examples thereof include a method of stirring the monomer, emulsifier and water using a stirrer such as a homogenizer or a disk turbine. ..
  • the amount of water used is usually 1 to 1,000 parts by weight, preferably 5 to 500 parts by weight, more preferably 10 to 300 parts by weight, and particularly preferably 15 to 150 parts by weight with respect to 100 parts by weight of the monomer component. Parts, most preferably in the range of 20-80 parts by weight.
  • the polymerization catalyst used is not particularly limited as long as it is usually used in emulsion polymerization, but for example, a redox catalyst composed of a radical generator and a reducing agent can be used.
  • radical generator examples include peroxides and azo compounds, and peroxides are preferable.
  • peroxide an inorganic peroxide or an organic peroxide is used.
  • inorganic peroxide examples include sodium persulfate, potassium persulfate, hydrogen peroxide, ammonium persulfate and the like.
  • potassium persulfate, hydrogen peroxide and ammonium persulfate are preferable, and potassium persulfate is particularly preferable. preferable.
  • the organic peroxide is not particularly limited as long as it is a known organic peroxide used in emulsion polymerization.
  • azo compound examples include azobisisobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis [2- (2-imidazolin-2-yl) propane, 2,2. '-Azobis (Propane-2-carboamidine), 2,2'-Azobis [N- (2-carboxyethyl) -2-methylpropaneamide], 2,2'-Azobis ⁇ 2- [1- (2- (2-) Hydroxyethyl) -2-imidazolin-2-yl] propane ⁇ , 2,2'-azobis (1-imino-1-pyrrolidino-2-methylpropane) and 2,2'-azobis ⁇ 2-methyl-N- [ 1,1-bis (hydroxymethyl) -2-hydroxyethyl] propanamide ⁇ and the like can be mentioned.
  • Each of these radical generators can be used alone or in combination of two or more, and the amount used is usually 0.0001 to 5 parts by weight, preferably 0.0001 to 5 parts by weight, based on 100 parts by weight of the monomer component. It is in the range of 0.0005 to 1 part by weight, more preferably 0.001 to 0.5 parts by weight.
  • any one used in the redox catalyst of emulsion polymerization can be used without particular limitation, but in the present invention, it is particularly preferable to use at least two kinds of reducing agents.
  • the at least two types of reducing agents for example, a combination of a metal ion compound in a reduced state and another reducing agent is suitable.
  • the metal ion compound in the reduced state is not particularly limited, and examples thereof include ferrous sulfate, sodium hexamethylenediamine tetraacetate, and cuprous naphthenate, and among these, ferrous sulfate is preferable.
  • Each of these reduced metal ion compounds can be used alone or in combination of two or more, and the amount used is usually 0.000001 to 0. With respect to 100 parts by weight of the monomer component. It is in the range of 01 parts by weight, preferably 0.00001 to 0.001 parts by weight, and more preferably 0.00005 to 0.0005 parts by weight.
  • the reducing agent other than the metal ion compound in the reduced state is not particularly limited, and is, for example, ascorbic acid such as ascorbic acid, sodium ascorbate, potassium ascorbate or a salt thereof; erythorbic acid, sodium erythorbicate, erythorbin.
  • Elysorbic acid such as potassium acid or a salt thereof; sulphinate such as sodium hydroxymethane sulfite; sodium sulfite, potassium sulfite, sodium hydrogen sulfite, aldehyde sodium hydrogen sulfite, potassium hydrogen sulfite sulfite; sodium pyrosulfite, potassium pyrosulfite , Pyro sulfites such as sodium pyrosulfite and potassium hydrogen sulfite; thiosulfates such as sodium thiosulfite and potassium thiosulfite; of sodium bisulfite, sodium bisulfite, potassium bisulfite, sodium hydrogen sulfite, potassium hydrogen sulfite Pyrophosphoric acid or a salt thereof; pyroaphosphate or a salt thereof such as pyrosulfite, sodium pyrophosphite, potassium pyrosulfite, sodium hydrogen pyrosulfite, potassium hydrogen pyr
  • the reducing agents other than the metal ion compounds in the reduced state can be used alone or in combination of two or more, and the amount used is usually 0.001 with respect to 100 parts by weight of the monomer component. It is in the range of ⁇ 1 part by weight, preferably 0.005 to 0.5 parts by weight, and more preferably 0.01 to 0.3 parts by weight.
  • a preferred combination of the reducing metal ion compound and the other reducing agent is ferrous sulfate and ascorbic acid or a salt thereof and / or sodium formaldehyde sulfoxylate, more preferably ferrous sulfate and ascorbate. And / or sodium formaldehyde sulfoxylate, most preferably a combination of ferrous sulfate and alcorbate.
  • the amount of ferrous sulfate used is usually 0.000001 to 0.01 parts by weight, preferably 0.00001 to 0.001 parts by weight, more preferably 0.00001 parts by weight, based on 100 parts by weight of the monomer component.
  • the amount of ascorbic acid or a salt thereof and / or sodium formaldehyde sulfoxylate used is usually 0.001 to 1 part by weight with respect to 100 parts by weight of the monomer component. It is preferably in the range of 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.3 parts by weight.
  • the amount of water used in the emulsion polymerization reaction may be only the one used at the time of emulsification of the monomer component, but is usually 10 to 1,000 parts by weight, preferably 10 to 1,000 parts by weight, based on 100 parts by weight of the monomer component used for polymerization. Is adjusted to be in the range of 50 to 500 parts by weight, more preferably 80 to 400 parts by weight, and most preferably 100 to 300 parts by weight.
  • the emulsion polymerization reaction may be carried out according to a conventional method, and may be a batch type, a semi-batch type, or a continuous type.
  • the polymerization temperature and the polymerization time are not particularly limited and can be appropriately selected from the type of polymerization initiator used and the like.
  • the polymerization temperature is usually in the range of 0 to 100 ° C., preferably 5 to 80 ° C., more preferably 10 to 50 ° C., and the polymerization time is usually 0.5 to 100 hours, preferably 1 to 10 hours.
  • the polymerization conversion rate of the emulsion polymerization reaction is not particularly limited, but is excellent in the strength characteristics of the acrylic rubber sheet usually produced when it is usually 80% by weight or more, preferably 90% by weight or more, and more preferably 95% by weight or more. Moreover, there is no monomeric odor and it is suitable.
  • a polymerization inhibitor may be used to terminate the polymerization.
  • the antiaging agent addition step in the method for producing an acrylic rubber sheet of the present invention is characterized by adding a phenolic antiaging agent to the emulsion polymerization solution after the emulsion polymerization.
  • the amount of the phenolic antioxidant used may be appropriately selected so as to be the content of the phenolic antioxidant in the acrylic rubber sheet of the present invention, and is usually selected with respect to 100 parts by weight of the monomer component. 0.001 to 15 parts by weight, preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, particularly preferably 0.3 to 3 parts by weight, most preferably 0.5 to 2 parts by weight. Is the range of.
  • the method of adding the phenolic antioxidant to the emulsion polymerization solution is not particularly limited, but for example, the phenolic antioxidant is emulsified with an emulsifier and water and added as an emulsion containing the phenolic antioxidant.
  • the antioxidant is easily dispersed in the acrylic rubber, and is further finely dispersed in the screw type extruder, and the anti-aging effect is maximized, which is suitable.
  • the method of emulsifying the phenolic antiaging agent is not particularly limited, but it is usually made into an emulsion with water and an emulsifier, and then the phenolic antiaging agent is added and stirred until uniformly dispersed. Can be manufactured.
  • the water for emulsifying the phenolic antiaging agent is preferably warm water, and when the temperature is usually 40 ° C. or higher, preferably 50 to 90 ° C., and more preferably 60 to 80 ° C. It is suitable because the anti-aging agent can be easily emulsified and uniformly dispersed.
  • the temperature of the water for emulsifying the phenolic antiaging agent is also above the melting point of the phenolic antiaging agent used, preferably at a melting point of + 5 ° C. or higher, more preferably at a melting point of + 10 ° C. or higher. It is suitable because it is easy to emulsify the agent and it enables uniform dispersion.
  • the emulsifier for emulsifying the phenolic anti-aging agent is not particularly limited, but the same emulsifier used when emulsifying the monomer component can be used to isolate the acrylic rubber in the subsequent step. It is stable and suitable on the above. Specific examples thereof include anionic emulsifiers, cationic emulsifiers, nonionic emulsifiers, etc., preferably anionic emulsifiers, more preferably phosphoric acid ester salts, sulfate ester salts, and particularly preferably phosphoric acid ester salts. ..
  • the amount of the emulsifier used for emulsifying the phenolic anti-aging agent may be appropriately selected depending on the molecular weight, melting point, SP value, etc. of the anti-aging agent to be used, but with respect to the emulsion of water and the emulsifier, Phenolic anti-aging is usually in the range of 1% by weight or more, preferably 2 to 40% by weight, more preferably 3 to 30% by weight, particularly preferably 4 to 20% by weight, and most preferably 5 to 15% by weight.
  • the agent is suitable because it can be easily emulsified and uniformly dispersed.
  • the stirring time for emulsifying the phenolic anti-aging agent is not particularly limited to the time until the anti-aging agent is uniformly dispersed, but it is usually 1 hour or more, preferably 1 to 5 hours, preferably 1 to 5 hours. Is in the range of 1 to 4 hours, more preferably 1 to 3 hours.
  • the phenol-based anti-aging agent-containing emulsion added to the emulsion polymerization solution thus obtained, the phenol-based anti-aging agent is uniformly dispersed.
  • the uniform dispersibility of the phenolic anti-aging agent in the phenol-based anti-aging agent-containing emulsion can be determined, for example, as follows. The glass container that was once filled with the phenol-based anti-aging agent-containing emulsion and then removed was allowed to stand, and the wall surface of the glass container was not contaminated after the adhered phenol-based anti-aging agent-containing emulsion hung down on the wall surface. Those with good uniform dispersion can be judged as those with white powder attached, and those with white powder attached can be judged as poor uniform dispersion.
  • the phenolic anti-aging agent-containing emulsion once uniformly dispersed is unlikely to re-coagulate even if it is allowed to stand, but if it becomes poorly dispersed, it can be used after being stirred again and readjuste
  • the phenol-based anti-aging agent content of the phenol-based anti-aging agent-containing emulsion is appropriately selected depending on the intended use, but is usually 10 to 80% by weight, preferably 20 to 60% by weight, and more preferably 30 to 45% by weight. When it is%, the storage stability and heat resistance of the acrylic rubber sheet can be highly improved, which is preferable.
  • the emulsifier concentration of the phenolic antioxidant-containing emulsion is not particularly limited, but is usually 1% by weight or more, preferably 1 to 30% by weight, more preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight, most. It is preferable that the storage stability, heat resistance and water resistance of the acrylic rubber sheet can be highly balanced when the content is in the range of 5 to 10% by weight.
  • the pH of the phenolic antioxidant-containing emulsion is not particularly limited, but is usually 6 or less, preferably 2 to 6, more preferably 3 to 6, and the storage stability of the acrylic rubber sheet. It has excellent heat resistance and is suitable.
  • the method of adding the phenol-based anti-aging agent or the phenol-based anti-aging agent-containing emulsion to the emulsion polymerization solution is not particularly limited and may follow a conventional method.
  • the coagulation step in the method for producing acrylic rubber of the present invention is a step of bringing the emulsion polymerization solution to which the phenolic antiaging agent is added into contact with the coagulation solution to form a hydrous crumb.
  • the solid content concentration of the emulsion polymerization solution used in the coagulation step is not particularly limited, but is usually adjusted to the range of 5 to 50% by weight, preferably 10 to 45% by weight, and more preferably 20 to 40% by weight. To.
  • the coagulant used is not particularly limited, but usually a metal salt is used.
  • the metal salt include alkali metals, Group 2 metal salts of the Periodic Table, and other metal salts, preferably alkali metal salts, Group 2 metal salts of the Periodic Table, and more preferably Group 2 of the Periodic Table.
  • alkali metal salt examples include sodium salts such as sodium chloride, sodium nitrate and sodium sulfate; potassium salts such as potassium chloride, potassium nitrate and potassium sulfate; and lithium salts such as lithium chloride, lithium nitrate and lithium sulfate.
  • sodium salts are preferable, and sodium chloride and sodium sulfate are particularly preferable.
  • Examples of the Group 2 metal salt in the periodic table include magnesium chloride, calcium chloride, magnesium nitrate, calcium nitrate, magnesium sulfate, calcium sulfate and the like, and calcium chloride and magnesium sulfate are preferable.
  • metal salts include, for example, zinc chloride, titanium chloride, manganese chloride, iron chloride, cobalt chloride, nickel chloride, aluminum chloride, tin chloride, zinc nitrate, titanium nitrate, manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate. , Aluminum nitrate, tin nitrate, zinc sulfate, titanium sulfate, manganese sulfate, iron sulfate, cobalt sulfate, nickel sulfate, aluminum sulfate, tin sulfate and the like.
  • Each of these coagulants can be used alone or in combination of two or more, and the amount used is usually 0.01 to 100 parts by weight, preferably 0, with respect to 100 parts by weight of the monomer component. It is in the range of 1 to 50 parts by weight, more preferably 1 to 30 parts by weight. When the coagulant is in this range, it is preferable because the acrylic rubber can be sufficiently coagulated, and the compression set resistance and water resistance when the acrylic rubber sheet is crosslinked can be highly improved.
  • the coagulant concentration of the coagulant used is usually in the range of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, and particularly preferably 1.5 to 5% by weight. It is preferable that the particle size of the hydrous crumb generated in the above case can be uniformly focused in a specific region.
  • the temperature of the coagulating liquid is not particularly limited, but is preferably 40 ° C. or higher, preferably 40 to 90 ° C., more preferably 50 to 80 ° C., because a uniform water-containing crumb is produced.
  • the contact between the emulsion polymerization solution and the coagulation solution is not particularly limited, but for example, a method of adding the emulsion polymerization solution to the agitated coagulation solution, or adding the coagulation solution to the agitated emulsion polymerization solution.
  • a method of adding the emulsion polymerization solution to the agitated coagulating liquid is a method of uniformly focusing the shape and crumb diameter of the water-containing crumb to be generated in a specific region and cleaning the emulsifier and coagulant. It is suitable because the efficiency can be significantly improved.
  • the stirring speed (rotation speed) of the coagulated liquid being stirred is represented by the rotation speed of the stirring blade of the stirring device provided in the coagulation bath in the present invention, and is usually 100 rpm or more, preferably 200 to 1,000 rpm. It is more preferably in the range of 300 to 900 rpm, and particularly preferably in the range of 400 to 800 rpm.
  • the rotation speed at which the coagulating liquid is vigorously agitated to some extent is suitable because the hydrous crumb particle size to be generated can be made small and uniform, and by setting it to the above lower limit or more, the crumb particle size becomes excessive. It is possible to suppress the formation of large and small ones, and by setting the amount to the upper limit or less, the solidification reaction can be more easily controlled.
  • the peripheral speed of the agitated coagulant is represented by the linear velocity of the outer circumference of the stirring blade of the agitator provided in the coagulation bath, but the water-containing crumb particle size generated when the agitator is vigorously agitated to a certain degree.
  • the peripheral speed is usually 0.5 m / s or more, preferably 1 m / s or more, more preferably 1.5 m / s or more, particularly preferably 2 m / s or more, and most preferably 2. It is 5 m / s or more.
  • the upper limit of the peripheral speed is not particularly limited, but usually solidifies when it is 50 m / s or less, preferably 30 m / s or less, more preferably 25 m / s or less, and most preferably 20 m / s or less. It is suitable because the reaction can be easily controlled.
  • the cleaning method is not particularly limited and may follow a conventional method.
  • the produced hydrous crumb can be mixed with a large amount of water.
  • the amount of water used is not particularly limited, but the amount per washing with water is usually 50 parts by weight or more, preferably 50 to 15,000 parts by weight, based on 100 parts by weight of the monomer component.
  • the amount of ash in the acrylic rubber can be effectively reduced, preferably in the range of 100 to 10,000 parts by weight, particularly preferably in the range of 150 to 5,000 parts by weight.
  • the temperature of the water to be washed with water is not particularly limited, but the washing efficiency is usually 40 ° C. or higher, preferably 40 to 100 ° C., more preferably 50 to 90 ° C., and most preferably 60 to 80 ° C. It is suitable because it can be raised remarkably.
  • the emulsifier and coagulant are released from the hydrous crumb to further improve the washing efficiency.
  • the cleaning time is not particularly limited, but is usually in the range of 1 to 120 minutes, preferably 2 to 60 minutes, and more preferably 3 to 30 minutes.
  • the number of washings is not particularly limited, and is usually 1 to 10 times, preferably a plurality of times, and more preferably 2 to 3 times. From the viewpoint of reducing the residual amount of the coagulant in the finally obtained acrylic rubber sheet, it is desirable that the number of times of washing with water is large, but the shape and diameter of the water-containing crumb should be specified and / Alternatively, the number of cleanings can be significantly reduced by setting the cleaning temperature within the above range.
  • the washed water-containing crumb is subjected to a dehydration barrel having a dehydration slit, a drying barrel under reduced pressure, and a screw type extruder having a die at the tip. It is characterized by dehydrating to a water content of 1 to 40% by weight in a dehydration barrel and then drying to less than 1% by weight in a drying barrel to extrude a sheet-shaped dry rubber from a die.
  • the water-containing crumb supplied to the screw type extruder is preferably one in which free water is removed (drained) after washing.
  • Draining step In the method for producing an acrylic rubber sheet of the present invention, it is possible to provide a draining step for separating free water from the water-containing crumb after washing with a drainer after the washing step and before the dehydration / drying / molding step. It is suitable for increasing efficiency.
  • a known one can be used without particular limitation, and examples thereof include a wire mesh, a screen, an electric sieve, and the like, preferably a wire mesh and a screen.
  • the opening of the drainer is not particularly limited, but when it is usually in the range of 0.01 to 5 mm, preferably 0.1 to 1 mm, and more preferably 0.2 to 0.6 mm, the water content crumb loss is small. Moreover, draining can be done efficiently, which is suitable.
  • the water content of the water-containing crumb after draining is not particularly limited, but is usually 50 to 80% by weight, preferably 50 to 70% by weight. , More preferably in the range of 50-60% by weight.
  • the temperature of the hydrous crumb after draining that is, the temperature of the hydrous crumb put into the dehydration / drying / molding step is not particularly limited, but is usually 40 ° C. or higher, preferably 40 to 100 ° C., more preferably 50 ° C.
  • the specific heat is as high as 1.5 to 2.5 KJ / kg ⁇ K like the acrylic rubber of the present invention. It is suitable because the water-containing crumb that is difficult to raise can be efficiently dehydrated and dried with a screw type extruder.
  • Dehydration of hydrous crumbs Dehydration barrel
  • Dehydration of the water-containing crumb is performed in a dehydration barrel having a dehydration slit provided in the screw type extruder.
  • the opening of the dehydration slit may be appropriately selected according to the conditions of use, but is usually in the range of 0.01 to 5 mm, preferably 0.1 to 1 mm, and more preferably 0.2 to 0.6 mm.
  • the number of dehydration barrels in the screw extruder is not particularly limited, but usually a plurality, preferably 2 to 10, more preferably 3 to 6, is used to dehydrate the adhesive acrylic rubber. It is suitable for efficient operation.
  • the set temperature of the dehydration barrel is appropriately selected depending on the monomer composition, ash content, water content, operating conditions, etc. of the acrylic rubber, but is usually 60 to 150 ° C., preferably 70 to 140 ° C., more preferably 80 to 80 to It is in the range of 130 ° C.
  • the set temperature of the dehydration barrel that dehydrates in the drained state is usually 60 ° C. to 120 ° C., preferably 70 to 110 ° C., and more preferably 80 to 100 ° C.
  • the set temperature of the dehydration barrel that is pre-dried in the exhausted steam state is usually in the range of 100 to 150 ° C., preferably 105 to 140 ° C., and more preferably 110 to 130 ° C.
  • the water content of the crumb after dehydration of the drainage type dehydration that squeezes water from the water-containing crumb, that is, after passing through the drainage type dehydration barrel is not particularly limited, but is usually 1 to 45% by weight, preferably 1 to 40% by weight. , More preferably 5 to 35% by weight, particularly preferably 10 to 35% by weight, and most preferably 15 to 35% by weight, the productivity and the ash removal efficiency are highly balanced and preferable.
  • the water content of the water-containing crumb is usually 5 to 45% by weight, preferably 10 to 40% by weight after dehydration in the drainage type dehydration barrel portion.
  • the water content after pre-drying in the exhaust steam type dehydration barrel portion is preferably 15 to 35% by weight, usually 1 to 30% by weight, preferably 3 to 20% by weight, and more preferably 5 to 15% by weight.
  • the dehydration time can be shortened and deterioration of acrylic rubber can be suppressed, and by setting it to be lower than the upper limit, the amount of ash can be sufficiently reduced.
  • hydrous crumb dry barrel
  • the hydrous crumb after dehydration is dried in a drying barrel portion under reduced pressure.
  • the degree of decompression of the drying barrel may be appropriately selected, but it is preferable that the hydrous crumb can be efficiently dried when it is usually 1 to 50 kPa, preferably 2 to 30 kPa, and more preferably 3 to 20 kPa.
  • the set temperature of the drying barrel may be appropriately selected, but when it is usually in the range of 100 to 250 ° C., preferably 110 to 200 ° C., more preferably 120 to 180 ° C., there is no discoloration or deterioration of the acrylic rubber. It is suitable because it can be dried efficiently and the amount of gel in the acrylic rubber sheet can be reduced.
  • the number of drying barrels in the screw type extruder is not particularly limited, but is usually a plurality, preferably 2 to 10, and more preferably 3 to 8.
  • the decompression degree may be an approximate decompression degree for all the dry barrels, or may be changed.
  • the set temperature may be an approximate temperature for all the drying barrels or may be changed, but it is closer to the discharge part (closer to the die) than the temperature of the introduction part (closer to the dehydration barrel). It is preferable that the temperature of (1) is higher because the drying efficiency can be increased.
  • the water content of the dried rubber after drying is usually less than 1% by weight, preferably 0.8% by weight or less, and more preferably 0.6% by weight or less.
  • the phenolic anti-aging agent and acrylic rubber are melt-kneaded and extruded at this value (with almost all water removed), especially in a screw-type extruder, to achieve storage stability and heat resistance.
  • Acrylic rubber sheets with highly improved properties can be manufactured, which is suitable.
  • the acrylic rubber is melt-kneaded in a state where almost all water is removed, so that the gel amount of the methyl ethyl ketone insoluble portion of the acrylic rubber sheet can be reduced and the processability of the acrylic rubber sheet can be remarkably improved. Is.
  • Dry rubber (die part) The dried rubber dehydrated and dried by the screw portion of the dehydration barrel and the drying barrel is sent to the rectifying die portion without a screw.
  • a breaker plate or wire mesh may or may not be provided between the screw portion and the die portion.
  • the extruded dry rubber is suitable because the die shape is made substantially rectangular and the die is formed into a sheet, so that air entrainment is small, the specific gravity is large, and the dry rubber is excellent in storage stability.
  • the resin pressure in the die portion is not particularly limited, but when it is usually in the range of 0.1 to 10 MPa, preferably 0.5 to 5 MPa, and more preferably 1 to 3 MPa, less air entrainment (high specific gravity). Moreover, it is excellent in productivity and suitable.
  • Screw type extruder and operating conditions The screw length (L) of the screw type extruder used may be appropriately selected according to the purpose of use, but is usually 3,000 to 15,000 mm, preferably 4,000 to. It is in the range of 10,000 mm, more preferably 4,500 to 8,000 mm.
  • the screw diameter (D) of the screw type extruder used may be appropriately selected according to the purpose of use, but is usually in the range of 50 to 250 mm, preferably 100 to 200 mm, and more preferably 120 to 160 mm.
  • the ratio (L / D) of the screw length (L) to the screw diameter (D) of the screw type extruder used is not particularly limited, but is usually 10 to 100, preferably 20 to 80, and more. It is preferable that the water content is less than 1% by weight without lowering the molecular weight or burning of the dried rubber when it is in the range of 30 to 60.
  • the rotation speed (N) of the screw type extruder used may be appropriately selected according to various conditions, but is usually 10 to 1,000 rpm, preferably 50 to 750 rpm, more preferably 100 to 500 rpm, and most preferably. Is suitable because it can efficiently reduce the water content and gel amount of acrylic rubber when the speed is 120 to 300 rpm.
  • the extrusion amount (Q) of the screw type extruder used is not particularly limited, but is usually 100 to 1,500 kg / hr, preferably 300 to 1,200 kg / hr, more preferably 400 to 1,000 kg / hr. Most preferably, it is in the range of 500 to 800 kg / hr.
  • the ratio (Q / N) of the extrusion amount (Q) to the rotation speed (N) of the screw type extruder used is not particularly limited, but is usually 2 to 10, preferably 3 to 8, more preferably. Is in the range of 4-6.
  • Sheet-shaped dry rubber The shape of the dry rubber extruded from the screw-type extruder is sheet-like, and at this time, the specific gravity can be increased without entraining air, and the storage stability is highly improved, which is suitable.
  • the sheet-shaped dry rubber extruded from the screw type extruder is preferably cut after cooling and used as an acrylic rubber sheet.
  • the thickness of the sheet-shaped dry rubber extruded from the screw type extruder is not particularly limited, but is usually in the range of 1 to 40 mm, preferably 2 to 35 mm, more preferably 3 to 30 mm, and most preferably 5 to 25 mm. It is suitable because it has excellent workability and productivity at some time. In particular, since the thermal conductivity of the sheet-shaped dry rubber is as low as 0.15 to 0.35 W / mK, the thickness of the sheet-shaped dry rubber is usually 1 to 30 mm when the cooling efficiency is increased and the productivity is remarkably improved.
  • the range is preferably 2 to 25 mm, more preferably 3 to 15 mm, and particularly preferably 4 to 12 mm.
  • the width of the sheet-shaped dry rubber extruded from the screw type extruder is appropriately selected according to the purpose of use, but is usually in the range of 300 to 1,200 mm, preferably 400 to 1,000 mm, and more preferably 500 to 800 mm. is there.
  • the temperature of the dry rubber extruded from the screw type extruder is not particularly limited, but is usually in the range of 100 to 200 ° C, preferably 110 to 180 ° C, and more preferably 120 to 160 ° C.
  • the water content of the dried rubber extruded from the screw type extruder is not particularly limited, but is usually less than 1% by weight, preferably 0.8% by weight or less, and more preferably 0.6% by weight or less.
  • the complex viscosity ([ ⁇ ] 100 ° C.) of the sheet-shaped dry rubber extruded from the screw type extruder at 100 ° C. is not particularly limited, but is usually 1,500 to 6,000 Pa ⁇ s, preferably 2.
  • Extrudability and shape retention as a sheet when the range is 5,000 to 5,000 Pa ⁇ s, more preferably 2,500 to 4,000 Pa ⁇ s, and most preferably 2,500 to 3,500 Pa ⁇ s. Is highly balanced and suitable. That is, when it is at least the lower limit, the extrudability can be improved, and when it is at least the upper limit, the shape of the sheet-shaped dry rubber can be suppressed from collapsing or breaking.
  • the sheet-shaped dry rubber extruded from the screw type extruder may be used by folding it as it is, but it can be preferably cut and used.
  • the cutting of the sheet-shaped dry rubber is not particularly limited, but since the acrylic rubber of the acrylic rubber sheet of the present invention has strong adhesiveness, the sheet-shaped dry rubber is used in order to continuously cut without entraining air. It is preferable to cool it down.
  • the cutting temperature of the sheet-shaped dry rubber is not particularly limited, but when it is usually 60 ° C. or lower, preferably 55 ° C. or lower, more preferably 50 ° C. or lower, the cutability and productivity are highly balanced and preferable. Is.
  • the complex viscosity ([ ⁇ ] 60 ° C.) of the sheet-shaped dry rubber at 60 ° C. is not particularly limited, but is usually 15,000 Pa ⁇ s or less, preferably 2,000 to 10,000 Pa ⁇ s. When it is preferably in the range of 2,500 to 7,000 Pa ⁇ s, most preferably 2,700 to 5,500 Pa ⁇ s, it is preferable that it can be cut continuously without entraining air.
  • the ratio ([ ⁇ ] 100 ° C./[ ⁇ ] 60 ° C.) of the complex viscosity at 100 ° C. ([ ⁇ ] 100 ° C.) of the sheet-shaped dried rubber to the complex viscosity ([ ⁇ ] 60 ° C.) at 60 ° C. is although there is no particular limitation, it is usually 0.5 or more, preferably 0.6 to 0.98, more preferably 0.75 to 0.95, particularly preferably 0.8 to 0.94, and most preferably 0.83. When the range is in the range of about 0.93, the air entrainment property is low, and cutting and productivity are highly balanced, which is preferable.
  • the method for cooling the sheet-shaped dry rubber is not particularly limited and may be left at room temperature. However, since the thermal conductivity of the sheet-shaped dry rubber is very small, 0.15 to 0.35 W / mK, it is blown or blown. Forced cooling such as an air cooling method under cooling, a water spraying method in which water is sprayed, or an immersion method in which water is immersed is preferable in order to increase productivity, and an air cooling method in which air is blown or cooled is particularly preferable.
  • the sheet-shaped dry rubber can be extruded from a screw-type extruder onto a conveyor such as a belt conveyor, and can be conveyed and cooled while blowing cold air.
  • the temperature of the cold air is not particularly limited, but is usually in the range of 0 to 25 ° C, preferably 5 to 25 ° C, and more preferably 10 to 20 ° C.
  • the length to be cooled is not particularly limited, but is usually in the range of 5 to 500 m, preferably 10 to 200 m, and more preferably 20 to 100 m.
  • the cooling rate of the sheet-shaped dry rubber is not particularly limited, but it is particularly easy to cut when it is usually 50 ° C./hr or more, more preferably 100 ° C./hr or more, and more preferably 150 ° C./hr or more. It is suitable.
  • the cutting length of the sheet-shaped dry rubber is not particularly limited and is appropriately selected according to the purpose of use, but is usually in the range of 100 to 800 mm, preferably 200 to 500 mm, and more preferably 250 to 450 mm.
  • the acrylic rubber sheet thus obtained has excellent operability and storage stability as compared with crumb-shaped acrylic rubber, and can be used as it is or laminated and veiled.
  • the acrylic rubber veil of the present invention is characterized in that the acrylic rubber sheets are laminated and integrated.
  • the number of layers is appropriately selected according to the size or weight of the acrylic rubber veil.
  • the size of the acrylic rubber veil of the present invention is not particularly limited, but the width is usually in the range of 100 to 800 mm, preferably 200 to 500 mm, more preferably 250 to 450 mm, and the length is usually 300 to 1. , 200 mm, preferably 400 to 1,000 mm, more preferably 500 to 800 mm, and height usually 50 to 500 mm, preferably 100 to 300 mm, more preferably 150 to 250 mm.
  • Reactive group content, water content, ash content, component content and ratio in ash, specific gravity, gel amount, pH, complex viscosity at 60 ° C. ([ ⁇ ] 60 ° C.), at 100 ° C. of the acrylic rubber veil of the present invention Complex viscosity ([ ⁇ ] 100 ° C), ratio of complex viscosity at 100 ° C ([ ⁇ ] 100 ° C) to complex viscosity at 60 ° C ([ ⁇ ] 60 ° C) ([ ⁇ ] 100 ° C / [ ⁇ ] ] 60 ° C.) and Mooney viscosity (ML1 + 4,100 ° C.) are the same as the respective characteristic values of the acrylic rubber sheet.
  • the method for producing the acrylic rubber veil of the present invention is not particularly limited, but it can be easily produced by cooling and cutting the sheet-shaped dry rubber extruded from the screw type extruder and then laminating it.
  • the laminating temperature of the sheet-shaped dry rubber is not particularly limited, but is preferably 30 ° C. or higher, preferably 35 ° C. or higher, more preferably 40 ° C. or higher, because air entrained during laminating can be released.
  • the number of laminated layers may be appropriately selected according to the size or weight of the acrylic rubber veil. In the acrylic rubber veil of the present invention, laminated sheet-shaped dry rubber is integrated by its own weight.
  • the acrylic rubber veil of the present invention thus obtained is superior in operability, storage stability and water resistance as compared with crumb-shaped acrylic rubber, and the acrylic rubber veil can be used as it is or by cutting a required amount into a banbury, roll, etc. It can be used by putting it in a mixer.
  • the rubber mixture of the present invention is characterized in that the acrylic rubber sheet or acrylic rubber veil is mixed with a filler and a cross-linking agent.
  • the filler is not particularly limited, but examples thereof include a reinforcing filler and a non-reinforcing filler, and a reinforcing filler is preferable.
  • Examples of the reinforcing filler include carbon black such as furnace black, acetylene black, thermal black, channel black, and graphite; silica such as wet silica, dry silica, and colloidal silica; and the like.
  • Examples of the non-reinforcing filler include quartz powder, silica soil, zinc oxide, basic magnesium carbonate, activated calcium carbonate, magnesium silicate, aluminum silicate, titanium dioxide, talc, aluminum sulfate, calcium sulfate, barium sulfate and the like. be able to.
  • fillers can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected within a range not impairing the effect of the present invention, and 100 parts by weight of the acrylic rubber sheet or the acrylic rubber veil is selected. On the other hand, it is usually in the range of 1 to 200 parts by weight, preferably 10 to 150 parts by weight, and more preferably 20 to 100 parts by weight.
  • the cross-linking agent may be appropriately selected depending on the type and application of the reactive group contained in the acrylic rubber constituting the acrylic rubber sheet or the acrylic rubber bale, but can cross-link the acrylic rubber sheet or the acrylic rubber bale. If this is the case, the present invention is not particularly limited, and for example, a polyvalent amine compound such as a diamine compound and a carbonate thereof; a sulfur compound; a sulfur conjugate; a triazinethiol compound; a polyvalent epoxy compound; an ammonium salt of an organic carboxylate; Conventionally known cross-linking agents such as oxides; polyvalent carboxylic acids; quaternary onium salts; imidazole compounds; isocyanuric acid compounds; organic peroxides; triazine compounds; can be used.
  • polyvalent amine compounds ammonium carboxylates, metal dithiocarbamic acid salts and triazinethiol compounds are preferable, hexamethylenediamine carbamate, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, and benzoate.
  • Ammonium acid, 2,4,6-trimercapto-1,3,5-triazine is particularly preferred.
  • the acrylic rubber sheet or acrylic rubber veil to be used is composed of a carboxyl group-containing acrylic rubber
  • a polyvalent amine compound and a carbonate thereof as a cross-linking agent.
  • the polyvalent amine compound include aliphatic polyvalent amine compounds such as hexamethylenediamine, hexamethylenediamine carbamate, and N, N'-dicinnamylidene-1,6-hexanediamine; 4,4'-methylenedianiline, p.
  • the acrylic rubber sheet or acrylic rubber veil to be used is composed of epoxy group-containing acrylic rubber, aliphatic polyvalent amine compounds such as hexamethylenediamine and hexamethylenediamine carbamate and their carbonates; 4, Aromatic polyvalent amine compounds such as 4'-methylenedianiline; ammonium carboxylic acids such as ammonium benzoate and ammonium adipate; metal dithiocarbamates such as zinc dimethyldithiocarbamate; polyvalent carboxylic acids such as tetradecanedioic acid; A quaternary onium salt such as cetyltrimethylammonium bromide; an imidazole compound such as 2-methylimidazole; an isocyanuric acid compound such as ammonium isocyanurate; and the like can be used, and among these, ammonium carboxylic acid salt and metal dithiocarbamate salt are preferable. , Ammonium benzoate is more preferred.
  • the acrylic rubber sheet or acrylic rubber veil to be used is composed of halogen atom-containing acrylic rubber
  • sulfur it is preferable to use sulfur, a sulfur donor, or a triazine thiol compound as a cross-linking agent.
  • sulfur donor include dipentamethylene thiuram hexasulfide and triethyl thiuram disulfide.
  • triazine compound examples include 6-trimercapto-s-triazine, 2-anilino-4,6-dithiol-s-triazine, 1-dibutylamino-3,5-dimercaptotriazine, 2-dibutylamino-4, 6-Dithiol-s-Triazine, 1-Phenylamino-3,5-Dimercaptotriazine, 2,4,6-Trimercapto-1,3,5-Triazine, 1-Hexylamino-3,5-Dimercaptotriazine Among these, 2,4,6-trimercapto-1,3,5-triazine is preferable.
  • Each of these cross-linking agents can be used alone or in combination of two or more, and the blending amount thereof is usually 0.001 to 20 parts by weight, preferably 0.001 to 20 parts by weight, based on 100 parts by weight of the acrylic rubber sheet or acrylic rubber veil. Is 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.
  • rubber mixture of the present invention other rubber components other than the acrylic rubber sheet or the acrylic rubber veil can be used, if necessary.
  • Other rubber components used as needed are not particularly limited, for example, natural rubber, polybutadiene rubber, polyisoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, silicon rubber, fluororubber, olefin-based. Examples thereof include elastomers, styrene-based elastomers, vinyl chloride-based elastomers, polyester-based elastomers, polyamide-based elastomers, polyurethane-based elastomers, and polysiloxane-based elastomers.
  • the shape of the other rubber components is not particularly limited, and may be, for example, a powder or granular material, a pellet, a crumb, a sheet, or a veil.
  • These other rubber components can be used alone or in combination of two or more.
  • the amount of these other rubber components used is appropriately selected within a range that does not impair the effects of the present invention.
  • the rubber mixture of the present invention can be blended with an anti-aging agent as needed.
  • the anti-aging agent is not particularly limited, but is 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butylphenol, butylhydroxyaniline, 2,6-di-t-butyl-.
  • Kinolin-based anti-aging agents hydroquinone-based anti-aging agents such as 2,5-di- (t-amyl) hydroquinone; and the like. Of these, amine-based anti-aging agents are particularly preferable.
  • the anti-aging agent used here may be the same as or different from the anti-aging agent used in the emulsion polymerization step.
  • anti-aging agents can be used alone or in combination of two or more, and the blending amount thereof is 0.01 to 15 parts by weight with respect to 100 parts by weight of the acrylic rubber sheet or acrylic rubber veil. It is preferably in the range of 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight.
  • the rubber mixture of the present invention contains the acrylic rubber sheet or acrylic rubber veil of the present invention, a filler, a cross-linking agent and, if necessary, other rubber components and an anti-aging agent, and further, if necessary, in the art.
  • Other commonly used additives such as cross-linking aids, cross-linking accelerators, cross-linking retarders, silane coupling agents, plasticizing agents, processing aids, rubbers, pigments, colorants, antioxidants, foaming agents, etc. Can be arbitrarily blended.
  • These other compounding agents can be used alone or in combination of two or more, and the compounding amount thereof is appropriately selected within a range that does not impair the effects of the present invention.
  • ⁇ Manufacturing method of rubber mixture As a method for producing a rubber mixture of the present invention, the filler, a cross-linking agent and other rubber components, an antiaging agent and other compounding agents which can be contained in the acrylic rubber sheet or the acrylic rubber veil of the present invention as needed.
  • any means conventionally used in the field of rubber processing for example, an open roll, a Banbury mixer, various kneaders, and the like can be used. That is, using these mixers, the acrylic rubber sheet or the acrylic rubber veil can be mixed by directly mixing the filler, the cross-linking agent, or the like, preferably by directly kneading.
  • the acrylic rubber sheet or acrylic rubber bale may be used as it is or by dividing (cutting, etc.) the obtained sheet or bale.
  • each component is not particularly limited, but for example, after sufficiently mixing the components that are difficult to react or decompose with heat, the reaction or decomposition occurs with a cross-linking agent that is a component that easily reacts or decomposes with heat.
  • Two-step mixing is preferred, in which the mixture is mixed in a short time at no temperature. Specifically, it is preferable to mix the acrylic rubber sheet or acrylic rubber veil and the filler in the first stage, and then mix the cross-linking agent in the second stage.
  • Other rubber components and anti-aging agents are usually mixed in the first stage, the cross-linking accelerator may be selected in the second stage, and other compounding agents may be appropriately selected.
  • the Mooney viscosity (ML1 + 4,100 ° C.; compound Mooney) of the rubber mixture of the present invention thus obtained is not particularly limited, but is usually in the range of 10 to 150, preferably 20 to 100, and more preferably 25 to 80. Is.
  • the rubber crosslinked product of the present invention is obtained by cross-linking the above rubber mixture.
  • the rubber crosslinked product of the present invention is formed by using the rubber mixture of the present invention with a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, a roll, or the like, and is crosslinked by heating. It can be produced by carrying out a reaction and fixing the shape as a rubber crosslinked product. In this case, cross-linking may be performed after molding in advance, or cross-linking may be performed at the same time as molding.
  • the molding temperature is usually 10 to 200 ° C, preferably 25 to 150 ° C.
  • the crosslinking temperature is usually 100 to 250 ° C., preferably 130 to 220 ° C., more preferably 150 to 200 ° C.
  • the crosslinking time is usually 0.1 minutes to 10 hours, preferably 1 minute to 5 hours.
  • a method used for cross-linking rubber such as press heating, steam heating, oven heating, and hot air heating may be appropriately selected.
  • the rubber crosslinked product of the present invention may be further heated for secondary cross-linking depending on the shape and size of the rubber cross-linked product.
  • the secondary cross-linking varies depending on the heating method, cross-linking temperature, shape and the like, but is preferably carried out for 1 to 48 hours.
  • the heating method and heating temperature may be appropriately selected.
  • the rubber crosslinked product of the present invention is, for example, a sealing material such as an O-ring, packing, diaphragm, oil seal, shaft seal, bearing sheath, mechanical seal, well head seal, seal for electric / electronic equipment, and seal for air compression equipment.
  • a sealing material such as an O-ring, packing, diaphragm, oil seal, shaft seal, bearing sheath, mechanical seal, well head seal, seal for electric / electronic equipment, and seal for air compression equipment.
  • gaskets such as gaskets for fuel cell separators and gaskets for top covers of hard disk drives mounted between a pair of sandwiched housings; cushioning material, vibration isolator; wire coating material; industrial belts; tubes and hoses; sheets It is preferably used as;
  • the rubber cross-linked product of the present invention is also used as an extruded molded product and a molded cross-linked product for automobile applications, for example, fuel oil for fuel tanks such as fuel hoses, filler neck hoses, bent hoses, paper hoses, and oil hoses. It is suitably used for various hoses such as air hoses such as system hoses, turbo air hoses and mission control hoses, radiator hoses, heater hoses, brake hoses and air conditioner hoses.
  • FIG. 1 is a diagram schematically showing an example of an acrylic rubber manufacturing system having an apparatus configuration used for manufacturing an acrylic rubber sheet according to an embodiment of the present invention.
  • the acrylic rubber production system 1 shown in FIG. 1 can be used.
  • the acrylic rubber manufacturing system 1 shown in FIG. 1 is composed of an emulsion polymerization reactor (not shown), a coagulation device 3, a cleaning device 4, a drainer 43, a screw type extruder 5, a cooling device 6, and a bale device 7. ..
  • the emulsion polymerization reactor is configured to perform the treatment related to the emulsion polymerization step described above.
  • this emulsion polymerization reactor includes, for example, a polymerization reaction tank, a temperature control unit for controlling the reaction temperature, a motor, and a stirring device including a stirring blade.
  • water and an emulsifier are mixed with a monomer component for forming acrylic rubber, emulsified while appropriately stirring with a stirrer, and emulsion polymerization is carried out in the presence of a polymerization catalyst to obtain an emulsion polymerization solution. Can be obtained.
  • the addition of the phenol-based anti-aging agent or the phenol-based anti-aging agent-containing emulsion to the emulsion polymerization solution can be carried out as it is in the emulsion polymerization reactor.
  • the emulsion polymerization reactor may be a batch type, a semi-batch type, or a continuous type, and may be any of a tank type reactor and a tube type reactor.
  • the coagulation device 3 shown in FIG. 1 is configured to perform the process related to the coagulation step described above.
  • the coagulation device 3 includes, for example, a stirring tank 30, a heating unit 31 for heating the inside of the stirring tank 30, and a temperature control unit (not shown) for controlling the temperature inside the stirring tank 30. It has a stirring device 34 including a motor 32 and a stirring blade 33, and a drive control unit (not shown) that controls the rotation speed and rotation speed of the stirring blade 33.
  • a hydrous crumb can be produced by bringing the emulsion polymerization solution obtained by the emulsion polymerization reactor into contact with the coagulation solution and coagulating it.
  • the contact between the emulsion polymerization solution and the coagulation solution adopts a method of adding the emulsion polymerization solution to the stirring coagulation solution. That is, a hydrous crumb is generated by filling the stirring tank 30 of the coagulation device 3 with a coagulation liquid and adding and contacting the emulsion polymerization liquid with the coagulation liquid to coagulate the emulsion polymerization liquid.
  • the heating unit 31 of the coagulation device 3 is configured to heat the coagulation liquid filled in the stirring tank 30. Further, the temperature control unit of the coagulation device 3 controls the temperature inside the stirring tank 30 by controlling the heating operation by the heating unit 31 while monitoring the temperature inside the stirring tank 30 measured by the thermometer. It is configured. The temperature of the coagulating liquid in the stirring tank 30 is controlled by the temperature control unit so as to be usually in the range of 40 ° C. or higher, preferably 40 to 90 ° C., and more preferably 50 to 80 ° C.
  • the stirring device 34 of the coagulating device 3 is configured to stir the coagulating liquid filled in the stirring tank 30.
  • the stirring device 34 includes a motor 32 that generates rotational power and a stirring blade 33 that extends in a direction perpendicular to the rotation axis of the motor 32.
  • the stirring blade 33 can flow the coagulating liquid by rotating around the rotation axis by the rotational power of the motor 32 in the coagulating liquid filled in the stirring tank 30.
  • the shape and size of the stirring blade 33, the number of installations, and the like are not particularly limited.
  • the drive control unit of the coagulation device 3 is configured to control the rotational drive of the motor 32 of the stirring device 34 to set the rotation speed and the rotation speed of the stirring blade 33 of the stirring device 34 to predetermined values.
  • the rotation of the stirring blade 33 by the drive control unit so that the stirring number of the coagulating liquid is, for example, usually 100 rpm or more, preferably 200 to 1,000 rpm, more preferably 300 to 900 rpm, and particularly preferably 400 to 800 rpm. Is controlled.
  • the peripheral speed of the coagulant is usually 0.5 m / s or more, preferably 1 m / s or more, more preferably 1.5 m / s or more, particularly preferably 2 m / s or more, and most preferably 2.5 m / s or more.
  • the rotation of the stirring blade 33 is controlled by the drive control unit. Further, the drive control unit agitates the coagulant so that the upper limit of the peripheral speed is usually 50 m / s or less, preferably 30 m / s or less, more preferably 25 m / s or less, and most preferably 20 m / s or less.
  • the rotation of the wing 33 is controlled.
  • the cleaning device 4 shown in FIG. 1 is configured to perform the processing related to the cleaning process described above.
  • the cleaning device 4 includes, for example, a cleaning tank 40, a heating unit 41 that heats the inside of the cleaning tank 40, and a temperature control unit (not shown) that controls the temperature inside the cleaning tank 40.
  • a temperature control unit not shown
  • the amount of ash in the finally obtained acrylic rubber sheet can be effectively reduced by mixing the water-containing crumbs generated by the solidifying device 3 with a large amount of water and cleaning.
  • the heating unit 41 of the cleaning device 4 is configured to heat the inside of the cleaning tank 40. Further, the temperature control unit of the cleaning device 4 controls the temperature inside the cleaning tank 40 by controlling the heating operation by the heating unit 41 while monitoring the temperature inside the cleaning tank 40 measured by the thermometer. It is configured. As described above, the temperature of the washing water in the washing tank 40 is usually controlled to be in the range of 40 ° C. or higher, preferably 40 to 100 ° C., more preferably 50 to 90 ° C., and most preferably 60 to 80 ° C. To.
  • the water-containing crumb washed by the washing device 4 is supplied to the screw type extruder 5 that performs the dehydration step and the drying step. At this time, it is preferable that the water-containing crumb after cleaning is supplied to the screw type extruder 5 through a drainer 43 capable of separating free water.
  • a drainer 43 capable of separating free water.
  • a wire mesh, a screen, an electric sieve, or the like can be used.
  • the temperature of the water-containing crumb is preferably 40 ° C. or higher, more preferably 60 ° C. or higher.
  • the temperature of the water-containing crumb when supplied to the screw type extruder 5 is maintained at 60 ° C. or higher.
  • the temperature of the hydrous crumb may be 40 ° C. or higher, preferably 60 ° C. or higher when it is conveyed from the cleaning device 4 to the screw type extruder 5.
  • the screw type extruder 5 shown in FIG. 1 is configured to perform the processes related to the above-mentioned dehydration step and drying step.
  • a centrifuge, a squeezer, or the like may be used as the dehydrator for performing the treatment related to the dehydration step, and the treatment related to the drying step may be performed.
  • a hot air dryer, a vacuum dryer, an expander dryer, a kneader type dryer, or the like may be used as the dryer.
  • the screw type extruder 5 is configured to mold the dried rubber obtained through the dehydration step and the drying step into a predetermined shape and discharge it.
  • the screw type extruder 5 has a dehydration barrel portion 53 having a function as a dehydrator for dehydrating the hydrous crumb washed by the cleaning device 4, and a dryer having a function as a dryer for drying the hydrous crumb.
  • a barrel portion 54 is provided, and a die 59 having a molding function for forming a water-containing crumb is provided on the downstream side of the screw type extruder 5.
  • FIG. 2 shows a configuration of a specific example suitable for the screw type extruder 5 shown in FIG.
  • the above-mentioned dehydration / drying step can be suitably performed.
  • the screw type extruder 5 shown in FIG. 2 is a twin-screw type extruder / dryer provided with a pair of screws (not shown) in the barrel unit 51.
  • the screw type extruder 5 has a drive unit 50 that rotationally drives a pair of screws in the barrel unit 51.
  • the drive unit 50 is attached to the upstream end (left end in FIG. 2) of the barrel unit 51.
  • the screw type extruder 5 has a die 59 at the downstream end (right end in FIG. 2) of the barrel unit 51.
  • the barrel unit 51 has a supply barrel portion 52, a dehydration barrel portion 53, and a dry barrel portion 54 from the upstream side to the downstream side (from the left side to the right side in FIG. 2).
  • the supply barrel portion 52 is composed of two supply barrels, that is, a first supply barrel 52a and a second supply barrel 52b.
  • the dehydration barrel portion 53 is composed of three dehydration barrels, that is, a first dehydration barrel 53a, a second dehydration barrel 53b, and a third dehydration barrel 53c.
  • the drying barrel portion 54 includes eight drying barrels, that is, a first drying barrel 54a, a second drying barrel 54b, a third drying barrel 54c, a fourth drying barrel 54d, and a fifth drying barrel 54e. , A sixth dry barrel 54f, a seventh dry barrel 54g, and an eighth dry barrel 54h.
  • the barrel unit 51 is configured by connecting 13 divided barrels 52a to 52b, 53a to 53c, 54a to 54h from the upstream side to the downstream side.
  • the screw type extruder 5 individually heats the barrels 52a to 52b, 53a to 53c, 54a to 54h, and determines the water content crumbs in the barrels 52a to 52b, 53a to 53c, 54a to 54h, respectively. It has a heating means (not shown) for heating to a temperature.
  • the heating means includes a number corresponding to each barrel 52a to 52b, 53a to 53c, 54a to 54h.
  • a heating means for example, a configuration is adopted in which high-temperature steam is supplied from the steam supply means to the steam distribution jackets formed in the barrels 52a to 52b, 53a to 53c, 54a to 54h. It is not limited to this.
  • the screw type extruder 5 has a temperature control means (not shown) that controls a set temperature of each heating means corresponding to each barrel 52a to 52b, 53a to 53c, 54a to 54h.
  • the number of supply barrels, dehydration barrels, and drying barrels that constitute each barrel portion 52, 53, 54 in the barrel unit 51 is not limited to the mode shown in FIG. 2, and the acrylic rubber to be dried is used.
  • the number can be set according to the water content of the water-containing crumb.
  • the number of supply barrels installed in the supply barrel portion 52 is, for example, 1 to 3.
  • the number of dehydration barrels installed in the dehydration barrel portion 53 is preferably, for example, 2 to 10, and more preferably 3 to 6, because dehydration of the water-containing crumb of the adhesive acrylic rubber can be efficiently performed.
  • the number of dry barrels installed in the dry barrel portion 54 is preferably, for example, 2 to 10, and more preferably 3 to 8.
  • the pair of screws in the barrel unit 51 are rotationally driven by a driving means such as a motor housed in the driving unit 50.
  • the pair of screws extend from the upstream side to the downstream side in the barrel unit 51, and by being rotationally driven, the water-containing crumbs supplied to the supply barrel portion 52 can be conveyed to the downstream side while being mixed. It has become like.
  • the pair of screws is preferably a biaxial meshing type in which the peaks and valleys are meshed with each other, whereby the dehydration efficiency and the drying efficiency of the hydrous crumb can be improved.
  • the rotation direction of the pair of screws may be the same direction or different directions, but from the viewpoint of self-cleaning performance, a type that rotates in the same direction is preferable.
  • the screw shape of the pair of screws is not particularly limited as long as it is a shape required for each barrel portion 52, 53, 54, and is not particularly limited.
  • the supply barrel portion 52 is an area for supplying the hydrous crumb into the barrel unit 51.
  • the first supply barrel 52a of the supply barrel portion 52 has a feed port 55 for supplying a water-containing crumb in the barrel unit 51.
  • the dehydration barrel portion 53 is a region for separating and discharging a liquid (serum water) containing a coagulant or the like from the hydrous crumb.
  • the first to third dehydration barrels 53a to 53c constituting the dehydration barrel portion 53 have dehydration slits 56a, 56b, and 56c for discharging the water content of the hydrous crumb to the outside, respectively.
  • a plurality of the dehydration slits 56a, 56b, 56c are formed in the dehydration barrels 53a to 53c, respectively.
  • the slit widths that is, the openings of the dehydration slits 56a, 56b, and 56c may be appropriately selected according to the usage conditions, and are usually 0.01 to 5 mm, so that the water-containing crumbs are less damaged and the water-containing crumbs have little loss. From the viewpoint of efficient dehydration, it is preferably 0.1 to 1 mm, and more preferably 0.2 to 0.6 mm.
  • the dehydration barrel portion 53 is suitable because it is possible to efficiently reduce the water content of the adhesive acrylic rubber by combining drainage and exhaust steam.
  • which of the first to third dehydration barrels 53a to 53c is used for drainage or exhaust steam may be appropriately set according to the purpose of use, but is usually manufactured.
  • the dehydration barrel portion 53 has four dehydration barrels
  • drainage may be performed by three dehydration barrels on the upstream side, and steam may be exhausted by one dehydration barrel on the downstream side.
  • steam may be exhausted by one dehydration barrel on the downstream side.
  • the set temperature of the dehydration barrel portion 53 is usually in the range of 60 to 150 ° C., preferably 70 to 140 ° C., more preferably 80 to 130 ° C., and is dehydrated in the drained state.
  • the set temperature of the dehydration barrel to be dehydrated is usually 60 ° C. to 120 ° C., preferably 70 to 110 ° C., more preferably 80 to 100 ° C.
  • the set temperature of the dehydration barrel to be dehydrated in the exhausted steam state is usually 100 to 150 ° C.
  • the temperature is preferably in the range of 105 to 140 ° C, more preferably 110 to 130 ° C.
  • the drying barrel portion 54 is a region where the hydrous crumb after dehydration is dried under reduced pressure.
  • the second dry barrel 54b, the fourth dry barrel 54d, the sixth dry barrel 54f, and the eighth dry barrel 54h are It has vent ports 58a, 58b, 58c, and 58d for degassing, respectively. Vent pipes (not shown) are connected to the vent ports 58a, 58b, 58c, and 58d, respectively.
  • Vacuum pumps (not shown) are connected to the ends of each vent pipe, and the operation of these vacuum pumps reduces the pressure inside the drying barrel portion 54 to a predetermined pressure.
  • the screw type extruder 5 has a pressure control means (not shown) that controls the operation of these vacuum pumps to control the degree of decompression in the drying barrel portion 54.
  • the degree of decompression in the dry barrel portion 54 may be appropriately selected, but as described above, it is usually set to 1 to 50 kPa, preferably 2 to 30 kPa, and more preferably 3 to 20 kPa.
  • the set temperature in the drying barrel portion 54 may be appropriately selected, but as described above, it is usually set to 100 to 250 ° C, preferably 110 to 200 ° C, and more preferably 120 to 180 ° C.
  • the set temperatures in all the dry barrels 54a to 54h may be approximated or different, but on the upstream side (dehydrated barrel portion). It is preferable to set the temperature on the downstream side (die 59 side) to a higher temperature than the temperature on the downstream side (53 side) because the drying efficiency is improved.
  • the die 59 is a mold arranged at the downstream end of the barrel unit 51 and has a discharge port having a predetermined nozzle shape.
  • the acrylic rubber dried in the drying barrel portion 54 is extruded into a shape corresponding to a predetermined nozzle shape by passing through the discharge port of the die 59.
  • the shape of the acrylic rubber passing through the die 59 can be extruded into a sheet shape by making the nozzle shape of the die 59 substantially rectangular.
  • a breaker plate or wire mesh may or may not be provided between the screw and the die 59.
  • the water-containing crumb of the raw material acrylic rubber is extruded into a sheet-shaped dry rubber as follows.
  • the water-containing crumb of acrylic rubber obtained through the cleaning step is supplied from the feed port 55 to the supply barrel portion 52.
  • the water-containing crumb supplied to the supply barrel portion 52 is sent from the supply barrel portion 52 to the dehydration barrel portion 53 by the rotation of the pair of screws in the barrel unit 51.
  • the dehydration barrel portion 53 as described above, the moisture contained in the water-containing crumb is drained and exhausted from the dehydration slits 56a, 56b, 56c provided in the first to third dehydration barrels 53a to 53c, respectively. ,
  • the hydrous crumb is dehydrated.
  • the water-containing crumb dehydrated by the dehydration barrel portion 53 is sent to the dry barrel portion 54 by the rotation of a pair of screws in the barrel unit 51.
  • the hydrous crumb sent to the dry barrel portion 54 is plasticized and mixed to form a melt, which generates heat and is carried to the downstream side while raising the temperature. Then, the water contained in the melt of the acrylic rubber is vaporized, and the water (steam) is discharged to the outside through vent pipes (not shown) connected to the vent ports 58a, 58b, 58c, and 58d, respectively.
  • the hydrous crumb is dried and becomes a melt of acrylic rubber, and the acrylic rubber is supplied to the die 59 by the rotation of a pair of screws in the barrel unit 51 to form a sheet. It is extruded from the die 59 as a dry rubber.
  • the rotation speed (N) of the pair of screws in the barrel unit 51 may be appropriately selected according to various conditions, and is usually 10 to 1,000 rpm, and the water content and gel amount of the acrylic rubber sheet can be efficiently adjusted. From the viewpoint of reduction, it is preferably 50 to 750 rpm, more preferably 100 to 500 rpm, and most preferably 120 to 300 rpm.
  • the extrusion amount (Q) of acrylic rubber is not particularly limited, but is usually 100 to 1,500 kg / hr, preferably 300 to 1,200 kg / hr, and more preferably 400 to 1,000 kg / hr. There is, and 500 to 800 kg / hr is the most preferable.
  • the ratio (Q / N) of the extrusion amount (Q) of the acrylic rubber to the rotation speed (N) of the screw is not particularly limited, but is usually 1 to 20, preferably 2 to 10, and more preferably. It is 3 to 8, and 4 to 6 is particularly preferable.
  • the cooling device 6 shown in FIG. 1 is configured to cool the dried rubber obtained through the dehydration step by the dehydrator and the drying step by the dryer.
  • the cooling method by the cooling device 6 various methods including an air cooling method by blowing air or cooling, a water spraying method of spraying water, a dipping method of immersing in water, and the like can be adopted. Further, the dried rubber may be cooled by leaving it at room temperature.
  • the transport type cooling device 60 for cooling the sheet-shaped dry rubber 10 formed into a sheet shape will be described with reference to FIG.
  • FIG. 3 shows the configuration of a transport type cooling device 60 suitable as the cooling device 6 shown in FIG.
  • the transport type cooling device 60 shown in FIG. 3 is configured to cool the sheet-shaped dry rubber 10 discharged from the discharge port of the die 59 of the screw type extruder 5 by an air cooling method while transporting the sheet-shaped dry rubber 10.
  • this transport type cooling device 60 the sheet-shaped dry rubber discharged from the screw type extruder 5 can be suitably cooled.
  • the transport type cooling device 60 shown in FIG. 3 is used, for example, directly connected to the die 59 of the screw type extruder 5 shown in FIG. 2 or installed in the vicinity of the die 59.
  • the transport type cooling device 60 sends cold air to the conveyor 61 that conveys the sheet-shaped dry rubber 10 discharged from the die 59 of the screw type extruder 5 in the direction of arrow A in FIG. 3 and the sheet-shaped dry rubber 10 on the conveyor 61. It has a cooling means 65 for spraying.
  • the conveyor 61 has rollers 62 and 63, and a conveyor belt 64 that is wound around the rollers 62 and 63 and on which the sheet-shaped dry rubber 10 is placed.
  • the conveyor 61 is configured to continuously convey the sheet-shaped dry rubber 10 discharged from the die 59 of the screw type extruder 5 to the downstream side (right side in FIG. 3) on the conveyor belt 64.
  • the cooling means 65 is not particularly limited, but has, for example, a structure capable of blowing the cooling air sent from the cooling air generating means (not shown) onto the surface of the sheet-shaped dry rubber 10 on the conveyor belt 64. And so on.
  • the length L1 of the conveyor 61 and the cooling means 65 of the transport type cooling device 60 (the length of the portion where the cooling air can be blown) is not particularly limited, but is, for example, 10 to 100 m, preferably 20 to 50 m. ..
  • the transport speed of the sheet-shaped dry rubber 10 in the transport-type cooling device 60 is the length L1 of the conveyor 61 and the cooling means 65, the discharge speed of the sheet-shaped dry rubber 10 discharged from the die 59 of the screw type extruder 5. It may be appropriately adjusted according to the target cooling rate, cooling time, etc., but is, for example, 10 to 100 m / hr, more preferably 15 to 70 m / hr.
  • the sheet-shaped dry rubber 10 discharged from the die 59 of the screw type extruder 5 is conveyed by the conveyor 61, and the sheet-shaped dry rubber 10 is transported from the cooling means 65.
  • the sheet-shaped dry rubber 10 is cooled by blowing cooling air.
  • the transport type cooling device 60 is not particularly limited to a configuration including one conveyor 61 and one cooling means 65 as shown in FIG. 3, and two or more conveyors 61 and two or more corresponding conveyors 61. It may be configured to include the cooling means 65 of the above. In that case, the total length of each of the two or more conveyors 61 and the cooling means 65 may be within the above range.
  • the bale device 7 shown in FIG. 1 is configured to extrude from a screw type extruder 5 and further process a dry rubber cooled by the cooling device 6 to produce a bale which is a block.
  • the weight and shape of the acrylic rubber bale produced by the bale-forming device 7 are not particularly limited, but for example, an acrylic rubber bale having a substantially rectangular parallelepiped shape of about 20 kg is produced.
  • the sheet-shaped dry rubber 10 manufactured by the screw type extruder 5 may be laminated to manufacture an acrylic rubber veil.
  • the bale-forming device 7 arranged on the downstream side of the transport-type cooling device 60 shown in FIG. 3 may be provided with a cutting mechanism for cutting the sheet-shaped dry rubber 10.
  • the cutting mechanism of the bale device 7 continuously cuts the cooled sheet-shaped dry rubber 10 at predetermined intervals and processes it into a cut sheet-shaped dry rubber 16 having a predetermined size. It is configured as follows. By laminating a plurality of cut sheet-shaped dry rubbers 16 cut to a predetermined size by a cutting mechanism, an acrylic rubber veil in which the cut-sheet-shaped dry rubbers 16 are laminated can be manufactured.
  • the cut sheet-shaped dry rubber 16 When producing an acrylic rubber veil on which the cut sheet-shaped dry rubber 16 is laminated, it is preferable to laminate the cut sheet-shaped dry rubber 16 at 40 ° C. or higher, for example. By laminating the cut sheet-shaped dry rubber 16 at 40 ° C. or higher, good air release is realized by further cooling and compression by its own weight.
  • the content ratio of each monomer unit in acrylic rubber was calculated from the amount used in the polymerization reaction of each monomer and the polymerization conversion rate. Specifically, since the polymerization reaction was an emulsion polymerization reaction and the polymerization conversion rate was approximately 100% in which none of the unreacted monomers could be confirmed, the content ratio of each monomer unit was set to a single amount. It was the same as the amount used by the body.
  • the content of the reactive group of the acrylic rubber was measured by the following method in the acrylic rubber sheet or the acrylic rubber veil.
  • the amount of carboxyl groups was calculated by dissolving an acrylic rubber sheet or an acrylic rubber veil in acetone and performing potentiometric titration with a potassium hydroxide solution.
  • the amount of epoxy group was calculated by dissolving an acrylic rubber sheet or acrylic rubber veil in methyl ethyl ketone, adding a specified amount of hydrochloric acid to react with the epoxy group, and titrating the remaining amount of hydrochloric acid with potassium hydroxide. ..
  • the amount of chlorine was calculated by completely burning an acrylic rubber sheet or an acrylic rubber veil in a combustion flask, absorbing the generated chlorine in water, and titrating with silver nitrate.
  • the content (%) of the antioxidant in the acrylic rubber sheet or acrylic rubber bale is determined by dissolving the acrylic rubber sheet or acrylic rubber veil in tetrahydrofuran and performing gel permeation chromatography (GPC) measurement. Calculated based on the calibration curve.
  • the amount of each component (ppm) in the acrylic rubber sheet or acrylic rubber bale ash content is measured by XRF using ZSX Primus (manufactured by Rigaku) by pressing the ash content collected during the above ash content measurement onto a ⁇ 20 mm titration filter paper. did.
  • the gel amount (%) of the acrylic rubber sheet or the acrylic rubber veil was the amount of the insoluble matter in methyl ethyl ketone, and was determined by the following method.
  • Glass transition temperature (Tg) The glass transition temperature (Tg) of acrylic rubber was measured using a differential scanning calorimeter (DSC, product name "X-DSC7000", manufactured by Hitachi High-Tech Science Co., Ltd.).
  • the pH of the acrylic rubber sheet or acrylic rubber bale is determined by dissolving 6 g ( ⁇ 0.05 g) of the acrylic rubber sheet or acrylic rubber bale in 100 g of tetrahydrofuran, adding 2.0 ml of distilled water, and confirming that the mixture is completely dissolved. Measured with an electrode.
  • the water content (%) of the acrylic rubber sheet or the acrylic rubber veil was measured according to the JIS K6238-1: Oven A (volatile matter measurement) method.
  • the weight average molecular weight (Mw) and molecular weight distribution (Mz / Mw) of acrylic rubber are determined by adding lithium chloride at a concentration of 0.05 mol / L and 37% concentrated hydrochloric acid at a concentration of 0.01% to dimethylformamide as a solvent. It is an absolute molecular weight and an absolute molecular weight distribution measured by the GPC-MALS method using.
  • a multi-angle laser light scattering photometric meter (MALS) and a differential refractometer (RI) are incorporated into a GPC (Gel Permeation Chromatography) device, and the light scattering intensity and refraction of the molecular chain solution size-sorted by the GPC device are incorporated.
  • the molecular weight of the solute and its content were sequentially calculated and obtained by measuring the rate difference with the elution time.
  • the measurement conditions and measurement method by the GPC device are as follows.
  • the complex viscosity ⁇ of the acrylic rubber sheet or acrylic rubber bale is temperature-dispersed at a strain of 473% and 1 Hz (40 to 40) using a dynamic viscoelasticity measuring device “Rubber Process Analyzer RPA-2000” (manufactured by Alpha Technology). 120 ° C.) was measured, and the complex viscoelasticity ⁇ at each temperature was determined.
  • the dynamic viscoelasticity at 60 ° C. is defined as the complex viscoelasticity ⁇ (60 ° C.)
  • the dynamic viscoelasticity at 100 ° C. is defined as the complex viscoelasticity ⁇ (100 ° C.).
  • the values of ° C.) / ⁇ (60 ° C.) and ⁇ (60 ° C.) / ⁇ (100 ° C.) were calculated.
  • the normal physical properties of the rubber sample were evaluated according to the following criteria by measuring the breaking strength, 100% tensile stress and breaking elongation of the crosslinked rubber sample of the rubber sample according to JIS K6251. (1) The breaking strength was evaluated as ⁇ for 10 MPa or more and ⁇ for less than 10 MPa. (2) For 100% tensile stress, 5 MPa or more was evaluated as ⁇ , and less than 5 MPa was evaluated as x. (3) The elongation at break was evaluated as ⁇ for 150% or more and x for less than 150%.
  • the anti-aging agent-containing emulsion to be added to the emulsion after emulsion polymerization is prepared by charging a predetermined temperature and a predetermined amount of water into an adjustment tank having a stirring blade and adding a predetermined amount of emulsifier while stirring, based on the conditions shown in Table 1.
  • To prepare an emulsifier solution then add 1 part of an antioxidant to the emulsion, stir for 2 hours, measure the pH, and if the pH is not in the range of 3 to 6, use sulfuric acid or sodium hydroxide within the range. It was adjusted so that it would fit in.
  • the entire amount of the prepared anti-aging agent-containing emulsion was added to the emulsion polymerization solution after emulsion polymerization.
  • Example 1 In a mixing container equipped with a homomixer, 46 parts of pure water, 74.5 parts of ethyl acrylate, 17 parts of n-butyl acrylate, 7 parts of methoxyethyl acrylate, and 1.5 parts of mono-n-butyl fumarate, and 1.8 parts of octyloxydioxyethylene phosphate sodium salt was charged as an emulsifier and stirred to obtain a monomeric emulsion.
  • the anti-aging agent is contained in a 2% magnesium sulfate aqueous solution (coagulant) heated to 80 ° C. and vigorously stirred (600 rpm: peripheral speed 3.1 m / s).
  • coagulant 2% magnesium sulfate aqueous solution
  • the added emulsion polymerization solution was heated to 80 ° C. and continuously added to solidify the polymer and filtered off to obtain a hydrous crumb.
  • the screw type extruder used in the first embodiment has one supply barrel, three dehydration barrels (first to third dehydration barrels), and five drying barrels (first to fifth drying barrels). It is configured.
  • the first and second dehydration barrels are designed to drain water, and the third dehydration barrel is designed to drain steam.
  • the operating conditions of the screw type extruder are as follows.
  • Moisture content Moisture content of the hydrous crumb after drainage in the second dehydration barrel: 20% Moisture content of the hydrous crumb after steam exhaust in the third dehydration barrel: 10% Moisture content of the hydrous crumb after drying in the 5th drying barrel: 0.4% Rubber temperature: -The temperature of the hydrous crumb supplied to the first supply barrel: 65 ° C.
  • the extruded sheet-shaped dry rubber was cooled to 50 ° C. and then cut with a cutter to obtain an acrylic rubber sheet (A).
  • the obtained acrylic rubber sheet (A) was laminated so as to have 20 parts (20 kg) before the temperature became 40 ° C. or lower to obtain an acrylic rubber veil (A).
  • Acrylic rubber veil (A) was obtained by laminating 20 parts (20 kg) before the temperature fell below 40 ° C. Reactive group content, ash content, ash component content, specific gravity, gel amount, glass transition temperature (Tg), pH, antiaging agent content, water content, molecular weight, molecular weight distribution of the obtained acrylic rubber veil (A) And the complex viscosity was measured.
  • Example 2 The monomer component was 4.5 parts of ethyl acrylate, 64.5 parts of n-butyl acrylate, 29.5 parts of methoxyethyl acrylate and 1.5 parts of mono-n-butyl fumarate, and the emulsifier was nonylphenyloxy.
  • Acrylic rubber sheet (B) and acrylic rubber bale (B) were obtained in the same manner as in Example 1 except that the hexaoxyethylene phosphate sodium salt and the anti-aging agent-containing emulsion were changed to anti-aging emulsion 2. The characteristics were evaluated. The results of the acrylic rubber sheet (B) are shown in Tables 3-1 and 3-2.
  • Example 3 The monomer component is 48.25 parts of ethyl acrylate, 50 parts of n-butyl acrylate and 1.75 parts of mono n-butyl fumarate, and the emulsifier is tridecyloxyhexaoxyethylene phosphate sodium salt.
  • the same procedure as in Example 1 was carried out except that the anti-aging agent-containing emulsion was changed to anti-aging emulsion 3, and the acrylic rubber sheet (C) and acrylic rubber bale (C) were obtained and each characteristic (the compounding agent was changed to "formulation 2"). And) was evaluated.
  • the results of the acrylic rubber sheet (C) are shown in Tables 3-1 and 3-2.
  • Example 4 The temperature of the first dehydration barrel of the screw type extruder is changed to 100 ° C. and the temperature of the second dehydration barrel is changed to 120 ° C. so that drainage is performed only by the first dehydration barrel, and the first dehydration barrel is used.
  • Acrylic rubber sheet (D) and acrylic rubber bale (D) were obtained in the same manner as in Example 3 except that the water content of the water-containing crumb after drainage was changed to 30%, and each characteristic was evaluated. The results of the acrylic rubber sheet (D) are shown in Tables 3-1 and 3-2.
  • Example 5 Acrylic rubber was carried out in the same manner as in Example 4 except that the monomer component was changed to 28 parts of ethyl acrylate, 38 parts of n-butyl acrylate, 27 parts of methoxyethyl acrylate, 5 parts of acrylonitrile and 2 parts of allylglycidyl ether. A sheet (E) and an acrylic rubber bale (E) were obtained and each characteristic (the compounding agent was changed to "formulation 3") was evaluated. The results of the acrylic rubber sheet (E) are shown in Tables 3-1 and 3-2.
  • Example 6 Example 4 except that the monomer component is changed to 42.2 parts of ethyl acrylate, 35 parts of n-butyl acrylate, 20 parts of methoxyethyl acrylate, 1.5 parts of acrylonitrile and 1.3 parts of vinyl chloroacetate.
  • the same procedure as above was carried out to obtain an acrylic rubber sheet (F) and an acrylic rubber bale (F), and each characteristic (the compounding agent was changed to "formulation 4") was evaluated.
  • the results of the acrylic rubber sheet (F) are shown in Tables 3-1 and 3-2.
  • Example 7 Acrylic rubber sheet (G) and acrylic rubber veil (G) were obtained in the same manner as in Example 6 except that the emulsion containing the anti-aging agent was changed to anti-aging emulsion 4, and each characteristic was evaluated.
  • the results of the acrylic rubber sheet (G) are shown in Tables 3-1 and 3-2.
  • Example 8 Acrylic rubber sheet (H) and acrylic rubber veil (H) were obtained in the same manner as in Example 6 except that the emulsion containing the anti-aging agent was changed to anti-aging emulsion 5, and each characteristic was evaluated. The results of the acrylic rubber sheet (H) are shown in Tables 3-1 and 3-2.
  • a 0.7% sodium sulfate aqueous solution (coagulation solution) was continuously added to coagulate the polymer and filter it off to obtain a hydrous crumb.
  • coagulation solution 0.7% sodium sulfate aqueous solution
  • 194 parts of industrial water was added, and after stirring at 25 ° C. for 5 minutes, the hydrous crumb for discharging water from the coagulation tank was washed four times, and then a sulfuric acid aqueous solution having a pH of 3 194.
  • a crumb-shaped acrylic rubber (I) having a water content of 0.4% by weight was obtained by drying with a hot air dryer. Each property of the obtained crumb-shaped acrylic rubber (I) was evaluated and shown in Tables 3-1 and 3-2.
  • the weight average molecular weight (Mw) containing the (meth) acrylic acid ester of the present invention as a main component is 100,000 to 5,000,000, and the z average molecular weight (Mz) and weight.
  • Acrylic rubber sheets (A) to (H) consisting of acrylic rubber having a ratio (Mz / Mw) to the average molecular weight (Mw) of 1.3 or more, containing a phenolic antioxidant, and having a gel weight of 50% by weight or less. ), It can be seen that the storage stability and workability are remarkably improved without impairing the strength characteristics (Examples 1 to 8).
  • the acrylic rubber sheets (A) to (H) and the crumb-shaped acrylic rubbers (I) to (J) produced under the conditions of the Examples and Comparative Examples of the present application have absolute molecular weights measured by GPC-MALS.
  • the acrylic rubber sheets (A) to (H) are crumb-shaped acrylic rubber.
  • the specific surface area is overwhelmingly smaller, the specific gravity is larger, the structure is air-free and less likely to be oxidized, and the phenolic anti-aging agent is uniformly fine in the acrylic rubber sheets (A) to (H). It is considered that the effect of storage stability is different due to the dispersion (comparison between Examples 1 to 8 and Comparative Example 1). Further, after the storage stability test, no change in color of the acrylic rubber sheet of the present invention was observed, but the crumb-shaped acrylic sheets (I) to (J) of Comparative Examples were yellowed.
  • the acrylic rubber sheets (A) to (H) of the present invention use a phenolic antiaging agent added to the emulsion polymer solution as a phenolic antiaging agent with water and an emulsifier. It is made into an agent-containing emulsion, and the emulsifier concentration of the phenol-based anti-aging agent-containing emulsion is set to a predetermined value or higher, and the water temperature at the time of preparing the emulsion is set to a predetermined level or higher or the melting point of the phenol-based anti-aging agent or higher. It can be seen that the stability can be improved (comparison between Examples 1 to 7 and Example 8).
  • the polymerization conversion rate of emulsion polymerization is increased in order to improve the strength characteristics of the sheet, but as the polymerization conversion rate is increased, the gel amount of the methyl ethyl ketone insoluble content rapidly increases and acrylic rubber.
  • the gel of methyl ethyl ketone insoluble content that rapidly increased by drying and kneading in a screw type extruder to a state where there is no water (water content less than 1%) disappears. There is.
  • it is difficult to make acrylic rubber having a large specific heat and a reactive group substantially free of water and as shown in the examples, the water content crumb temperature to be charged and the conditions of the screw type extruder are applied. Can be achieved by.
  • a phenolic antiaging agent having a specific melting point is further contained, and the specific gravity, gel amount, glass transition temperature (Tg), pH, antiaging agent content, water content, and weight average molecular weight ( Mw), ratio of z average molecular weight (Mz) to weight average molecular weight (Mw) (Mz / Mw), complex viscosity ⁇ (100 ° C) at 100 ° C, complex viscosity ⁇ (60 ° C) at 60 ° C, 100 Acrylic rubber sheets (A) to (H) having a ratio of complex viscosity ratios ( ⁇ 100 ° C./ ⁇ 60 ° C.) at ° C. to 60 ° C. in a specific range do not impair the normal physical properties including strength characteristics, and have storage stability and workability. Is highly excellent (Examples 1 to 8).
  • the characteristic values of the acrylic rubber veils (A) to (H) of the present invention in which the acrylic rubber sheets (A) to (H) are laminated are the same as the characteristic values of the respective acrylic rubber sheets to be laminated. there were.

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EP20843788.9A EP4001323A4 (en) 2019-07-19 2020-06-05 ACRYLIC RUBBER LAYER WITH GOOD PRESERVATION STABILITY AND PROCESSABILITY
CN202080048274.1A CN114072460A (zh) 2019-07-19 2020-06-05 保存稳定性和加工性优异的丙烯酸橡胶片
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WO2021261214A1 (ja) * 2020-06-23 2021-12-30 日本ゼオン株式会社 バンバリー加工性に優れるアクリルゴムベール

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