WO2021014797A1 - Acrylic-rubber bale with excellent storage stability and processability - Google Patents

Acrylic-rubber bale with excellent storage stability and processability Download PDF

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Publication number
WO2021014797A1
WO2021014797A1 PCT/JP2020/022320 JP2020022320W WO2021014797A1 WO 2021014797 A1 WO2021014797 A1 WO 2021014797A1 JP 2020022320 W JP2020022320 W JP 2020022320W WO 2021014797 A1 WO2021014797 A1 WO 2021014797A1
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Prior art keywords
acrylic rubber
weight
rubber
acrylic
water
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PCT/JP2020/022320
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French (fr)
Japanese (ja)
Inventor
増田　浩文
川中　孝文
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日本ゼオン株式会社
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Priority claimed from JP2020015104A external-priority patent/JP7233388B2/en
Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to US17/626,633 priority Critical patent/US20220315683A1/en
Priority to EP20844898.5A priority patent/EP4001316A4/en
Priority to CN202080049000.4A priority patent/CN114072431A/en
Priority to KR1020227000567A priority patent/KR20220038334A/en
Priority to EP20844247.5A priority patent/EP4001315A4/en
Priority to PCT/JP2020/027947 priority patent/WO2021015143A1/en
Priority to KR1020217042526A priority patent/KR20220038295A/en
Priority to CN202080047949.0A priority patent/CN114051505B/en
Priority to US17/626,067 priority patent/US20220259345A1/en
Publication of WO2021014797A1 publication Critical patent/WO2021014797A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/22—Coagulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters

Definitions

  • the present invention relates to an acrylic rubber bale, a method for producing the same, a rubber mixture and a rubber crosslinked product. More specifically, the present invention relates to an acrylic rubber bale having excellent storage stability and processability, a method for producing the same, and a rubber obtained by mixing the acrylic rubber bale. The present invention relates to a mixture and a rubber crosslinked product obtained by cross-linking the mixture.
  • 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, and is widely used in automobile-related fields and the like.
  • Such acrylic rubber is usually emulsion-polymerized with the monomer components constituting the acrylic rubber, brought into contact with the obtained emulsion polymerization solution and a coagulant, and the obtained hydrous crumb is dried and then veiled and commercialized. To.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2006-3282359 describes a step of obtaining a crumb slurry containing a crumb-like rubber polymer by contacting a polymer latex with a coagulating liquid, and a stirring power of 1 kW / m3 or more.
  • a method for producing a rubber polymer comprising a step and a step of heating and drying the moisture-removed crumb-like rubber polymer is disclosed, and the dried crumb is introduced into a baler in the form of flakes, compressed and veiled. It is stated that it will be polymerized. Further, it is described that it is preferable to adjust the maximum width of the crumb to about 3 to 20 mm for crushing with a mixer having a stirring / crushing function.
  • an unsaturated nitrile-conjugated diene copolymer latex obtained by emulsification polymerization is specifically shown, and ethyl acrylate / n-butyl acrylate copolymer and ethyl acrylate / It has been shown that it can be applied to copolymers composed only of acrylates such as n-butyl acrylate / 2-methoxyethyl acrylate copolymers.
  • acrylic rubber composed only of acrylate has a problem that it is inferior in crosslinked rubber characteristics such as heat resistance and compression set resistance.
  • Acrylic rubber having a reactive group having excellent heat resistance and compression set resistance are described in Patent Document 2 (International Publication No. 2018/116828) as ethyl acrylate, n-butyl acrylate and fumaric acid.
  • Acrylic rubber latex obtained by emulsifying a monomer component composed of mono-n-butyl with sodium lauryl sulfate as an emulsifier, polyethylene glycol monostearate and water, and emulsion polymerization in the presence of a polymerization initiator until the polymerization conversion rate reaches 95%.
  • Patent Document 3 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.
  • An acrylic rubber composition composed of a sex 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 an acrylic rubber having a high gel fraction (60%) obtained in a normal acidic region (pH 4 before polymerization, pH 3.4 after polymerization). On the other hand, it is obtained by adjusting the pH of the polymerization solution to 6 to 8 with sodium hydrogen carbonate or the like.
  • Patent Document 4 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 amount of gel which is a THF (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. , It is stated that the extrudability deteriorates when the gel 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 is no description of a method for improving workability such as Banbury.
  • the present invention has been made in view of such circumstances, and provides an acrylic rubber veil having excellent storage stability and processability, a method for producing the same, a rubber mixture containing the acrylic rubber veil, and a crosslinked rubber product thereof. With the goal.
  • an acrylic rubber veil having a reactive group and having a specific molecular weight, an amount of gel insoluble in methyl ethyl ketone and a specific gravity is suitable for storage stability and during kneading such as Banbury. We have found that it is highly workable.
  • the present inventors also obtain storage stability by specifying the gel amount variation of the methyl ethyl ketone insoluble portion of the acrylic rubber veil, the molecular weight distribution focusing on the high molecular weight region, the complex viscosity at a specific temperature, and the ash content. It was found that the workability can be further improved.
  • the present inventors also perform emulsion polymerization of a monomer component containing a reactive group-containing monomer, wash the hydrous crumb produced by the coagulation reaction, and then dry it to a specific hydrous content with a screw extruder to bale it. It was found that an acrylic rubber bale with high storage stability and workability can be produced.
  • the gel amount of acrylic rubber is very difficult to control in the manufacturing process, and the gel amount of the methyl ethyl ketone insoluble content of the acrylic rubber veil to be manufactured is greatly changed, which is optimal for Banbury kneading and the like. It was found that the physical properties of the rubber mixture and the rubber crosslinked product were impaired because the kneading time varied.
  • the gel amount of the methyl ethyl ketone insoluble matter in the acrylic rubber rapidly increases and the processability is deteriorated, but it is substantially dried to a specific water content using a screw type extruder.
  • the present inventors completely differ in the gel of the acrylic rubber veil depending on the SP value of the solvent used, for example, the gel amount of the tetrahydrofuran-insoluble portion of the acrylic rubber and the gel amount of the methyl ethyl ketone insoluble portion are completely correlated.
  • the characteristics of the gel are also different and that the amount of gel in which the methyl ethyl ketone insoluble component of acrylic rubber is insoluble correlates with the processability at the time of kneading such as Banbury.
  • the present inventors also reduced the amount of ash in the acrylic rubber veil by providing a dehydration step for squeezing water from the hydrous crumb and specifying the coagulation method of the emulsion polymerization solution, and also improved water resistance and storage stability. It was found that it was enhanced and the variation in workability was reduced.
  • the present inventors have completed the present invention based on these findings.
  • the weight average molecular weight (Mw) having a reactive group is 100,000 to 5,000,000
  • the gel is made of acrylic rubber
  • the amount of gel insoluble in methyl ethyl ketone is 50% by weight or less
  • the specific gravity is 0.
  • Acrylic rubber veils of 8 or more are provided.
  • the gel amount of the insoluble methyl ethyl ketone is preferably 20% by weight or less.
  • the value when the gel amount of the methyl ethyl ketone insoluble portion of the acrylic rubber bale is arbitrarily measured at 20 points is measured within the range of (mean value -5) to (mean value + 5)% by weight. It is preferable that all 20 points are included.
  • the range of (mean value -5) to (mean value + 5)% by weight is, for example, 15 to 25% by weight when the average value of the measured gel amount of the insoluble methyl ethyl ketone is 20% by weight.
  • the weight average molecular weight (Mw) is preferably in the range of 1,000,000 to 5,000,000.
  • the ratio (Mz / Mw) of the z average molecular weight (Mz) to the weight average molecular weight (Mw) is preferably 1.3 or more.
  • the complex viscosity ([ ⁇ ] 100 ° C.) at 100 ° C. is preferably in the range of 1,500 to 6,000 Pa ⁇ s.
  • 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 ratio of the complex viscosity at 100 ° C. ([ ⁇ ] 100 ° C.) to the complex viscosity at 60 ° C. ([ ⁇ ] 60 ° C.) ([ ⁇ ] 100 ° C./[ ⁇ ] 60 ° C. ) Is more preferably 0.8 or more.
  • the pH is preferably 6 or less.
  • the ash content is preferably 0.5% 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 80% by weight or more.
  • a monomer component containing a (meth) acrylic acid ester and a reactive group-containing monomer is emulsionized with water and an emulsifier and emulsion-polymerized in the presence of a polymerization catalyst to obtain an emulsion polymerization solution.
  • the drying barrel After dehydration to a moisture content of 1 to 40% by weight in a dehydration barrel using a drying barrel under reduced pressure and a screw type extruder having a die at the tip, the drying barrel is dried to a moisture content of less than 1% by weight and dried in a sheet form. It is possible to provide a method for producing an acrylic rubber bale, which includes a dehydration / drying / molding step of extruding rubber from a die and a bale step of laminating and bale the extruded sheet-shaped dried rubber.
  • a rubber mixture obtained by mixing a filler and a cross-linking agent with the acrylic rubber veil.
  • a rubber crosslinked product obtained by cross-linking the rubber mixture is further provided.
  • an acrylic rubber veil having excellent storage stability and processability during kneading such as Banbury, a method for producing the same, a rubber mixture obtained by mixing the acrylic rubber veil, and a rubber crosslinked product obtained by cross-linking the acrylic rubber veil.
  • the acrylic rubber veil of the present invention is made of acrylic rubber having a reactive group and a weight average molecular weight (Mw) of 100,000 to 5,000,000, and the amount of gel insoluble in methyl ethyl ketone is 50% by weight or less and the specific gravity is 0. It is characterized by being 0.8 or more.
  • the acrylic rubber veil of the present invention is made of acrylic rubber having a reactive group.
  • the reactive group is appropriately selected according to the intended use without any particular limitation, but preferably at least one functional group, carboxyl group, or epoxy group selected from the group consisting of a carboxyl group, an epoxy group, and a halogen group.
  • it is at least one functional group selected from the group consisting of a group and a chlorine atom, the cross-linking property of the acrylic rubber veil can be highly improved, which is preferable.
  • 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 acrylic rubber constituting the acrylic rubber veil of the present invention preferably contains (meth) acrylic acid ester, and is selected from the group consisting of (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester. It preferably contains at least one (meth) acrylic acid ester.
  • the acrylic rubber having a preferable reactive group 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, and a reactive group.
  • examples thereof include those composed of a contained monomer and other monomers copolymerizable as required.
  • 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% by weight or more, 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 according to the intended use without any particular limitation, but is a single amount having at least one functional group selected from the group consisting of a carboxyl group, an epoxy group and a halogen group.
  • the body is preferred.
  • 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 veil of the present invention is characterized by having a reactive group.
  • the content of the reactive group may be appropriately selected according to the purpose of use, but is usually 0.001 to 5% by weight, preferably 0.01 to 3% by weight, based on the weight ratio of the reactive group itself.
  • Workability, strength characteristics, compression set resistance, oil resistance, cold resistance, water resistance, etc. are preferably in the range of 0.05 to 1% by weight, particularly preferably 0.1 to 0.5% by weight. The characteristics are highly balanced and suitable.
  • the acrylic rubber constituting the acrylic rubber veil 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 group-containing monomer is usually 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more preferably. It is in the range of 0.5 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, more preferably. It is in the range of 0 to 15% by weight, particularly preferably 0 to 10% by weight.
  • the object of the present invention can be highly achieved, and when the acrylic rubber veil is used as a crosslinked product, water resistance and compression resistance permanent strain characteristics are remarkably improved. It is improved and suitable.
  • the weight average molecular weight (Mw) of the acrylic rubber constituting the acrylic rubber veil 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. 000, more preferably 1,000,000 to 5,000,000, particularly preferably 1,100,000 to 3,500,000, most preferably in the range of 1,200,000 to 2,500,000.
  • GPC-MALS absolute molecular weight measured by GPC-MALS
  • 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 veil of the present invention is not particularly limited, but is measured by GPC-MALS.
  • the processability and strength characteristics of the acrylic rubber veil are highly balanced and preserved when the absolute molecular weight distribution is usually in the range of 1.3 or more, preferably 1.4 to 5, more preferably 1.5 to 2. It is suitable because it can alleviate changes in physical properties over time.
  • the glass transition temperature (Tg) of the acrylic rubber constituting the acrylic rubber veil 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) of acrylic rubber 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 veil of the present invention is appropriately selected according to the purpose of use, but is usually 95% by weight or more, preferably 97% by weight or more, and more preferably 98% by weight or more.
  • the acrylic rubber veil of the present invention is made of the above acrylic rubber, and is characterized in that the gel amount and specific gravity of the insoluble methyl ethyl ketone are specified.
  • 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.
  • the gel amount of the acrylic rubber veil 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, particularly preferably 10% by weight or less, and most preferably 5. When it is less than% by weight, the workability is highly improved and is suitable.
  • the amount of gel, which is the insoluble matter of methyl ethyl ketone in the acrylic rubber veil of the present invention, has different characteristics depending on the solvent used, and does not particularly correlate with the amount of THF (tetrahydrofuran) insoluble gel.
  • the value when the gel amount of the methyl ethyl ketone insoluble portion of the acrylic rubber veil of the present invention is arbitrarily measured at 20 points is not particularly limited, but it is preferable that all 20 points are within the range of the average value ⁇ 5. Is suitable because there is no workability variation and various physical properties of the rubber mixture and the rubber crosslinked product are stabilized when all 20 points are within the range of the average value of ⁇ 3.
  • the specific gravity of the acrylic rubber veil of the present invention is not particularly limited, but is usually 0.8 or more, preferably 0.8 to 1.4, more preferably 0.9 to 1.3, and particularly preferably 0.95.
  • the range is 1.25, most preferably 1.0 to 1.2, the storage stability is highly excellent and suitable.
  • the specific gravity of the acrylic rubber veil is excessively small, it indicates that the amount of air entrained in the acrylic rubber veil is large, which greatly affects the storage stability including oxidative deterioration, which is not preferable.
  • the water content of the acrylic rubber veil of the present invention is not particularly limited, but the vulcanization property 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 optimized and has excellent properties such as heat resistance and water resistance, and is suitable.
  • the pH of the acrylic rubber veil 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 ash content of the acrylic rubber veil of the present invention is. Although not particularly limited, it is usually 0.5% by weight or less, preferably 0.4% by weight or less, more preferably 0.3% by weight or less, particularly preferably 0.2% by weight or less, and most preferably 0. When it is .15% by weight or less, it is excellent in storage stability and water resistance and is suitable.
  • the lower limit of the ash content of the acrylic rubber veil 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 veil of the present invention are highly balanced is usually 0.0001 to 0.5% by weight, preferably 0.0005 to 0.4% 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 veil of the present invention is not particularly limited, but is based on the total ash content.
  • the storage stability and water resistance are highly excellent and suitable when the ratio is usually at least 30% by weight, preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more.
  • the total amount of sodium and sulfur in the ash content of the acrylic rubber veil 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 veil of the present invention is 0.4 to 2.5, preferably 0.6 to 2, preferably 0 by weight. When it is in the range of .8 to 1.7, 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 veil 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 veil 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 complex viscosity ([ ⁇ ] 60 ° C.) of the acrylic rubber veil 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 veil 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 ([ ⁇ ] 100 ° C.) of the acrylic rubber veil of the present invention at 100 ° C. to the complex viscosity ([ ⁇ ] 60 ° C.) at 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 ° C.) of the complex viscosity at 100 ° C. ([ ⁇ ] 100 ° C.) to the complex viscosity at 60 ° C.
  • ([ ⁇ ] 60 ° C.) is usually 0. Workability, oil resistance, and workability, oil resistance, and when the range is 5 to 0.99, preferably 0.5 to 0.98, more preferably 0.6 to 0.95, and most preferably 0.75 to 0.93.
  • the shape retention is highly balanced and suitable.
  • the Mooney viscosity (ML1 + 4,100 ° C.) of the acrylic rubber veil 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 method for producing the acrylic rubber bale is not particularly limited, but for example, a monomer component containing a (meth) acrylic acid ester and a reactive group-containing monomer is emulsion-polymerized with water and an emulsifier.
  • a coagulation step in which the obtained emulsion polymerization solution and the coagulation solution are brought into contact with each other to form a hydrous crumb, A cleaning process to clean the generated hydrous crumbs,
  • the washed water-containing crumb is dehydrated to a water content of 1 to 40% by weight in a dehydration barrel using a dehydration barrel having a dehydration slit, a drying barrel under reduced pressure, and a screw type extruder having a die at the tip, and then contained in the drying barrel.
  • Dehydration / drying / molding process that dries to less than 1% by weight of water and extrudes sheet-shaped dry rubber from the die.
  • the acrylic rubber veil according to the present invention can be easily produced by including the above.
  • a monomer component containing a (meth) acrylic acid ester and a reactive group-containing monomer is emulsified with water and an emulsifier and emulsified in the presence of a polymerization catalyst. This is a step of polymerizing to obtain an emulsion polymerization solution.
  • the monomer component used is the same as that described in the monomer component, and the amount used may be appropriately selected so as to have the monomer composition of the acrylic rubber constituting the acrylic rubber veil. Often, the amount is usually the same as the monomer composition of the acrylic rubber constituting the acrylic rubber veil.
  • the emulsifier used is not particularly limited and may follow a conventional method, and examples thereof include anionic emulsifiers, cationic emulsifiers, and nonionic emulsifiers. Among these, anionic emulsifiers and nonionic emulsifiers are preferable, anionic emulsifiers are more preferable, phosphoric acid-based emulsifiers and sulfuric acid-based emulsifiers are particularly preferable, and phosphoric acid-based emulsifiers are most preferable.
  • anionic emulsifier those usually used are used without particular limitation, and examples thereof include fatty acid-based emulsifiers, sulfonic acid-based emulsifiers, sulfosuccinic acid-based emulsifiers, sulfuric acid-based emulsifiers, and phosphoric acid-based emulsifiers, and are preferable. It is a sulfuric acid-based emulsifier.
  • fatty acid-based emulsifiers examples include sodium octanate, sodium decanoate, sodium laurate, sodium myristate, sodium palmitate, sodium stearate, and the like.
  • sulfonic acid-based emulsifier examples include sodium hexane sulfonate, sodium octane sulfonate, sodium decane sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, sodium octylbenzene sulfonate, sodium dodecylbenzene sulfonate, and dodecylbenzene sulfonic acid.
  • examples thereof include ammonium, sodium naphthalene sulfonate, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate and the like.
  • sulfosuccinic acid-based emulsifier examples include sodium dioctyl sulfosuccinate and sodium dihexyl sulfosuccinate.
  • the sulfuric acid-based emulsifier is not particularly limited and may follow a conventional method, but a sulfate ester salt can be preferably used.
  • a sulfate ester salt examples include sodium lauryl sulfate, ammonium lauryl sulfate, sodium myristyl sulfate, sodium laureth sulfate, sodium polyoxyethylene alkyl sulfate, sodium polyoxyethylene alkylaryl sulfate, and the like, and sodium lauryl sulfate is preferable.
  • Examples of the phosphoric acid-based emulsifier include sodium lauryl phosphate, potassium lauryl phosphate, sodium polyoxyalkylene alkyl ether phosphoric acid ester, and the like.
  • 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 0.1 parts by weight, based on 100 parts by weight of the monomer component. It is in the range of up 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 in the range of 10 to 750 parts by weight, preferably 50 to 500 parts by weight, and more preferably 100 to 400 parts by weight with respect to 100 parts by weight of the monomer component.
  • 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 bale 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 coagulation step in the method for producing an acrylic rubber sheet of the present invention is characterized in that the obtained emulsion polymerization solution is added to a stirring coagulation solution (coagulant-containing aqueous solution) to generate 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 Metals 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, preferably calcium chloride, magnesium sulfate, and more preferably magnesium sulfate.
  • 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.
  • the acrylic rubber can be sufficiently solidified, and the compression-resistant permanent strain resistance and water resistance when the acrylic rubber veil is crosslinked can be highly improved, which is preferable.
  • the coagulant concentration of the coagulant 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 suitable because the particle size of the hydrous crumb that is sometimes generated 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 stirring speed (rotation speed) of the coagulated liquid being stirred is, that is, the rotation speed of the stirring blade of the stirring device, and is not particularly limited, but is usually 100 rpm or more, preferably 200 to 1,000 rpm, and more preferably 300. It is in the range of ⁇ 900 rpm, particularly preferably 400 to 800 rpm. It is preferable that the rotation speed is a rotation speed that is vigorously agitated to some extent so that the hydrous crumb particle size to be generated can be made small and uniform. By setting the rotation speed to the above lower limit or more, the crumb particle size is excessively large or small. The formation of and can be suppressed, and the solidification reaction can be more easily controlled by setting the content to the upper limit or less.
  • the peripheral speed of the coagulated liquid being agitated that is, the speed of the outer circumference of the stirring blade of the agitating device is not particularly limited, but the water-containing crumb particle size generated by vigorously agitating to a certain degree is smaller and It can be made uniform and is preferable, 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 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 step in the method for producing an acrylic rubber veil of the present invention is a step of cleaning the produced hydrous crumb with water.
  • 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 it is preferable to use warm water, 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 the cleaning efficiency can be significantly increased at °C.
  • 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, 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 / or By setting the cleaning temperature within the above range, the number of cleanings can be significantly reduced.
  • the above-cleaned 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 bale of the present invention, providing 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 step improves the dehydration efficiency. It is suitable for raising.
  • 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, and more. It is preferably in the range of 50 to 60% by weight.
  • the temperature of the hydrous crumb after draining that is, the temperature of the hydrous crumb put into the dehydration / drying step is not particularly limited, but is usually 40 ° C. or higher, preferably 40 to 100 ° C., more preferably 50 to 90 ° C.
  • the temperature is in the range of ° C., particularly preferably 55 to 85 ° C., most preferably 60 to 80 ° C., the temperature is raised as high as 1.5 to 2.5 KJ / kg ⁇ K as in the acrylic rubber of the present invention. It is suitable because difficult water-containing crumbs can be efficiently dehydrated and dried using a screw type extruder.
  • Dehydration of hydrous crumbs Dehydration barrel
  • Dehydration of the hydrous crumb is carried out in a dehydration barrel having a dehydration slit.
  • 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 selection of the drainage type dehydration barrel or the exhaust steam type dehydration barrel of the screw type extruder equipped with three or more dehydration barrels may be appropriately performed according to the purpose of use, but the amount of ash in the acrylic rubber usually produced is small. In this case, the number of drainage barrels is increased. For example, when there are three dehydration barrels, two drainage barrels are selected, and when there are four dehydration barrels, three drainage barrels are appropriately selected.
  • the set temperature of the dehydration barrel is appropriately selected depending on the type of acrylic rubber, ash content, water content, operating conditions, etc., but is usually 60 to 150 ° C., preferably 70 to 140 ° C., more preferably 80 to 130 ° C. The range.
  • 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 dries 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 after dehydration of the drainage type that squeezes water from the water-containing crumb 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, and particularly preferably. Is suitable because the productivity and the ash removal efficiency are highly balanced when the content is 10 to 35% by weight.
  • the water content after drainage in the drainage type dehydration barrel portion is usually 5 to 45% by weight, preferably 10 to 40% by weight, more preferably. Is 15 to 35% by weight, and the water content after pre-drying in the exhaust steam type dehydration barrel portion is 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 of the methyl ethyl ketone insoluble component of acrylic rubber 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 gel amount of the methyl ethyl ketone insoluble portion of the acrylic rubber veil can be reduced by melt-extruding the dry rubber with the water content of the dry rubber set to this value (in a state where most of the water is removed), particularly in the screw type extruder. Suitable.
  • Acrylic rubber shape (die part)
  • the acrylic 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 usually cooled and cut to be 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 dry rubber extruded from the screw type extruder is 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 is suitable because it is laminated after cutting and veiled because the amount of air involved is small and the storage stability is excellent.
  • the cutting of the sheet-shaped dry rubber is not particularly limited, but since the acrylic rubber of the acrylic rubber veil of the present invention has strong adhesiveness, the sheet-shaped dry rubber is used for continuous cutting 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 ([ ⁇ ] 100 ° C.) of the sheet-shaped dried rubber at 100 ° C. to the complex viscosity ([ ⁇ ] 60 ° C.) at 60 ° C. is Although there is no particular limitation, air is usually in the range of 0.5 or more, preferably 0.5 to 0.98, more preferably 0.6 to 0.95, and most preferably 0.75 to 0.93. It is suitable because it has low entanglement and has a high balance between cutting and productivity.
  • 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 may be appropriately selected according to the size of the acrylic rubber bale to be manufactured, but is usually 100 to 800 mm, preferably 200 to 500 mm, more preferably 250 to 450 mm. Is the range of.
  • the bale step in the method for producing an acrylic rubber veil of the present invention is to laminate the above sheet-shaped dry rubber to make a veil.
  • 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.
  • the acrylic rubber veil of the present invention thus obtained has excellent operability and storage stability as compared with crumb-shaped acrylic rubber, and the acrylic rubber veil can be used as it is or cut into a required amount and put into a mixer such as a vanbury or roll. Can be used.
  • the rubber mixture of the present invention is characterized in that the 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.
  • Each of these fillers can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected within a range that does not impair the effect of the present invention, with respect to 100 parts by weight of the acrylic rubber veil. 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 according to the type and application of the reactive group contained in the acrylic rubber constituting the acrylic rubber bale, but is not particularly limited as long as it can cross-link the acrylic rubber bale.
  • polyvalent amine compounds such as diamine compounds, and carbonates thereof; sulfur compounds; sulfur donors; triazinethiol compounds; polyvalent epoxy compounds; ammonium organic carboxylates; organic peroxides; polyvalent carboxylic acids;
  • Conventionally known cross-linking agents such as a secondary onium salt; an imidazole compound; an isocyanuric acid compound; an organic peroxide; and a triazine compound; 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 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 cross-linking agent is an aliphatic polyvalent amine compound such as hexamethylenediamine or hexamethylenediamine carbamate, and a carbonate thereof; 4,4'-methylene.
  • Aromatic polyvalent amine compounds such as dianiline; ammonium carboxylic acid salts such as ammonium benzoate and ammonium adipate; metal dithiocarbamic acid salts such as zinc dimethyldithiocarbamate; polyvalent carboxylic acids such as tetradecanodic acid; cetyltrimethylammonium bromide Tertiary onium salts such as; imidazole compounds such as 2-methylimidazole; isocyanuric acid compounds such as ammonium isocyanurate; among these, ammonium carboxylic acid salt and metal dithiocarbamate salt are preferable, and ammonium benzoate is preferable. Is more preferable.
  • the 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.
  • 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 0.1, based on 100 parts by weight of the acrylic rubber veil. It is ⁇ 10 parts by weight, more preferably 0.1 ⁇ 5 parts by weight.
  • 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 crumb shape, a sheet shape, a veil shape, or the like.
  • 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, butylhydroxyanisole, 2,6-di-t-butyl-.
  • 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, preferably 0.% by weight, based on 100 parts by weight of the acrylic rubber veil. It is in the range of 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 veil of the present invention, a filler, a cross-linking agent and, if necessary, other rubber components and an anti-aging agent, and is usually used in the art as necessary.
  • additional blending of other additives such as cross-linking aids, cross-linking accelerators, cross-linking retarders, silane coupling agents, plasticizers, processing aids, rubbers, pigments, colorants, antistatic agents, foaming agents, etc. it can.
  • 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.
  • the acrylic rubber veil of the present invention is mixed with the filler, a cross-linking agent and other rubber components, an antiaging agent and other compounding agents which can be contained if necessary.
  • any means conventionally used in the rubber processing field for example, an open roll, a Banbury mixer, various kneaders and the like can be used. That is, using these mixers, the acrylic rubber veil can be mixed by directly mixing the filler, the cross-linking agent and the like, preferably by directly kneading.
  • the acrylic rubber bale may be used as it is or divided (cut, etc.).
  • 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 veil and the filler in the first step and then mix the cross-linking agent in the second step.
  • 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 veil 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 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 as a coagulant 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 veil can be effectively reduced by mixing the hydrous crumb generated by the coagulation 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 acrylic rubber that passes through the die 59 is formed into various shapes such as granular, columnar, round bar, and sheet depending on the nozzle shape of the die 59. For example, by making the discharge port of the die 59 substantially rectangular, the acrylic rubber can be extruded into a sheet shape.
  • 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 veil 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 dried rubber discharged from the screw type extruder 5 is extruded into various shapes such as granular, columnar, round bar, and sheet according to the nozzle shape of the die 59.
  • 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 screw type extruder 5 can extrude the dried rubber into various shapes such as granular, columnar, round bar, and sheet, and the bale device 7 has various shapes as described above. It is configured to veil dry rubber molded into a shape.
  • 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 bale device 7 may include, for example, a baler, and may manufacture an acrylic rubber bale by compressing the cooled dry rubber with the baler.
  • 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 in the acrylic rubber veil by the following method.
  • the amount of carboxyl groups was calculated by dissolving 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 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 veil in a combustion flask, absorbing the generated chlorine in water, and titrating with silver nitrate.
  • the amount of each component (ppm) in the acrylic rubber veil ash content was measured by XRF using ZSX Primus (manufactured by Rigaku) by pressing the ash content collected at the time of the above ash content measurement onto a ⁇ 20 mm titration filter paper.
  • the gel amount (%) of 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 water content (%) of the acrylic rubber veil was measured according to JIS K6238-1: Oven A (volatile content 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 bale is subjected to temperature dispersion (40 to 120 ° C.) at a strain of 473% and 1 Hz using a dynamic viscoelasticity measuring device “Rubber Process Analyzer RPA-2000” (manufactured by Alpha Technology). The measurement was performed to determine the complex viscoelasticity ⁇ at each temperature.
  • 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 water resistance of the rubber sample is determined by immersing the crosslinked product of the rubber sample in distilled water at a temperature of 85 ° C. for 100 hours in accordance with JIS K6258, performing a dipping test, and calculating the volume change rate before and after dipping according to the following formula. It was evaluated by an index with 2 as 100 (the smaller the index, the better the water resistance).
  • Volume change rate before and after immersion ((Test piece volume after immersion-Test piece volume before immersion) / Test piece volume before immersion) x 100
  • 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%.
  • Example 1 In a mixing container equipped with a homomixer, 46 parts of pure water, 28 parts of ethyl acrylate, 38 parts of n-butyl acrylate, 27 parts of methoxyethyl acrylate, 5 parts of acrylonitrile and 2 parts of allyl glycidyl ether, and nonylphenyl as an emulsifier. 1.8 parts of oxyhexaoxyethylene phosphate sodium salt was charged and stirred to obtain a monomeric emulsion.
  • Emulsion polymerization obtained in a 2% magnesium sulfate aqueous solution (coagulant) heated to 80 ° C. and vigorously stirred (600 rpm: peripheral speed 3.1 m / s) in a coagulation tank equipped with a thermometer and a stirrer. The liquid was heated to 80 ° C. and continuously added to solidify the polymer and filtered off to obtain a hydrous crumb.
  • coagulant 2% magnesium sulfate aqueous solution heated to 80 ° C. and vigorously stirred (600 rpm: peripheral speed 3.1 m / s) in a coagulation tank equipped with a thermometer and a stirrer.
  • the liquid 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. ⁇ Temperature of rubber discharged from screw type extruder: 140 °C
  • the extruded sheet-shaped dry rubber was cooled to 50 ° C., cut with a cutter, and laminated to 20 parts (20 kg) before the temperature fell below 40 ° C. to obtain an acrylic rubber veil (A).
  • A acrylic rubber veil
  • the viscosities (ML1 + 4,100 ° C.) were measured and the results are shown in Table 2.
  • the variation in the gel amount of the acrylic rubber veil (A) was evaluated, and the results are shown in Table 2.
  • the obtained rubber mixture was placed in a mold having a length of 15 cm, a width of 15 cm, and a depth of 0.2 cm, and was first crosslinked by pressing at 180 ° C. for 10 minutes while pressurizing at a press pressure of 10 MPa, and then obtained.
  • the primary crosslinked product was further heated in a gear oven at 180 ° C. for 2 hours for secondary cross-linking to obtain a sheet-shaped rubber crosslinked product.
  • a 3 cm ⁇ 2 cm ⁇ 0.2 cm test piece was cut out from the obtained sheet-shaped rubber crosslinked product, and the water resistance evaluation and the normal physical properties were evaluated, and the results are shown in Table 2.
  • Example 2 The monomer component was 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, and the emulsifier was tridecyloxyhexa.
  • Acrylic rubber veil (B) was obtained in the same manner as in Example 1 except that the sodium salt was changed to oxyethylene phosphate sodium salt, and each characteristic (changed to "formulation 2”) was evaluated. The results are shown in Table 2.
  • Example 3 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.
  • the same procedure as in Example 1 was carried out except that the water content of the water-containing crumb after drainage was changed to 30%, and an acrylic rubber bale (C) was obtained and each characteristic was evaluated. The results are shown in Table 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.
  • the same procedure as in Example 2 was carried out except that the water content of the water-containing crumb after drainage was changed to 30%, and acrylic rubber barrels (D) were obtained and each characteristic was evaluated. The results are shown in Table 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 water-containing crumb for discharging water from the coagulation tank was washed four times, and then a sulfuric acid aqueous solution having a pH of 3 was washed. After adding 194 parts and stirring at 25 ° C.
  • a crumb-shaped acrylic rubber (F) having a water content of 0.4% by weight was obtained by drying with a hot air dryer at ° C. Each characteristic (“blending 2”) of the obtained crumb-shaped acrylic rubber (F) was evaluated and shown in Table 2.
  • the weight average molecular weight (Mw) having the reactive group of the present invention is 100,000 to 5,000,000, and it is made of acrylic rubber.
  • the amount of gel insoluble in methyl ethyl ketone is 50% by weight or less, and the specific gravity is 0.
  • Acrylic rubber veils (A) to (D) having a value of 9 or more are highly excellent in storage stability and processability during Banbury kneading, and also have variations in gel amount (as a result, variations in processability and cross-linking described below). It can be seen that it is also excellent in normal physical properties including water resistance and strength characteristics (variations in physical properties) (Examples 1 to 4).
  • the acrylic rubbers (E) to (F) have a weight average molecular weight (Mw) of the absolute molecular weight measured by GPC-MALS exceeding 100,000, and an absolute emphasis on the high molecular weight region measured by GPC-MALS. Since the ratio (Mz / Mw) of the z average molecular weight (Mz) and the weight average molecular weight (Mw) of the molecular weight distribution is much larger than 1.3, it can be seen that it is excellent in all the characteristics of normal physical properties.
  • Example 1 Examples 1 to 6 and Comparative Examples 1 to 2.
  • the crumb-shaped acrylic rubber (E) of Comparative Example 1 is excellent in normal physical properties, the gel amount varies, the processability and water resistance are significantly inferior, and the crumb-shaped acrylic rubber (F) of Comparative Example 2 is a gel. It can be seen that none of the characteristics of quantity variation, storage stability, processability and water resistance is sufficient.
  • the rate of change in the minimum viscosity (Vm) of the Mooney scorch before and after putting it in the constant temperature and humidity chamber of 45 ° C. ⁇ 80% RH is evaluated.
  • the acrylic rubber veils (A) to (D) of the present invention are evaluated. Is overwhelmingly superior to the crumb-shaped acrylic rubbers (E) and (F) (comparison between Examples 1 to 4 and Comparative Examples 1 and 2). This is because the specific gravities of the acrylic rubber veils (A) to (D) are much higher than those of the crumb-shaped acrylic rubbers (E) and (F), and the storage stability is high because they contain almost no air. It seems to be improving.
  • the difference in storage stability is the difference in specific gravity (amount of air entrainment) between the acrylic rubber veils (A) to (D) of the present invention and the crumb-shaped acrylic rubbers (E) to (F) of the comparative example.
  • Table 2 does not show these conditions for the small amount (content) of air entrained in the acrylic rubber veils (A) to (E) of the present invention, but a detailed description of the method for producing the acrylic rubber bale of the present application and the implementation of the present application.
  • the temperature and resin pressure of the die part are specified to extrude the sheet-shaped dry rubber with a specific water content, and the extruded sheet-shaped dry rubber is extruded. It can be seen that this can be achieved by cooling to a specific temperature, cutting, and laminating at a specific temperature.
  • the amount of gel at 20 points arbitrarily selected was measured, and whether or not all the measured values of all 20 points measured within the range of the mean value ⁇ 3 were included, or It was judged whether or not all the measured values of 20 points were within the range of the average value ⁇ 5, but the acrylic rubber veils (A) to (D) of the present invention were crumb-shaped acrylic rubbers (E) and (F). ) Is overwhelmingly excellent in variation, and it can be seen that there is little variation in the amount of gel of the methyl ethyl ketone insoluble matter in the veil (comparison between Examples 1 to 4 and Comparative Example 1).
  • the amount of gel of the insoluble methyl ethyl ketone directly affects the processability of Banbury and the like, and if this is changed, the physical properties of the rubber mixture and the crosslinked rubber will vary, resulting in deterioration of the physical properties, which is not preferable.
  • the acrylic rubber veils (A) to (D) of the present invention have no variation in the gel amount of the methyl ethyl ketone insoluble matter, and can provide a stable rubber mixture or rubber crosslinked product.
  • the polymerization conversion rate of emulsion polymerization is increased in order to improve the strength characteristics, but as the polymerization conversion rate is increased, the gel amount of the insoluble methyl ethyl ketone rapidly increases and the processing of acrylic rubber Although the properties were deteriorated, the rapidly increased amount of methyl ethyl ketone insoluble gel disappeared when it was dried and melt-kneaded in a screw-type extruder to a state where there was virtually no water content (water content less than 1%). It can be seen that the processability and strength of the acrylic rubber bale are highly balanced (comparison between Examples 1 to 4 and Comparative Example 1).
  • Water resistance is a secondary effect in producing an acrylic rubber veil that has excellent storage stability and workability during kneading such as Banbury. That is, in order to achieve the subject of the present application, it is important to reduce the water content of acrylic rubber having a large specific gravity to less than 1% by weight in a short screw type extruder, and for that purpose, a crumb shape that is easily dehydrated by a solidification reaction. Is made, and the hydrous crumb is washed with warm water and put into the screw type extruder at the same temperature, and the dehydration efficiency in the screw type extruder is improved, so that the dry barrel part is melt-mixed in a state of substantially no moisture.
  • the problem is achieved by enabling smelting, eliminating the gel amount of the insoluble methyl ethyl ketone, reducing the resin pressure of the die portion, enabling sheet-like extrusion, and increasing the specific gravity of the acrylic rubber bale.
  • Table 2 it can be seen that the ash content of the acrylic rubber veil is dramatically reduced and the water resistance is significantly improved.
  • Acrylic rubber veils (A) to (D) having a Mooney viscosity (1 + 4,100 ° C.) in a specific range are remarkably excellent in storage stability and processability, as well as variations in the amount of gel in which methyl ethyl ketone is insoluble, water resistance, and normal physical characteristics. It can be seen that it is also excellent in (strength characteristics) (Examples 1 to 4).
  • Example 5 Examples except that the monomer component was changed to 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.
  • Acrylic rubber bale (G) was obtained in the same manner as in 1. Measurement and evaluation of each characteristic of the obtained acrylic rubber veil (G) (Compounding agent B of the rubber mixture is 0.5 part of hexamethylenediamine carbamate and Lenogran XLA-60 (active amine and retarder synthetic mixture: manufactured by Rankses).
  • Acrylic rubber veil (H) was carried out in the same manner as in Example 2 except that the monomer component was changed to 48.25 parts of ethyl acrylate, 50 parts of n-butyl acrylate, and 1.75 parts of mono-n-butyl fumarate.

Abstract

Provided are an acrylic-rubber bale excellent in terms of storage stability and processability, a production method therefor, a rubber mixture obtained from ingredients including the acrylic rubber bale, and a crosslinked rubber object obtained therefrom. This acrylic-rubber bale comprises an acrylic rubber having a reactive group and having a weight-average molecular weight (Mw) of 100,000-5,000,000 and has a content of a gel insoluble in methyl ethyl ketone of 50 wt% or less and a specific gravity of 0.8 or greater.

Description

保存安定性と加工性に優れるアクリルゴムベールAcrylic rubber veil with excellent storage stability and workability
　本発明は、アクリルゴムベール、その製造方法、ゴム混合物及びゴム架橋物に関し、さらに詳しくは、保存安定性と加工性に優れるアクリルゴムベール、その製造方法、該アクリルゴムベールを混合してなるゴム混合物、及びそれを架橋してなるゴム架橋物に関する。 The present invention relates to an acrylic rubber bale, a method for producing the same, a rubber mixture and a rubber crosslinked product. More specifically, the present invention relates to an acrylic rubber bale having excellent storage stability and processability, a method for producing the same, and a rubber obtained by mixing the acrylic rubber bale. The present invention relates to a mixture and a rubber crosslinked product obtained by cross-linking the mixture.
　アクリルゴムは、アクリル酸エステルを主成分とする重合体であり、一般に耐熱性、耐油性及び耐オゾン性に優れたゴムとして知られ、自動車関連の分野などで広く用いられている。 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, and is widely used in automobile-related fields and the like.
　このようなアクリルゴムは、通常、アクリルゴムを構成する単量体成分を乳化重合し、得られた乳化重合液と凝固剤を接触させ、得られる含水クラムを乾燥した後にベール化され製品化される。 Such acrylic rubber is usually emulsion-polymerized with the monomer components constituting the acrylic rubber, brought into contact with the obtained emulsion polymerization solution and a coagulant, and the obtained hydrous crumb is dried and then veiled and commercialized. To.
　例えば、特許文献１（特開２００６－３２８２３９号公報）には、重合体ラテックスを凝固液と接触させることによりクラム状ゴム重合体を含むクラムスラリーを得る工程と、撹拌動力が１ｋＷ／ｍ３以上である撹拌・破砕機能付きミキサーでクラムスラリーに含まれているクラム状ゴム重合体の破砕を行う工程と、クラム状ゴム重合体が破砕されたクラムスラリーから水分を取り除きクラム状ゴム重合体を得る脱水工程と、水分の取り除かれたクラム状ゴム重合体を加熱乾燥する工程とを備えてなるゴム重合体の製造方法が開示され、乾燥されたクラムは、フレーク状でベーラーに導入されて圧縮されベール化されることが記載されている。また、撹拌・破砕機能付きミキサーでの破砕は、クラムの最大幅が３～２０ｍｍ程度に調整することが好ましいと記載されている。ここで使用されるゴム重合体としては、乳化重合により得られた不飽和ニトリル－共役ジエン共重合体ラテックスが具体的に示され、また、エチルアクリレート／ｎ－ブチルアクリレート共重合体、エチルアクリレート／ｎ－ブチルアクリレート／２－メトキシエチルアクリレート共重合体などのアクリレートのみで構成される共重合体などに適用できることが示されている。しかしながら、アクリレートのみで構成されたアクリルゴムでは、耐熱性や耐圧縮永久歪み特性などの架橋ゴム特性に劣る問題があった。 For example, Patent Document 1 (Japanese Unexamined Patent Publication No. 2006-328239) describes a step of obtaining a crumb slurry containing a crumb-like rubber polymer by contacting a polymer latex with a coagulating liquid, and a stirring power of 1 kW / m3 or more. A step of crushing the crumb-shaped rubber polymer contained in the crumb slurry with a mixer having a stirring / crushing function, and dehydration of removing water from the crumb slurry in which the crumb-shaped rubber polymer is crushed to obtain a crumb-shaped rubber polymer. A method for producing a rubber polymer comprising a step and a step of heating and drying the moisture-removed crumb-like rubber polymer is disclosed, and the dried crumb is introduced into a baler in the form of flakes, compressed and veiled. It is stated that it will be polymerized. Further, it is described that it is preferable to adjust the maximum width of the crumb to about 3 to 20 mm for crushing with a mixer having a stirring / crushing function. As the rubber polymer used here, an unsaturated nitrile-conjugated diene copolymer latex obtained by emulsification polymerization is specifically shown, and ethyl acrylate / n-butyl acrylate copolymer and ethyl acrylate / It has been shown that it can be applied to copolymers composed only of acrylates such as n-butyl acrylate / 2-methoxyethyl acrylate copolymers. However, acrylic rubber composed only of acrylate has a problem that it is inferior in crosslinked rubber characteristics such as heat resistance and compression set resistance.
　耐熱性や耐圧縮永久歪み特性に優れる反応性基を有するアクリルゴムとしては、例えば、特許文献２（国際公開第２０１８／１１６８２８号パンフレット）には、アクリル酸エチル、アクリル酸ｎ－ブチル及びフマル酸モノｎ－ブチルからなる単量体成分を、乳化剤としてのラウリル硫酸ナトリウムとモノステアリン酸ポリエチレングリコールと水とでエマルジョン化し重合開始剤存在下で重合転化率９５％に達するまで乳化重合したアクリルゴムラテックスを、硫酸マグネシウムと高分子凝集剤であるジメチルアミン－アンモニア－エピクロロヒドリン重縮合物との水溶液中に添加した後に８５℃で撹拌してクラムスラリーを生成させ、次に該クラムスラリーを１回水洗後に１００メッシュの金網に全量通させ固形分のみを捕捉しクラム状のアクリルゴムを回収する方法が開示されている。この方法によれば、得られた含水状態のクラムは、遠心分離などで脱水し、バンドドライヤーなどにより５０～１２０℃で乾燥し、ベーラーに導入されて圧縮されベール化されることが記載されている。しかしながら、かかる方法では、凝固反応で半凝固状態の含水クラムが多数発生し、凝固槽に多量に付着する問題や、洗浄による凝固剤や乳化剤の除去が十分にできないなどの問題があり、また、耐水性や保存安定性に劣り、また、バンバリーなどでの加工性に劣る問題があった。 Examples of acrylic rubber having a reactive group having excellent heat resistance and compression set resistance are described in Patent Document 2 (International Publication No. 2018/116828) as ethyl acrylate, n-butyl acrylate and fumaric acid. Acrylic rubber latex obtained by emulsifying a monomer component composed of mono-n-butyl with sodium lauryl sulfate as an emulsifier, polyethylene glycol monostearate and water, and emulsion polymerization in the presence of a polymerization initiator until the polymerization conversion rate reaches 95%. Was added to an aqueous solution of magnesium sulfate and a polymer flocculant dimethylamine-ammonia-epichlorohydrin polycondensate, and then stirred at 85 ° C. to generate a crumb slurry, and then the crumb slurry was added to 1 A method of recovering a crumb-shaped acrylic rubber by passing the entire amount through a 100-mesh wire net after washing with water to capture only the solid content is disclosed. According to this method, it is described that the obtained hydrous crumb is dehydrated by centrifugation or the like, dried at 50 to 120 ° C. by a band dryer or the like, introduced into a baler, compressed and veiled. There is. However, such a method has problems that a large amount of water-containing crumbs in a semi-coagulated state are generated in the coagulation reaction and a large amount of them adhere to the coagulation tank, and that the coagulant and emulsifier cannot be sufficiently removed by washing. There is a problem that it is inferior in water resistance and storage stability, and also inferior in processability in an emulsifier or the like.
　アクリルゴムのゲル量に関しては、例えば、特許文献３（特許第３５９９９６２号公報）には、アルキルアクリレート又はアルコキシアルキルアクリレート９５～９９．９重量％と反応性の異なるラジカル反応性不飽和基を２個以上有する重合性単量体０．１～５重量％をラジカル重合開始剤の存在下に共重合して得られたアセトン不溶解分であるゲル分率が５重量％以下であるアクリルゴム、補強性充填剤及び有機過酸化物系加硫剤からなる押出速度、ダイスウエル、表面肌などの押出加工性に優れたアクリルゴム組成物が開示されている。ここで使用されるゲル分率が非常に小さいアクリルゴムは、重合液が通常の酸性領域（重合前ｐＨ４、重合後ｐＨ３．４）で得られるゲル分率が高い（６０％）のアクリルゴムに対し、重合液を炭酸水素ナトリウムなどでｐＨ６～８に調整することにより得られている。具体的には、水、乳化剤としてラウリル硫酸ナトリウムとポリオキシエチレンノニルフェニルエーテル、炭酸ナトリウム及びホウ酸を仕込んで７５℃に調整した後、ｔ－ブチルハイドロパーオキサイド、ロンガリット、エチレンジアミン四酢酸二ナトリウム、硫酸第一鉄を添加して（この時のｐＨは７．１）、次にエチルアクリレートとアリルメタクリレートの単量体成分を滴下して乳化重合行い、得られたエマルジョン（ｐＨ７）を硫酸ナトリウム水溶液を用いて塩析し、水洗・乾燥してアクリルゴムを得ている。しかしながら、（メタ）アクリル酸エステルを主成分とするアクリルゴムは、中性からアルカリ領域で分解し、加工性が改善されても保存安定性や強度特性に劣る問題があった。 Regarding the amount of gel of acrylic rubber, for example, Patent Document 3 (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, which is an acetone-insoluble component obtained by copolymerizing 0.1 to 5% by weight of the above-mentioned polymerizable monomer in the presence of a radical polymerization initiator, is reinforced. An acrylic rubber composition composed of a sex 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 an acrylic rubber having a high gel fraction (60%) obtained in a normal acidic region (pH 4 before polymerization, pH 3.4 after polymerization). On the other hand, it is obtained by adjusting the pH of the polymerization solution to 6 to 8 with sodium hydrogen carbonate or the like. Specifically, water, sodium lauryl sulfate and polyoxyethylene nonylphenyl ether as emulsifiers, sodium carbonate and boric acid were added and adjusted to 75 ° C., and then t-butyl hydroperoxide, longalite, disodium ethylenediamine tetraacetate, Ferrous sulfate was added (pH at this time was 7.1), then the monomer components of ethyl acrylate and allyl methacrylate were added dropwise to carry out emulsion polymerization, and the obtained emulsion (pH 7) was subjected to an aqueous sodium sulfate solution. Is salted using, washed with water and dried to obtain acrylic rubber. However, acrylic rubber containing (meth) acrylic ester as a main component decomposes in the neutral to alkaline region, and even if the processability is improved, there is a problem that the storage stability and strength characteristics are inferior.
　また、特許文献４（国際公開第２０１８／１４３１０１号パンフレット）には、（メタ）アクリル酸エステルとイオン架橋性単量体とを乳化重合し、１００℃における複素粘性率（［η］１００℃）が３，５００Ｐａ・ｓ以下で、６０℃における複素粘性率（［η］６０℃）と１００℃における複素粘性率（［η］１００℃）との比（［η］１００℃／［η］６０℃）が０．８以下であるアクリルゴムを用いて、補強剤と架橋剤を含むゴム組成物の押出成形性、特に吐出量、吐出長さ及び表面肌性を高める技術が開示されている。同技術で使用されるアクリルゴムのＴＨＦ（テトラヒドロフラン）不溶解分であるゲル量が、８０重量％以下、好ましくは５～８０重量％であり、７０％以下の範囲でできるだけ多く存在するのが好ましく、ゲル量が５％未満になると押出性が悪化すると記載されている。また、使用されるアクリルゴムの重量平均分子量（Ｍｗ）は、２００，０００～１，０００，０００であり、重量平均分子量（Ｍｗ）が１，０００，０００を超えるとアクリルゴムの粘弾性が高くなりすぎて好ましくないこと記載されている。しかしながら、バンバリーなどの加工性を改良する手法については記載されていない。 Further, in Patent Document 4 (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. ([η] 100 ° C.). Is 3,500 Pa · s or less, and the ratio of the complex viscosity at 60 ° C. ([η] 60 ° C.) to the complex viscosity at 100 ° C. ([η] 100 ° C.) ([η] 100 ° C./[η] 60 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 amount of gel, which is a THF (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. , It is stated that the extrudability deteriorates when the gel 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 is no description of a method for improving workability such as Banbury.
特開２００６－３２８２３９号公報Japanese Unexamined Patent Publication No. 2006-328239 国際公開第２０１８／１１６８２８号パンフレットInternational Publication No. 2018/116828 Pamphlet 特許第３５９９９６２号公報Japanese Patent No. 3599962 国際公開第２０１８／１４３１０１号パンフレットInternational Publication No. 2018/143101 Pamphlet
　本発明は、かかる実状に鑑みてなされたものであり、保存安定性と加工性に優れるアクリルゴムベール、その製造方法、アクリルゴムベールを含んでなるゴム混合物、及びそのゴム架橋物を提供することを目的とする。 The present invention has been made in view of such circumstances, and provides an acrylic rubber veil having excellent storage stability and processability, a method for producing the same, a rubber mixture containing the acrylic rubber veil, and a crosslinked rubber product thereof. With the goal.
　本発明者らは、上記課題に鑑み鋭意研究した結果、反応性基を有し、分子量、メチルエチルケトン不溶解のゲル量及び比重が特定であるアクリルゴムベールが保存安定性とバンバリー等混錬時の加工性に高度に優れることを見出した。 As a result of diligent research in view of the above problems, the present inventors have found that an acrylic rubber veil having a reactive group and having a specific molecular weight, an amount of gel insoluble in methyl ethyl ketone and a specific gravity is suitable for storage stability and during kneading such as Banbury. We have found that it is highly workable.
　本発明者らは、また、アクリルゴムベールのメチルエチルケトン不溶解分のゲル量バラツキ、高分子量領域を重点にした分子量分布、特定温度における複素粘性率及び灰分量を特定にすることで保存安定性と加工性が更に改善できることを見出した。 The present inventors also obtain storage stability by specifying the gel amount variation of the methyl ethyl ketone insoluble portion of the acrylic rubber veil, the molecular weight distribution focusing on the high molecular weight region, the complex viscosity at a specific temperature, and the ash content. It was found that the workability can be further improved.
　本発明者らは、また、反応性基含有単量体を含む単量体成分を乳化重合し凝固反応で生成した含水クラムを洗浄後にスクリュー型押出機で特定含水量まで乾燥しベール化することで保存安定性と加工性が高度に優れるアクリルゴムベールが製造できることを見出した。 The present inventors also perform emulsion polymerization of a monomer component containing a reactive group-containing monomer, wash the hydrous crumb produced by the coagulation reaction, and then dry it to a specific hydrous content with a screw extruder to bale it. It was found that an acrylic rubber bale with high storage stability and workability can be produced.
　本発明者らは、また、アクリルゴムのゲル量は、製造工程でコントロールするのが非常に困難で製造されるアクリルゴムベールのメチルエチルケトン不溶解分のゲル量を大きく変化しバンバリー混錬などの最適混錬時間をバラツカさせてしまうためにゴム混合物やゴム架橋物の物性を損ねていることがわかった。本発明においては、重合転化率を高めて乳化重合するとアクリルゴム中のメチルエチルケトン不溶解分のゲル量が急増し加工性を悪化させるが、スクリュー型押出機を用いて特定含水量まで乾燥し実質的に水分を含まない状態でアクリルゴムを溶融混錬することで急増したメチルエチルケトン不溶解分のゲル量が消失し、製造されるアクリルゴムベールの加工性が高度に改善され且つ加工性のバラツキが少なく安定化することを見出した。 We also found that the gel amount of acrylic rubber is very difficult to control in the manufacturing process, and the gel amount of the methyl ethyl ketone insoluble content of the acrylic rubber veil to be manufactured is greatly changed, which is optimal for Banbury kneading and the like. It was found that the physical properties of the rubber mixture and the rubber crosslinked product were impaired because the kneading time varied. In the present invention, when the polymerization conversion rate is increased and emulsion polymerization is carried out, the gel amount of the methyl ethyl ketone insoluble matter in the acrylic rubber rapidly increases and the processability is deteriorated, but it is substantially dried to a specific water content using a screw type extruder. By melt-kneading acrylic rubber in a state where it does not contain water, the gel amount of the methyl ethyl ketone insoluble component that rapidly increased disappears, the processability of the produced acrylic rubber veil is highly improved, and there is little variation in processability. Found to stabilize.
　本発明者らは、また、アクリルゴムベールのゲルは、使用する溶媒のＳＰ値などにより全く異なり、例えば、アクリルゴムのテトラヒドロフラン不溶解分のゲル量とメチルエチルケトン不溶解分のゲル量では全く相関せず、そのゲルの特性も異なっていること及びアクリルゴムのメチルエチルケトン不溶解分のゲル量がバンバリー等の混錬時の加工性に相関していることを見出した。 In addition, the present inventors completely differ in the gel of the acrylic rubber veil depending on the SP value of the solvent used, for example, the gel amount of the tetrahydrofuran-insoluble portion of the acrylic rubber and the gel amount of the methyl ethyl ketone insoluble portion are completely correlated. However, it was found that the characteristics of the gel are also different and that the amount of gel in which the methyl ethyl ketone insoluble component of acrylic rubber is insoluble correlates with the processability at the time of kneading such as Banbury.
　本発明者らは、また、含水クラムから水分を絞り出す脱水工程を設けること及び乳化重合液の凝固方法を特定することでアクリルゴムベール中の灰分量を低減させるとともに、耐水性と保存安定性を高め且つ加工性のバラツキを低減していることを見出した。 The present inventors also reduced the amount of ash in the acrylic rubber veil by providing a dehydration step for squeezing water from the hydrous crumb and specifying the coagulation method of the emulsion polymerization solution, and also improved water resistance and storage stability. It was found that it was enhanced and the variation in workability was reduced.
　本発明者らは、これらの知見に基づいて本発明を完成させるに至ったものである。 The present inventors have completed the present invention based on these findings.
　かくして本発明によれば、反応性基を有する重量平均分子量（Ｍｗ）が１００，０００～５，０００，０００でアクリルゴムからなり、メチルエチルケトン不溶解なゲル量が５０重量％以下で比重が０．８以上であるアクリルゴムベールが提供される。 Thus, according to the present invention, the weight average molecular weight (Mw) having a reactive group is 100,000 to 5,000,000, the gel is made of acrylic rubber, the amount of gel insoluble in methyl ethyl ketone is 50% by weight or less, and the specific gravity is 0. Acrylic rubber veils of 8 or more are provided.
　本発明のアクリルゴムベールにおいて、メチルエチルケトン不溶解分のゲル量が、２０重量％以下であることが好ましい。 In the acrylic rubber veil of the present invention, the gel amount of the insoluble methyl ethyl ketone is preferably 20% by weight or less.
　本発明のアクリルゴムベールにおいて、アクリルゴムベールのメチルエチルケトン不溶解分のゲル量を任意に２０点測定したときの値が、（平均値－５）～（平均値＋５）重量％の範囲内に測定した２０点全てが入ることが好ましい。なお、（平均値－５）～（平均値＋５）重量％の範囲とは、例えば測定したメチルエチルケトン不溶解分のゲル量の平均値が２０重量％であった場合には１５～２５重量％の範囲を意味する。本明細書では、当該範囲を「平均値±５の範囲」のように表記する。当該範囲には下限値が含まれてもよく含まれなくてもよい。同様に、当該範囲には上限値が含まれてもよく含まれなくてもよい。 In the acrylic rubber bale of the present invention, the value when the gel amount of the methyl ethyl ketone insoluble portion of the acrylic rubber bale is arbitrarily measured at 20 points is measured within the range of (mean value -5) to (mean value + 5)% by weight. It is preferable that all 20 points are included. The range of (mean value -5) to (mean value + 5)% by weight is, for example, 15 to 25% by weight when the average value of the measured gel amount of the insoluble methyl ethyl ketone is 20% by weight. Means a range. In the present specification, the range is expressed as "a range of mean ± 5". The range may or may not include a lower limit. Similarly, the range may or may not include an upper limit.
　本発明のアクリルゴムベールにおいて、重量平均分子量（Ｍｗ）が、１，０００，０００～５，０００，０００の範囲であることが好ましい。 In the acrylic rubber veil of the present invention, the weight average molecular weight (Mw) is preferably in the range of 1,000,000 to 5,000,000.
　本発明のアクリルゴムベールにおいて、ｚ平均分子量（Ｍｚ）と重量平均分子量（Ｍｗ）との比（Ｍｚ／Ｍｗ）が、１．３以上であることが好ましい。 In the acrylic rubber veil of the present invention, the ratio (Mz / Mw) of the z average molecular weight (Mz) to the weight average molecular weight (Mw) is preferably 1.3 or more.
　本発明のアクリルゴムベールにおいて、１００℃における複素粘性率（［η］１００℃）が、１，５００～６，０００Ｐａ・ｓの範囲であることが好ましい。 In the acrylic rubber veil of the present invention, the complex viscosity ([η] 100 ° C.) at 100 ° C. is preferably in the range of 1,500 to 6,000 Pa · s.
　本発明のアクリルゴムベールにおいて、１００℃における複素粘性率（［η］１００℃）と６０℃における複素粘性率（［η］６０℃）との比（［η］１００℃／［η］６０℃）が、０．５以上であることが好ましい。 In the acrylic rubber veil of the present invention, the ratio of the complex viscosity at 100 ° C. ([η] 100 ° C.) to the complex viscosity at 60 ° C. ([η] 60 ° C.) ([η] 100 ° C./[η] 60 ° C. ) Is preferably 0.5 or more.
　本発明のアクリルゴムベールにおいて、１００℃における複素粘性率（［η］１００℃）と６０℃における複素粘性率（［η］６０℃）との比（［η］１００℃／［η］６０℃）が、０．８以上であることがさらに好ましい。 In the acrylic rubber veil of the present invention, the ratio of the complex viscosity at 100 ° C. ([η] 100 ° C.) to the complex viscosity at 60 ° C. ([η] 60 ° C.) ([η] 100 ° C./[η] 60 ° C. ) Is more preferably 0.8 or more.
　本発明のアクリルゴムベールにおいて、ｐＨが、６以下であることが好ましい。 In the acrylic rubber veil of the present invention, the pH is preferably 6 or less.
　本発明のアクリルゴムベールにおいて、灰分が、０．５重量％以下であることが好ましい。 In the acrylic rubber veil of the present invention, the ash content is preferably 0.5% by weight or less.
　本発明のアクリルゴムベールにおいて、灰分中のナトリウム、イオウ、カルシウム、マグネシウム及びリンからなる群から選ばれる少なくとも１種の元素の含有量が、８０重量％以上であることが好ましい。 In the acrylic rubber veil of the present invention, the content of at least one element selected from the group consisting of sodium, sulfur, calcium, magnesium and phosphorus in the ash is preferably 80% by weight or more.
　本発明によれば、また、（メタ）アクリル酸エステルと反応性基含有単量体とを含む単量体成分を水と乳化剤とでエマルジョン化し重合触媒存在下に乳化重合し乳化重合液を得る乳化重合工程と、得られた乳化重合液と凝固液を接触させて含水クラムを生成する凝固工程と、生成した含水クラムを洗浄する洗浄工程と、洗浄した含水クラムを、脱水スリットを有する脱水バレルと減圧下の乾燥バレルと先端部にダイを有するスクリュー型押出機を用いて脱水バレルで含水量１～４０重量％まで脱水した後に乾燥バレルで含水量１重量％未満まで乾燥してシート状乾燥ゴムをダイから押し出す脱水・乾燥・成形工程と押し出されたシート状乾燥ゴムを積層してベール化するベール化工程と、を含むアクリルゴムベールの製造方法を提供することができる。 According to the present invention, a monomer component containing a (meth) acrylic acid ester and a reactive group-containing monomer is emulsionized with water and an emulsifier and emulsion-polymerized in the presence of a polymerization catalyst to obtain an emulsion polymerization solution. An emulsion polymerization step, a coagulation step of bringing the obtained emulsion polymerization solution into contact with a coagulating liquid to generate a hydrous crumb, a cleaning step of washing the produced hydrous crumb, and a dehydration barrel having a dehydration slit for the washed hydrous crumb. After dehydration to a moisture content of 1 to 40% by weight in a dehydration barrel using a drying barrel under reduced pressure and a screw type extruder having a die at the tip, the drying barrel is dried to a moisture content of less than 1% by weight and dried in a sheet form. It is possible to provide a method for producing an acrylic rubber bale, which includes a dehydration / drying / molding step of extruding rubber from a die and a bale step of laminating and bale the extruded sheet-shaped dried rubber.
　本発明によれば、また、前記アクリルゴムベールに、充填剤及び架橋剤を混合してなるゴム混合物が提供される。 According to the present invention, there is also provided a rubber mixture obtained by mixing a filler and a cross-linking agent with the acrylic rubber veil.
　本発明によれば、さらに、前記ゴム混合物を架橋してなるゴム架橋物が提供される。 According to the present invention, a rubber crosslinked product obtained by cross-linking the rubber mixture is further provided.
　本発明によれば、保存安定性とバンバリー等混錬時の加工性に優れるアクリルゴムベール、その製造方法、該アクリルゴムベールを混合してなるゴム混合物及びそれを架橋してなるゴム架橋物が提供される。 According to the present invention, an acrylic rubber veil having excellent storage stability and processability during kneading such as Banbury, a method for producing the same, a rubber mixture obtained by mixing the acrylic rubber veil, and a rubber crosslinked product obtained by cross-linking the acrylic rubber veil. Provided.
本発明の一実施形態に係るアクリルゴムベールの製造に用いられるアクリルゴム製造システムの一例を模式的に示す図である。It is a figure which shows typically an example of the acrylic rubber manufacturing system used for manufacturing the acrylic rubber veil which concerns on one Embodiment of this invention. 図１のスクリュー型押出機の構成を示す図である。It is a figure which shows the structure of the screw type extruder of FIG. 図１の冷却装置として用いられる搬送式冷却装置の構成を示す図である。It is a figure which shows the structure of the transport type cooling apparatus used as the cooling apparatus of FIG.
　本発明のアクリルゴムベールは、反応性基を有する重量平均分子量（Ｍｗ）が１００，０００～５，０００，０００でアクリルゴムからなり、メチルエチルケトン不溶解なゲル量が５０重量％以下で比重が０．８以上であることを特徴とする。 The acrylic rubber veil of the present invention is made of acrylic rubber having a reactive group and a weight average molecular weight (Mw) of 100,000 to 5,000,000, and the amount of gel insoluble in methyl ethyl ketone is 50% by weight or less and the specific gravity is 0. It is characterized by being 0.8 or more.
　＜単量体成分＞
　本発明のアクリルゴムベールは、反応性基を有するアクリルゴムからなる。 <Monomer component>
The acrylic rubber veil of the present invention is made of acrylic rubber having a reactive group.
　反応性基としては、格別な限定はなく使用目的に応じて適宜選択されるが、好ましくは、カルボキシル基、エポキシ基及びハロゲン基からなる群から選ばれる少なくとも１種の官能基、カルボキシル基、エポキシ基及び塩素原子からなる群から選ばれる少なくとも１種の官能基であるときにアクリルゴムベールの架橋特性を高度に改善でき好適である。かかる反応性基を有するアクリルゴムとしては、アクリルゴムに後反応で反応性基を付与してもよいが、好ましくは反応性基含有単量体を共重合したものが好ましい。 The reactive group is appropriately selected according to the intended use without any particular limitation, but preferably at least one functional group, carboxyl group, or epoxy group selected from the group consisting of a carboxyl group, an epoxy group, and a halogen group. When it is at least one functional group selected from the group consisting of a group and a chlorine atom, the cross-linking property of the acrylic rubber veil can be highly 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.
　本発明のアクリルゴムベールを構成するアクリルゴムとしては、また、(メタ)アクリル酸エステルを含むものが好ましく、（メタ）アクリル酸アルキルエステル及び（メタ）アクリル酸アルコキシアルキルエステルからなる群から選ばれる少なくとも１種の（メタ）アクリル酸エステルを含むものであることが好ましい。 The acrylic rubber constituting the acrylic rubber veil of the present invention preferably contains (meth) acrylic acid ester, and is selected from the group consisting of (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester. It preferably contains at least one (meth) acrylic acid ester.
　好ましい反応性基を有するアクリルゴムの具体例としては、（メタ）アクリル酸アルキルエステル及び（メタ）アクリル酸アルコキシアルキルエステルからなる群から選ばれる少なくとも１種の（メタ）アクリル酸エステル、反応性基含有単量体、及び必要に応じて共重合可能なその他の単量体からなるものが挙げられる。 Specific examples of the acrylic rubber having a preferable reactive group 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, and a reactive group. Examples thereof include those composed of a contained monomer and other monomers copolymerizable as required.
　（メタ）アクリル酸アルキルエステルとしては、格別な限定はないが、通常炭素数が１～１２のアルキル基を有する（メタ）アクリル酸アルキルエステル、好ましくは炭素数１～８のアルキル基を有する（メタ）アクリル酸アルキルエステル、より好ましくは炭素数２～６のアルキル基を有する（メタ）アクリル酸アルキルエステルである。 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.
　（メタ）アクリル酸アルキルエステルの具体例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸シクロヘキシルなどが挙げられ、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－ブチルが好ましく、アクリル酸エチル、アクリル酸ｎ－ブチルがより好ましい。 Specific examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n- (meth) acrylic acid. Butyl, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate and the like, ethyl (meth) acrylate, (meth) acrylate n-butyl is preferable, and ethyl acrylate and n-butyl acrylate are more preferable.
　（メタ）アクリル酸アルコキシアルキルエステルとしては、格別な限定はないが、通常２～１２のアルコキシアルキル基を有する（メタ）アクリル酸アルコキシアルキルエステル、好ましくは２～８のアルコキシアルキル基を有する（メタ）アクリル酸アルコキシアルキルエステル、より好ましくは炭素数２～６のアルコキシアルキル基を有する（メタ）アクリル酸アルコキシエステルである。 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.
　（メタ）アクリル酸アルコキシアルキルエステルの具体例としては、（メタ）アクリル酸メトキシメチル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸メトキシプロピル、（メタ）アクリル酸メトキシブチル、（メタ）アクリル酸エトキシメチル、（メタ）アクリル酸エトキシエチル、（メタ）アクリル酸プロポキシエチル、（メタ）アクリル酸ブトキシエチルなどが挙げられる。これらの中でも、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチルなどが好ましく、アクリル酸メトキシエチル、アクリル酸エトキシエチルがより好ましい。 Specific examples of the (meth) acrylic acid alkoxyalkyl ester 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. Among these, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and the like are preferable, and methoxyethyl acrylate and ethoxyethyl acrylate are more preferable.
　これら（メタ）アクリル酸アルキルエステル及び（メタ）アクリル酸アルコキシアルキルエステルからなる群から選ばれる少なくとも１種の（メタ）アクリル酸エステルは、それぞれ単独で、あるいは２種以上が組み合わせて用いられ、アクリルゴム中の割合は、通常５０重量％以上、好ましくは７０～９９．９重量％、より好ましくは８０～９９．５重量％、最も好ましくは８７～９９重量％である。単量体成分中の（メタ）アクリル酸エステル量が、過度に少ないと得られるアクリルゴムの耐候性、耐熱性、及び耐油性が低下するおそれがあり好ましくない。 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% by weight or more, 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.
　反応性基含有単量体としては、格別な限定はなく使用目的に応じて適宜選択されるが、カルボキシル基、エポキシ基及びハロゲン基からなる群から選ばれる少なくとも１種の官能基を有する単量体が好ましい。 The reactive group-containing monomer is appropriately selected according to the intended use without any particular limitation, but is a single amount having at least one functional group selected from the group consisting of a carboxyl group, an epoxy group and a halogen group. The body is preferred.
　カルボキシル基を有する単量体としては、格別な限定はないが、エチレン性不飽和カルボン酸を好適に用いることができる。エチレン性不飽和カルボン酸としては、例えば、エチレン性不飽和モノカルボン酸、エチレン性不飽和ジカルボン酸、エチレン性不飽和ジカルボン酸モノエステルなどが挙げられ、これらの中でも特にエチレン性不飽和ジカルボン酸モノエステルがアクリルゴムをゴム架橋物とした場合の耐圧縮永久歪み特性をより高めることができ好ましい。 The monomer having a carboxyl group is not particularly limited, but an ethylenically unsaturated carboxylic acid can be preferably used. Examples of 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.
　エチレン性不飽和モノカルボン酸としては、格別な限定はないが、炭素数３～１２のエチレン性不飽和モノカルボン酸が好ましく、例えば、アクリル酸、メタクリル酸、α－エチルアクリル酸、クロトン酸、ケイ皮酸などを挙げることができる。 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, α-ethylacrylic acid, crotonic acid, and the like. Examples thereof include crotonic acid.
　エチレン性不飽和ジカルボン酸としては、格別な限定はないが、炭素数４～１２のエチレン性不飽和ジカルボン酸が好ましく、例えば、フマル酸、マレイン酸などのブテンジオン酸、イタコン酸、シトラコン酸などを挙げることができる。なお、エチレン性不飽和ジカルボン酸は、無水物として存在しているものも含まれる。 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.
　エチレン性不飽和ジカルボン酸モノエステルとしては、格別な限定はないが、通常、炭素数４～１２のエチレン性不飽和ジカルボン酸と炭素数１～１２のアルキルモノエステル、好ましくは炭素数４～６のエチレン性不飽和ジカルボン酸と炭素数２～８のアルキルモノエステル、より好ましくは炭素数４のブテンジン酸の炭素数２～６のアルキルモノエステルである。 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. Ethylene unsaturated dicarboxylic acid and an alkyl monoester having 2 to 8 carbon atoms, more preferably an alkyl monoester having 2 to 6 carbon atoms of buthenic acid having 4 carbon atoms.
　エチレン性不飽和ジカルボン酸モノエステルの具体例としては、フマル酸モノメチル、フマル酸モノエチル、フマル酸モノｎ－ブチル、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノｎ－ブチル、フマル酸モノシクロペンチル、フマル酸モノシクロヘキシル、フマル酸モノシクロヘキセニル、マレイン酸モノシクロペンチル、マレイン酸モノシクロヘキシルなどのブテンジオン酸モノアルキルエステル；イタコン酸モノメチル、イタコン酸モノエチル、イタコン酸モノｎ－ブチル、イタコン酸モノシクロヘキシルなどのイタコン酸モノアルキルエステル；などが挙げられ、これらの中でもフマル酸モノｎ－ブチル、マレイン酸モノｎ－ブチルが好ましく、フマル酸モノｎ－ブチルが特に好ましい。 Specific examples of the ethylenically unsaturated dicarboxylic acid monoester 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.
　エポキシ基を有する単量体としては、例えば、（メタ）アクリル酸グリシジルなどのエポキシ基含有（メタ）アクリル酸エステル；アリルグリシジルエーテル、ビニルグリシジルエーテルなどのエポキシ基含有ビニルエーテル；などが挙げられる。 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.
　ハロゲン基を有する単量体としては、例えば、ハロゲン含有飽和カルボン酸の不飽和アルコールエステル、（メタ）アクリル酸ハロアルキルエステル、（メタ）アクリル酸ハロアシロキシアルキルエステル、（メタ）アクリル酸（ハロアセチルカルバモイルオキシ）アルキルエステル、ハロゲン含有不飽和エーテル、ハロゲン含有不飽和ケトン、ハロメチル基含有芳香族ビニル化合物、ハロゲン含有不飽和アミド、ハロアセチル基含有不飽和単量体などが挙げられる。 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.
　ハロゲン含有飽和カルボン酸の不飽和アルコールエステルとしては、例えば、クロロ酢酸ビニル、２－クロロプロピオン酸ビニル、クロロ酢酸アリルなどが挙げられる。（メタ）アクリル酸ハロアルキルエステルとしては、例えば、（メタ）アクリル酸クロロメチル、（メタ）アクリル酸１－クロロエチル、（メタ）アクリル酸２－クロロエチル、（メタ）アクリル酸１，２－ジクロロエチル、（メタ）アクリル酸２－クロロプロピル、（メタ）アクリル酸３－クロロプロピル、（メタ）アクリル酸２，３－ジクロロプロピルなどが挙げられる。（メタ）アクリル酸ハロアシロキシアルキルエステルとしては、例えば、（メタ）アクリル酸２－（クロロアセトキシ）エチル、（メタ）アクリル酸２－（クロロアセトキシ）プロピル、（メタ）アクリル酸３－（クロロアセトキシ）プロピル、（メタ）アクリル酸３－（ヒドロキシクロロアセトキシ）プロピルなどが挙げられる。（メタ）アクリル酸（ハロアセチルカルバモイルオキシ）アルキルエステルとしては、例えば、（メタ）アクリル酸２－（クロロアセチルカルバモイルオキシ）エチル、（メタ）アクリル酸３－（クロロアセチルカルバモイルオキシ）プロピルなどが挙げられる。ハロゲン含有不飽和エーテルとしては、例えば、クロロメチルビニルエーテル、２－クロロエチルビニルエーテル、３－クロロプロピルビニルエーテル、２－クロロエチルアリルエーテル、３－クロロプロピルアリルエーテルなどが挙げられる。ハロゲン含有不飽和ケトンとしては、例えば、２－クロロエチルビニルケトン、３－クロロプロピルビニルケトン、２－クロロエチルアリルケトンなどが挙げられる。ハロメチル基含有芳香族ビニル化合物としては、例えば、ｐ－クロロメチルスチレン、ｍ－クロロメチルスチレン、ｏ－クロロメチルスチレン、ｐ－クロロメチル－α－メチルスチレンなどが挙げられる。ハロゲン含有不飽和アミドとしては、例えば、Ｎ－クロロメチル（メタ）アクリルアミドなどが挙げられる。ハロアセチル基含有不飽和単量体としては、例えば、３－（ヒドロキシクロロアセトキシ）プロピルアリルエーテル、ｐ－ビニルベンジルクロロ酢酸エステルなどが挙げられる。 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. Examples of the halogen-containing unsaturated ketone include 2-chloroethyl vinyl ketone, 3-chloropropyl vinyl ketone, 2-chloroethyl allyl ketone and the like. Examples of the halomethyl group-containing aromatic vinyl compound include p-chloromethylstyrene, m-chloromethylstyrene, o-chloromethylstyrene, and p-chloromethyl-α-methylstyrene. Examples of the halogen-containing unsaturated amide include N-chloromethyl (meth) acrylamide. Examples of the haloacetyl group-containing unsaturated monomer include 3- (hydroxychloroacetoxy) propylallyl ether and p-vinylbenzylchloroacetic acid ester.
　これらの反応性基含有単量体は、それぞれ単独で、あるいは２種以上が組み合わせて用いられ、アクリルゴム中の割合は、通常０．０１～２０重量％、好ましくは０．１～１０重量％、より好ましくは０．５～５重量％、最も好ましくは１～３重量％である。 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.
　必要に応じて用いられるその他の単量体としては、上記単量体と共重合可能であれば格別な限定はなく、例えば、芳香族ビニル、エチレン性不飽和ニトリル、アクリルアミド系単量体、その他のオレフィン系単量体などが挙げられる。芳香族ビニルとしては、例えば、スチレン、α－メチルスチレン、ジビニルベンゼンなどが挙げられる。エチレン性不飽和ニトリルとしては、例えば、アクリロニトリル、メタクリロニトリルなどが挙げられる。アクリルアミド系単量体としては、例えば、アクリルアミド、メタクリルアミドなどが挙げられる。その他のオレフィン系単量体としては、例えば、エチレン、プロピレン、酢酸ビニル、エチルビニルエーテル、ブチルビニルエーテルなどが挙げられる。 The other monomer used as needed is not particularly limited as long as it can be copolymerized with the above-mentioned monomer. For example, aromatic vinyl, ethylenically unsaturated nitrile, acrylamide-based monomer, and the like. Olefin-based monomers and the like. Examples of the aromatic vinyl include styrene, α-methylstyrene, divinylbenzene and the like. Examples of the ethylenically unsaturated nitrile include acrylonitrile and methacrylonitrile. Examples of the acrylamide-based monomer include acrylamide and methacrylamide. Examples of other olefin-based monomers include ethylene, propylene, vinyl acetate, ethyl vinyl ether, and butyl vinyl ether.
　これらのその他の単量体は、それぞれ単独で、あるいは２種以上を組み合わせられて用いられ、アクリルゴム中の割合は、通常０～３０重量％、好ましくは０～２０重量％、より好ましくは０～１５重量％、最も好ましくは０～１０重量％の範囲である。 These other monomers are used alone or in combination of two or more, and 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.
　＜アクリルゴム＞
　本発明のアクリルゴムベールを構成するアクリルゴムは、反応性基を有することを特徴とする。 <Acrylic rubber>
The acrylic rubber constituting the acrylic rubber veil of the present invention is characterized by having a reactive group.
　反応性基の含有量は、使用目的に応じて適宜選択されればよいが、反応性基自体の重量割合で、通常０．００１～５重量％、好ましくは０．０１～３重量％、より好ましくは０．０５～１重量％、特に好ましくは０．１～０．５重量％の範囲あるときに加工性、強度特性、耐圧縮永久歪み特性、耐油性、耐寒性、及び耐水性などの特性が高度にバランスされ好適である。 The content of the reactive group may be appropriately selected according to the purpose of use, but is usually 0.001 to 5% by weight, preferably 0.01 to 3% by weight, based on the weight ratio of the reactive group itself. Workability, strength characteristics, compression set resistance, oil resistance, cold resistance, water resistance, etc. are preferably in the range of 0.05 to 1% by weight, particularly preferably 0.1 to 0.5% by weight. The characteristics are highly balanced and suitable.
　本発明のアクリルゴムベールを構成するアクリルゴムの具体例としては、（メタ）アクリル酸アルキルエステル及び（メタ）アクリル酸アルコキシアルキルエステルからなる群から選ばれる少なくとも１種の（メタ）アクリル酸エステル、反応性基含有単量体、及び必要に応じてその他の共重合可能な単量体からなり、それぞれのアクリルゴム中の割合は、（メタ）アクリル酸アルキルエステル及び（メタ）アクリル酸アルコキシアルキルエステルからなる群から選ばれる少なくとも１種の（メタ）アクリル酸エステル由来の結合単位が、通常５０～９９．９９重量％、好ましくは７０～９９．９重量％、より好ましくは８０～９９．５重量％、特に好ましくは８７～９９重量％の範囲であり、反応性基含有単量体由来の結合単位が、通常０．０１～２０重量％、好ましくは０．１～１０重量％、より好ましくは０．５～５重量％、特に好ましくは１～３重量％の範囲であり、その他の単量体由来の結合単位が、通常０～３０重量％、好ましくは０～２０重量％、より好ましくは０～１５重量％、特に好ましくは０～１０重量％の範囲である。アクリルゴムのこれらの単量体由来の結合単位をこの範囲にすることにより本発明の目的が高度に達成できるとともにアクリルゴムベールを架橋物としたときに耐水性や耐圧縮永久歪み特性が格段に改善され好適である。 Specific examples of the acrylic rubber constituting the acrylic rubber veil 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. %, Especially preferably in the range of 87 to 99% by weight, and the binding unit derived from the reactive group-containing monomer is usually 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more preferably. It is in the range of 0.5 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, more preferably. It is in the range of 0 to 15% by weight, particularly preferably 0 to 10% by weight. By setting the bonding unit derived from these monomers of acrylic rubber to this range, the object of the present invention can be highly achieved, and when the acrylic rubber veil is used as a crosslinked product, water resistance and compression resistance permanent strain characteristics are remarkably improved. It is improved and suitable.
　本発明のアクリルゴムベールを構成するアクリルゴムの重量平均分子量（Ｍｗ）は、ＧＰＣ－ＭＡＬＳで測定される絶対分子量で、１００，０００～５，０００，０００、好ましくは５００，０００～５，０００，０００、より好ましくは１，０００，０００～５，０００，０００、特に好ましくは１，１００，０００～３，５００，０００、最も好ましくは１，２００，０００～２，５００，０００の範囲であるときにアクリルゴムベールの混合時の加工性、強度特性、及び耐圧縮永久歪み特性が高度にバランスされ好適である。 The weight average molecular weight (Mw) of the acrylic rubber constituting the acrylic rubber veil 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. 000, more preferably 1,000,000 to 5,000,000, particularly preferably 1,100,000 to 3,500,000, most preferably in the range of 1,200,000 to 2,500,000. At one point, the processability, strength characteristics, and compression-resistant permanent strain characteristics of the acrylic rubber bale when mixed are highly balanced and suitable.
　本発明のアクリルゴムベールを構成するアクリルゴムのｚ平均分子量（Ｍｚ）と重量平均分子量（Ｍｗ）との比（Ｍｚ／Ｍｗ）は、格別限定されるものではないが、ＧＰＣ－ＭＡＬＳで測定される絶対分子量分布で、通常１．３以上、好ましくは１．４～５、より好ましくは１．５～２の範囲であるときにアクリルゴムベールの加工性と強度特性が高度にバランスされ且つ保存時の物性変化を緩和でき好適である。 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 veil of the present invention is not particularly limited, but is measured by GPC-MALS. The processability and strength characteristics of the acrylic rubber veil are highly balanced and preserved when the absolute molecular weight distribution is usually in the range of 1.3 or more, preferably 1.4 to 5, more preferably 1.5 to 2. It is suitable because it can alleviate changes in physical properties over time.
　本発明のアクリルゴムベールを構成するアクリルゴムのガラス転移温度（Ｔｇ）は、格別限定されるものではないが、通常２０℃以下、好ましくは１０℃以下、より好ましくは０℃以下である。アクリルゴムのガラス転移温度（Ｔｇ）の下限値は、格別限定されるものではないが、通常－８０℃以上、好ましくは－６０℃以上、より好ましくは－４０℃以上である。ガラス転移温度を前記下限以上とすることにより耐油性と耐熱性により優れたものとすることができ、前記上限以下とすることにより耐寒性と加工性により優れたものとすることができる。 The glass transition temperature (Tg) of the acrylic rubber constituting the acrylic rubber veil 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) of acrylic rubber is not particularly limited, but is usually −80 ° C. or higher, preferably −60 ° C. or higher, and more preferably −40 ° C. or higher. By setting the glass transition temperature to the lower limit or higher, the oil resistance and heat resistance can be improved, and by setting the glass transition temperature to the upper limit or lower, the cold resistance and workability can be improved.
　本発明のアクリルゴムベール中のアクリルゴムの含有量は、使用目的に応じて適宜選択されるが、通常９５重量％以上、好ましくは９７重量％以上、より好ましくは９８重量％以上である。 The content of acrylic rubber in the acrylic rubber veil of the present invention is appropriately selected according to the purpose of use, but is usually 95% by weight or more, preferably 97% by weight or more, and more preferably 98% by weight or more.
　＜アクリルゴムベール＞
　本発明のアクリルゴムベールは、上記アクリルゴムからなり、且つメチルエチルケトン不溶解分のゲル量と比重が特定であることを特徴とする。 <Acrylic rubber veil>
The acrylic rubber veil of the present invention is made of the above acrylic rubber, and is characterized in that the gel amount and specific gravity of the insoluble methyl ethyl ketone are specified.
　本発明のアクリルゴムベールの大きさは、格別限定されるものではないが、幅が通常１００～８００ｍｍ、好ましくは２００～５００ｍｍ、より好ましくは２５０～４５０ｍｍの範囲で、長さが通常３００～１，２００ｍｍ、好ましくは４００～１，０００ｍｍ、より好ましくは５００～８００ｍｍの範囲で、高さが通常５０～５００ｍｍ、好ましくは１００～３００ｍｍ、より好ましくは１５０～２５０ｍｍの範囲である。 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.
　本発明のアクリルゴムベールのゲル量は、メチルエチルケトンの不溶解分で、５０重量％以下、好ましくは３０重量％以下、より好ましくは２０重量％以下、特に好ましくは１０重量％以下、最も好ましくは５重量％以下であるときに、加工性が高度に改善され好適である。なお、本発明のアクリルゴムベール中のメチルエチルケトン不溶解分であるゲル量は、使用する溶媒により特性が異なり、特にＴＨＦ（テトラハイドロフラン）不溶解のゲル量とは相関していなかった。 The gel amount of the acrylic rubber veil 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, particularly preferably 10% by weight or less, and most preferably 5. When it is less than% by weight, the workability is highly improved and is suitable. The amount of gel, which is the insoluble matter of methyl ethyl ketone in the acrylic rubber veil of the present invention, has different characteristics depending on the solvent used, and does not particularly correlate with the amount of THF (tetrahydrofuran) insoluble gel.
　本発明のアクリルゴムベールのメチルエチルケトン不溶解分のゲル量を任意に２０点測定したときの値は、格別限定されるものではないが、平均値±５の範囲内に２０点全てが入る、好ましくは平均値±３の範囲内に２０点全てが入るときに加工性バラツキが無くゴム混合物やゴム架橋物の諸物性が安定化されて好適である。 The value when the gel amount of the methyl ethyl ketone insoluble portion of the acrylic rubber veil of the present invention is arbitrarily measured at 20 points is not particularly limited, but it is preferable that all 20 points are within the range of the average value ± 5. Is suitable because there is no workability variation and various physical properties of the rubber mixture and the rubber crosslinked product are stabilized when all 20 points are within the range of the average value of ± 3.
　本発明のアクリルゴムベールの比重は、格別限定はないが、通常０．８以上、好ましくは０．８～１．４、より好ましくは、０．９～１．３、特に好ましくは０．９５～１．２５、最も好ましくは１．０～１．２の範囲であるときに保存安定性が高度に優れ好適である。アクリルゴムベールの比重が過度に小さいときは、アクリルゴムベール中に巻き込まれる空気量が多いことを示し酸化劣化など含めて保存安定性に大きく影響し好ましくない。 The specific gravity of the acrylic rubber veil of the present invention is not particularly limited, but is usually 0.8 or more, preferably 0.8 to 1.4, more preferably 0.9 to 1.3, and particularly preferably 0.95. When the range is 1.25, most preferably 1.0 to 1.2, the storage stability is highly excellent and suitable. When the specific gravity of the acrylic rubber veil is excessively small, it indicates that the amount of air entrained in the acrylic rubber veil is large, which greatly affects the storage stability including oxidative deterioration, which is not preferable.
　本発明のアクリルゴムベールの含水量は、格別な限定はないが、通常１重量％未満、好ましくは０．８重量％以下、より好ましくは０．６重量％以下であるときに加硫特性が最適化され耐熱性や耐水性などの特性が高度に優れ好適である。 The water content of the acrylic rubber veil of the present invention is not particularly limited, but the vulcanization property 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 optimized and has excellent properties such as heat resistance and water resistance, and is suitable.
　本発明のアクリルゴムベールのｐＨは、格別な限定はないが、通常６以下、好ましくは２～６、より好ましくは２．５～５．５、特に好ましくは３～５の範囲であるときに保存安定性が高度に改善され好適である。 The pH of the acrylic rubber veil 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.
　本発明のアクリルゴムベールの灰分量は．格別限定されるものではないが、通常０．５重量％以下、好ましくは０．４重量％以下、より好ましくは０．３重量％以下、特に好ましくは０．２重量％以下、最も好ましくは０．１５重量％以下であるときに、保存安定性や耐水性に優れ好適である。 The ash content of the acrylic rubber veil of the present invention is. Although not particularly limited, it is usually 0.5% by weight or less, preferably 0.4% by weight or less, more preferably 0.3% by weight or less, particularly preferably 0.2% by weight or less, and most preferably 0. When it is .15% by weight or less, it is excellent in storage stability and water resistance and is suitable.
　本発明のアクリルゴムベールの灰分量の下限値は、格別限定されるものではないが、通常０．０００１重量％以上、好ましくは０．０００５重量％以上、より好ましくは０．００１重量％以上、特に好ましくは０．００５重量％以上、最も好ましくは０．０１重量％以上であるときに金属付着性が抑制され作業性に優れ好適である。 The lower limit of the ash content of the acrylic rubber veil 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.
　本発明のアクリルゴムベールの保存安定性、耐水性及び作業性が高度にバランスされる灰分量は、通常０．０００１～０．５重量％、好ましくは０．０００５～０．４重量％、より好ましくは０．００１～０．３重量％、特に好ましくは０．００５～０．２重量％、最も好ましくは０．０１～０．１５重量％の範囲である。 The amount of ash in which the storage stability, water resistance and workability of the acrylic rubber veil of the present invention are highly balanced is usually 0.0001 to 0.5% by weight, preferably 0.0005 to 0.4% 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.
　本発明のアクリルゴムベールの灰分中のナトリウム、イオウ、カルシウム、マグネシウム及びリンからなる群から選ばれる少なくとも１種の元素の含有量（合計量）は、格別な限定はないが、全灰分量に対する割合で、通常少なくとも３０重量％、好ましくは５０重量％以上、より好ましくは７０重量％以上、特に好ましくは８０重量％以上であるときに保存安定性と耐水性が高度に優れ好適である。 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 veil of the present invention is not particularly limited, but is based on the total ash content. The storage stability and water resistance are highly excellent and suitable when the ratio is usually at least 30% by weight, preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more.
　本発明のアクリルゴムベールの灰分中のナトリウムとイオウの合計量は、格別な限定はないが、全灰分量に対する割合で、通常３０重量％以上、好ましくは５０重量％以上、より好ましくは７０重量％以上、特に好ましくは８０重量％以上であるときに保存安定性と耐水性が高度に優れ好適である。 The total amount of sodium and sulfur in the ash content of the acrylic rubber veil 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.
　本発明のアクリルゴムベールの灰分中のナトリウムとイオウとの比（［Ｎａ］／［Ｓ］）は、重量比で、０．４～２．５、好ましくは０．６～２、好ましくは０．８～１．７、より好ましくは１～１．５の範囲であるときに耐水性が高度に優れ好適である。 The ratio of sodium to sulfur ([Na] / [S]) in the ash content of the acrylic rubber veil of the present invention is 0.4 to 2.5, preferably 0.6 to 2, preferably 0 by weight. When it is in the range of .8 to 1.7, more preferably 1 to 1.5, the water resistance is highly excellent and suitable.
　本発明のアクリルゴムベールの灰分中のマグネシウムとリンの合計量は、格別な限定はないが、全灰分量に対する割合で、通常３０重量％以上、好ましくは５０重量％以上、より好ましくは７０重量％以上、特に好ましくは８０重量％以上であるときに保存安定性と耐水性が高度に優れ好適である。 The total amount of magnesium and phosphorus in the ash content of the acrylic rubber veil 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.
　本発明のアクリルゴムベールの灰分中のマグネシウムとリンとの比（［Ｍｇ］／［Ｐ］）は、重量比で、格別な限定は無いが、通常０．４～２．５、好ましくは０．４～１．３、より好ましくは０．４～１、特に好ましくは０．４５～０．７５、最も好ましくは０．５～０．７の範囲であるときに保存安定性や耐水性が高度に優れ好適である。 The ratio of magnesium to phosphorus ([Mg] / [P]) in the ash content of the acrylic rubber veil 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.
　本発明のアクリルゴムベールの６０℃における複素粘性率（［η］６０℃）は、格別限定されるものではないが、通常１５，０００Ｐａ・ｓ以下、好ましくは２，０００～１０，０００Ｐａ・ｓ、より好ましくは２，５００～７，０００Ｐａ・ｓ、最も好ましくは２，７００～５，５００Ｐａ・ｓの範囲にあるとき加工性、耐油性及び形状保持性に優れ好適である。 The complex viscosity ([η] 60 ° C.) of the acrylic rubber veil 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.
　本発明のアクリルゴムベールの１００℃における複素粘性率（［η］１００℃）は、格別限定されるものではないが、通常１，５００～６，０００Ｐａ・ｓ、好ましくは２，０００～５，０００Ｐａ・ｓ、より好ましくは２，５００～４，０００Ｐａ・ｓ、最も好ましくは２，５００～３，５００Ｐａ・ｓの範囲であるときに加工性、耐油性、及び形状保持性に優れ好適である。 The complex viscosity ([η] 100 ° C.) of the acrylic rubber veil 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. ..
　本発明のアクリルゴムベールの１００℃における複素粘性率（［η］１００℃）と６０℃における複素粘性率（［η］６０℃）との比（［η］１００℃／［η］６０℃）は、格別限定はないが、通常０．５以上、好ましくは０．６以上、より好ましくは０．７以上、特に好ましくは０．８以上、最も好ましくは０．８３以上である。また、１００℃における複素粘性率（［η］１００℃）と６０℃における複素粘性率（［η］６０℃）との比（［η］１００℃／［η］６０℃）が、通常０．５～０．９９、好ましくは０．５～０．９８、より好ましくは０．６～０．９５、最も好ましくは０．７５～０．９３の範囲であるときに加工性、耐油性、及び形状保持性が高度にバランスされ好適である。 The ratio of the complex viscosity ([η] 100 ° C.) of the acrylic rubber veil of the present invention at 100 ° C. to the complex viscosity ([η] 60 ° C.) at 60 ° C. ([η] 100 ° C./[η] 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 ([η] 100 ° C./[η] 60 ° C.) of the complex viscosity at 100 ° C. ([η] 100 ° C.) to the complex viscosity at 60 ° C. ([η] 60 ° C.) is usually 0. Workability, oil resistance, and workability, oil resistance, and when the range is 5 to 0.99, preferably 0.5 to 0.98, more preferably 0.6 to 0.95, and most preferably 0.75 to 0.93. The shape retention is highly balanced and suitable.
　本発明のアクリルゴムベールのムーニー粘度（ＭＬ１＋４，１００℃）は、格別限定されるものではないが、通常１０～１５０、好ましくは２０～１００、より好ましくは２５～７０の範囲であるときに加工性や強度特性が高度にバランスされ好適である。 The Mooney viscosity (ML1 + 4,100 ° C.) of the acrylic rubber veil 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.
　＜アクリルゴムベールの製造方法＞
　上記アクリルゴムベールの製造方法は、格別限定されるものではないが、例えば、（メタ）アクリル酸エステルと反応性基含有単量体とを含む単量体成分を水と乳化剤とでエマルジョン化し重合触媒存在下に乳化重合し乳化重合液を得る乳化重合工程と、
　得られた乳化重合液と凝固液を接触させて含水クラムを生成する凝固工程と、
　生成した含水クラムを洗浄する洗浄工程と、
　洗浄した含水クラムを、脱水スリットを有する脱水バレルと減圧下の乾燥バレルと先端部にダイを有するスクリュー型押出機を用いて脱水バレルで含水量１～４０重量％まで脱水した後に乾燥バレルで含水量１重量％未満まで乾燥してシート状乾燥ゴムをダイから押し出す脱水・乾燥・成形工程と、
　を含むことで本発明に係るアクリルゴムベールを容易に製造することができる。 <Manufacturing method of acrylic rubber veil>
The method for producing the acrylic rubber bale is not particularly limited, but for example, a monomer component containing a (meth) acrylic acid ester and a reactive group-containing monomer is emulsion-polymerized with water and an emulsifier. In the emulsion polymerization step of obtaining an emulsion polymerization solution by emulsion polymerization in the presence of a catalyst,
A coagulation step in which the obtained emulsion polymerization solution and the coagulation solution are brought into contact with each other to form a hydrous crumb,
A cleaning process to clean the generated hydrous crumbs,
The washed water-containing crumb is dehydrated to a water content of 1 to 40% by weight in a dehydration barrel using a dehydration barrel having a dehydration slit, a drying barrel under reduced pressure, and a screw type extruder having a die at the tip, and then contained in the drying barrel. Dehydration / drying / molding process that dries to less than 1% by weight of water and extrudes sheet-shaped dry rubber from the die.
The acrylic rubber veil according to the present invention can be easily produced by including the above.
　（乳化重合工程）
　本発明のアクリルゴムベールの製造方法における乳化重合工程は、（メタ）アクリル酸エステルと反応性基含有単量体とを含む単量体成分を水と乳化剤とでエマルジョン化し重合触媒存在下に乳化重合し乳化重合液を得る工程である。 (Emulsion polymerization process)
In the emulsion polymerization step in the method for producing an acrylic rubber veil of the present invention, a monomer component containing a (meth) acrylic acid ester and a reactive group-containing monomer is emulsified with water and an emulsifier and emulsified in the presence of a polymerization catalyst. This is a step of polymerizing to obtain an emulsion polymerization solution.
　使用される単量体成分は、前記単量体成分で記載されたものと同様であり、使用量は前記アクリルゴムベールを構成するアクリルゴムの単量体組成になるように適宜選択されればよく、通常は、前記アクリルゴムベールを構成するアクリルゴムの単量体組成と同等の量である。 The monomer component used is the same as that described in the monomer component, and the amount used may be appropriately selected so as to have the monomer composition of the acrylic rubber constituting the acrylic rubber veil. Often, the amount is usually the same as the monomer composition of the acrylic rubber constituting the acrylic rubber veil.
　使用される乳化剤としては、格別な限定はなく常法に従えばよいが、例えば、アニオン性乳化剤、カチオン性乳化剤、ノニオン性乳化剤などを挙げることができる。これらの中でも、アニオン性乳化剤、ノニオン性乳化剤が好ましく、アニオン性乳化剤がより好ましく、リン酸系乳化剤、硫酸系乳化剤が特に好ましく、リン酸系乳化剤が最も好ましい。 The emulsifier used is not particularly limited and may follow a conventional method, and examples thereof include anionic emulsifiers, cationic emulsifiers, and nonionic emulsifiers. Among these, anionic emulsifiers and nonionic emulsifiers are preferable, anionic emulsifiers are more preferable, phosphoric acid-based emulsifiers and sulfuric acid-based emulsifiers are particularly preferable, and phosphoric acid-based emulsifiers are most preferable.
　アニオン性乳化剤としては、通常使用されるものを格別な限定なく使用され、例えば、脂肪酸系乳化剤、スルホン酸系乳化剤、スルホコハク酸系乳化剤、硫酸系乳化剤、リン酸系乳化剤などが挙げられ、好ましくは硫酸系乳化剤である。 As the anionic emulsifier, those usually used are used without particular limitation, and examples thereof include fatty acid-based emulsifiers, sulfonic acid-based emulsifiers, sulfosuccinic acid-based emulsifiers, sulfuric acid-based emulsifiers, and phosphoric acid-based emulsifiers, and are preferable. It is a sulfuric acid-based emulsifier.
　脂肪酸系乳化剤としては、例えば、オクタン酸ナトリウム、デカン酸ナトリウム、ラウリル酸ナトリウム、ミリスチン酸ナトリウム、パルミチン酸ナトリウム、ステアリン酸ナトリウムなどが挙げられる。 Examples of fatty acid-based emulsifiers include sodium octanate, sodium decanoate, sodium laurate, sodium myristate, sodium palmitate, sodium stearate, and the like.
　スルホン酸系乳化剤としては、例えば、ヘキサンスルホン酸ナトリウム、オクタンスルホン酸ナトリウム、デカンスルホン酸ナトリウム、トルエンスルホン酸ナトリウム、クメンスルホン酸ナトリウム、オクチルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸アンモニウム、ナフタレンスルホン酸ナトリウム、アルキルナフタレンスルホン酸ナトリウム、アルキルジフェニルエーテルジスルホン酸ナトリウムなどを挙げることができる。 Examples of the sulfonic acid-based emulsifier include sodium hexane sulfonate, sodium octane sulfonate, sodium decane sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, sodium octylbenzene sulfonate, sodium dodecylbenzene sulfonate, and dodecylbenzene sulfonic acid. Examples thereof include ammonium, sodium naphthalene sulfonate, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate and the like.
　スルホコハク酸系乳化剤としては、例えば、ジオクチルスルホコハク酸ナトリウム、ジヘキシルスルホコハク酸ナトリウムなどを挙げることができる。 Examples of the sulfosuccinic acid-based emulsifier include sodium dioctyl sulfosuccinate and sodium dihexyl sulfosuccinate.
　硫酸系乳化剤としては、格別な限定はなく常法に従えばよいが、硫酸エステル塩が好適に用いることができる。硫酸エステル塩としては、例えば、ラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム、ミリスチル硫酸ナトリウム、ラウレス硫酸ナトリウム、ポリオキシエチレンアルキル硫酸ナトリウム、ポリオキシエチレンアルキルアリール硫酸ナトリウムなどが挙げられ、好ましくはラウリル硫酸ナトリウムである。 The sulfuric acid-based emulsifier is not particularly limited and may follow a conventional method, but a sulfate ester salt can be preferably used. Examples of the sulfate ester salt include sodium lauryl sulfate, ammonium lauryl sulfate, sodium myristyl sulfate, sodium laureth sulfate, sodium polyoxyethylene alkyl sulfate, sodium polyoxyethylene alkylaryl sulfate, and the like, and sodium lauryl sulfate is preferable.
　リン酸系乳化剤としては、例えば、ラウリルリン酸ナトリウム、ラウリルリン酸カリウム、ポリオキシアルキレンアルキルエーテルリン酸エステルナトリウムなどを挙げることができる。 Examples of the phosphoric acid-based emulsifier include sodium lauryl phosphate, potassium lauryl phosphate, sodium polyoxyalkylene alkyl ether phosphoric acid ester, and the like.
　カチオン性乳化剤としては、例えば、アルキルトリメチルアンモニウムクロライド、ジアルキルアンモニウムクロライド、ベンジルアンモニウムクロライドなどを挙げることができる。 Examples of the cationic emulsifier include alkyltrimethylammonium chloride, dialkylammonium chloride, and benzylammonium chloride.
　ノニオン性乳化剤としては、特に限定されないが、例えば、ポリオキシエチレンステアリン酸エステルなどのポリオキシアルキレン脂肪酸エステル；ポリオキシエチレンドデシルエーテルなどのポリオキシアルキレンアルキルエーテル；ポリオキシエチレンノニルフェニルエーテルなどのポリオキシアルキレンアルキルフェノールエーテル；ポリオキシエチレンソルビタンアルキルエステルなどを挙げることができ、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルフェノールエーテルが好ましく、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェノールエーテルがより好ましい。 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. 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.
　これら乳化剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができ、その使用量は、単量体成分１００重量部に対して、通常０．０１～１０重量部、好ましくは０．１～５重量部、より好ましくは１～３重量部の範囲である。 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 0.1 parts by weight, based on 100 parts by weight of the monomer component. It is in the range of up to 5 parts by weight, more preferably 1 to 3 parts by weight.
　単量体成分と水と乳化剤との混合方法としては、常法に従えばよく、単量体と乳化剤と水とをホモジナイザーやディスクタービンなどの撹拌機などを用いて撹拌する方法などが挙げられる。水の使用量は、単量体成分１００重量部に対して、通常１０～７５０重量部、好ましくは５０～５００重量部、より好ましくは１００～４００重量部の範囲である。 As a method of mixing the monomer component, water and emulsifier, 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 in the range of 10 to 750 parts by weight, preferably 50 to 500 parts by weight, and more preferably 100 to 400 parts by weight with respect to 100 parts by weight of the monomer component.
　使用される重合触媒としては、乳化重合で通常使われるものであれば格別な限定はないが、例えば、ラジカル発生剤と還元剤とからなるレドックス触媒を用いることができる。 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.
　ラジカル発生剤としては、例えば、過酸化物、アゾ化合物などが挙げられ、好ましくは過酸化物である。過酸化物としては、無機系過酸化物や有機系過酸化物が用いられる。 Examples of the radical generator include peroxides and azo compounds, and peroxides are preferable. As the peroxide, an inorganic peroxide or an organic peroxide is used.
　無機系過酸化物としては、例えば、過硫酸ナトリウム、過硫酸カリウム、過酸化水素、過硫酸アンモニウムなどが挙げられ、これらの中でも過硫酸カリウム、過酸化水素、過硫酸アンモニウムが好ましく、過硫酸カリウムが特に好ましい。 Examples of the inorganic peroxide include sodium persulfate, potassium persulfate, hydrogen peroxide, ammonium persulfate and the like. Among these, potassium persulfate, hydrogen peroxide and ammonium persulfate are preferable, and potassium persulfate is particularly preferable. preferable.
　有機系過酸化物としては、乳化重合で使用される公知のものであれば格別な限定は無く、例えば、２，２－ジ（４，４－ジ－（ｔ－ブチルパーオキシ）シクロヘキシル）プロパン、１－ジ－（ｔ－ヘキシルパーオキシ）シクロヘキサン、１，１－ジ－（ｔ－ブチルパーオキシ）シクロヘキサン、４，４－ジ－（ｔ－ブチルパーオキシ）吉草酸ｎ－ブチル、２，２－ジ－（ｔ－ブチルパーオキシ）ブタン、ｔ－ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、パラメンタンハイドロパーオキサイド、ベンゾイルパーオキサイド、１，１，３，３－テトラエチルブチルハイドロパーオキサイド、ｔ－ブチルクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド、ジ－ｔ－ヘキシルパーオキサイド、ジ（２－ｔ－ブチルパーオキシイソプロピル）ベンゼン、ジクミルパーオキサイド、ジイソブチリルパーオキサイド、ジ（３，５，５－トリメチルヘキサノイル）パーオキサイド、ジラウロイルパーオキサイド、ジコハク酸パーオキサイド、ジベンゾイルパーオキサイド、ジ（３－メチルベンゾイル）パーオキサイド、ベンゾイル（３－メチルベンゾイル）パーオキサイド、ジイソブチリルパーオキシジカーボネート、ジ－ｎ－プロピルパーオキシジカーボネート、ジ（２－エチルヘキシル）パーオキシジカーボネート、ジ－ｓｅｃ－ブチルパーオキシジカーボネート、１，１，３，３－テトラメチルブチルパーオキシネオデカネート、ｔ－ヘキシルパーオキシピバレート、ｔ－ブチルパーオキシネオデカネート、ｔ－ヘキシルパーオキシピバレート、ｔ－ブチルパーオキシピバレート、２，５－ジメチル－２，５－ジ（２－エチルヘキサノイルパーオキシ）ヘキサン、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサネート、ｔ－ヘキシルパーオキシ－２－エチルヘキサネート、ｔ－ブチルパーオキシ－３，５，５－トリメチルヘキサネート、ｔ－ヘキシルパーオキシイソプロピルモノカーボネート、ｔ－ブチルパーオキシイソプロピルモノカーボネート、ｔ－ブイチルパーオキシ－２－エチルヘキシルモノカーボネート、２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン、ｔ－ブチルパーオキシアセテート、ｔ－ヘキシルパーオキシベンゾエート、ｔ－ブチルパーオキシベンゾエート、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサンなどが挙げられ、これらの中でもジイソプロピルベンゼンハイドロパーオキサイド、クメンハイドロパーオキサイド、パラメンタンハイドロパーオキサイド、ベンゾイルパーオキサイドなどが好ましい。 The organic peroxide is not particularly limited as long as it is a known organic peroxide used in emulsion polymerization. For example, 2,2-di (4,5-di- (t-butylperoxy) cyclohexyl) propane. , 1-di- (t-hexyl peroxy) cyclohexane, 1,1-di- (t-butyl peroxy) cyclohexane, 4,4-di- (t-butyl peroxy) n-butyl valerate, 2, 2-Di- (t-butylperoxy) butane, t-butylhydroperoxide, cumenehydroperoxide, diisopropylbenzenehydroperoxide, paramentanhydroperoxide, benzoyl peroxide, 1,1,3,3-tetraethyl Butylhydroperoxide, t-butylcumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, diisobutyryl peroxide , Di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, disuccinic acid peroxide, dibenzoyl peroxide, di (3-methylbenzoyl) peroxide, benzoyl (3-methylbenzoyl) peroxide , Diisobutyryl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3,3-tetramethylbutyl Peroxyneodecanate, t-hexylperoxypivarate, t-butylperoxyneodecanate, t-hexylperoxypivarate, t-butylperoxypivarate, 2,5-dimethyl-2,5-di (2-Ethylhexanoylperoxy) hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate, t-hexylperoxy-2-ethylhexanate, t-butylperoxy-3 , 5,5-trimethylhexanate, t-hexyl peroxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate, t-buylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5- Di (benzoylperoxy) hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butylperoxybenzoate, 2,5-dimethyl-2,5-di Examples thereof include (t-butylperoxy) hexane, and among these, diisopropylbenzene hydroperoxide, cumene hydroperoxide, paramentan hydroperoxide, benzoyl peroxide and the like are preferable.
　アゾ化合物としては、例えば、アゾビスイソプチロニトリル、４，４'－アゾビス（４－シアノ吉草酸）、２，２'－アゾビス［２－（２－イミダゾリン－２－イル）プロパン、２，２'－アゾビス（プロパン－２－カルボアミジン）、２，２'－アゾビス［Ｎ－（２－カルボキシエチル）－２－メチルプロパンアミド］、２，２'－アゾビス｛２－［１－（２－ヒドロキシエチル）－２－イミダゾリン－２－イル］プロパン｝、２，２'－アゾビス（１－イミノ－１－ピロリジノ－２－メチルプロパン）及び２，２'－アゾビス｛２－メチル－Ｎ－［１，１－ビス（ヒドロキシメチル）－２－ヒドロキシエチル］プロパンアミド｝などが挙げられる。 Examples of the azo compound 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.
　これらのラジカル発生剤は、それぞれ単独で、あるいは２種類以上を組み合わせて用いることができ、その使用量は、単量体成分１００重量部に対して、通常０．０００１～５重量部、好ましくは０．０００５～１重量部、より好ましくは０．００１～０．５重量部の範囲である。 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.
　還元剤としては、乳化重合のレドックス触媒で使用されるものであれば格別な限定なく用いることができるが、本発明においては、特に少なくとも２種の還元剤を用いることが好ましい。少なくとも２種の還元剤としては、例えば、還元状態にある金属イオン化合物とそれ以外の還元剤の組み合わせが好適である。 As the reducing agent, 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. As 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.
　還元状態にある金属イオン化合物としては、特に限定されないが、例えば、硫酸第一鉄、ヘキサメチレンジアミン四酢酸鉄ナトリウム、ナフテン酸第一銅などが挙げられ、これらの中でも硫酸第一鉄が好ましい。これらの還元状態にある金属イオン化合物は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができ、その使用量は、単量体成分１００重量部に対して、通常０．０００００１～０．０１重量部、好ましくは０．００００１～０．００１重量部、より好ましくは０．００００５～０．０００５重量部の範囲である。 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.
　それらの還元状態にある金属イオン化合物以外の還元剤としては、特に限定はないが、例えば、アスコルビン酸、アスコルビン酸ナトリウム、アスコルビン酸カリウムなどのアスコルビン酸又はその塩；エリソルビン酸、エリソルビン酸ナトリウム、エリソルビン酸カリウムなどのエリソルビン酸又はその塩；ヒドロキシメタンスルフィン酸ナトリウムなどのスルフィン酸塩；亜硫酸ナトリウム、亜硫酸カリウム、亜硫酸水素ナトリウム、アルデヒド亜硫酸水素ナトリウム、亜硫酸水素カリウムの亜硫酸塩；ピロ亜硫酸ナトリウム、ピロ亜硫酸カリウム、ピロ亜硫酸水素ナトリウム、ピロ亜硫酸水素カリウムなどのピロ亜硫酸塩；チオ硫酸ナトリウム、チオ硫酸カリウムなどのチオ硫酸塩；亜燐酸、亜燐酸ナトリウム、亜燐酸カリウム、亜燐酸水素ナトリウム、亜燐酸水素カリウムの亜燐酸又はその塩；ピロ亜燐酸、ピロ亜燐酸ナトリウム、ピロ亜燐酸カリウム、ピロ亜燐酸水素ナトリウム、ピロ亜燐酸水素カリウムなどのピロ亜燐酸又はその塩；ナトリウムホルムアルデヒドスルホキシレートなどが挙げられる。これらの中でも、アルコルビン酸又はその塩、ナトリウムホルムアルデヒドスルホキシレートなどが好ましく、特にアスコルビン酸又はその塩が好ましい。 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 pyrosulfite; sodium formaldehyde sulfoxylate and the like. Among these, alcorbic acid or a salt thereof, sodium formaldehyde sulfoxylate and the like are preferable, and ascorbic acid or a salt thereof is particularly preferable.
　これらの還元状態にある金属イオン化合物以外の還元剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができ、その使用量は、単量体成分１００重量部に対し、通常０．００１～１重量部、好ましくは０．００５～０．５重量部、より好ましくは０．０１～０．３重量部の範囲である。 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.
　還元状態にある金属イオン化合物とそれ以外の還元剤との好ましい組み合わせは、硫酸第一鉄とアスコルビン酸若しくはその塩及び／又はナトリウムホルムアルデヒドスルホキシレートで、より好ましくは硫酸第一鉄とアスコルビン酸塩及び／又はナトリウムホルムアルデヒドスルホキシレート、最も好ましくは硫酸第一鉄とアルコルビン酸塩の組み合わせである。この時の、硫酸第一鉄の使用量は、単量体成分１００重量部に対して、通常０．０００００１～０．０１重量部、好ましくは０．００００１～０．００１重量部、より好ましくは０．００００５～０．０００５重量部の範囲で、アスコルビン酸若しくはその塩及び／又はナトリウムホルムアルデヒドスルホキシレートの使用量は、単量体成分１００重量部に対し、通常０．００１～１重量部、好ましくは０．００５～０．５重量部、より好ましくは０．０１～０．３重量部の範囲である。 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. At this time, 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. In the range of 0.00005 to 0.0005 parts by weight, 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.
　乳化重合反応における水の使用量は、前記単量体成分エマルジョン化時に使用したものだけでもよいが、重合に用いる単量体成分１００重量部に対して、通常１０～１，０００重量部、好ましくは５０～５００重量部、より好ましくは８０～４００重量部、最も好ましくは１００～３００重量部の範囲になるように調整される。 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.
　乳化重合反応は、常法に従えばよく、回分式、半回分式、連続式のいずれでもよい。重合温度及び重合時間は、特に限定されず、使用する重合開始剤の種類などから適宜選択できる。重合温度は、通常０～１００℃、好ましくは５～８０℃、より好ましくは１０～５０℃の範囲であり、重合時間は通常０．５～１００時間、好ましくは１～１０時間である。 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.
　乳化重合反応の重合転化率は、格別限定はないが、通常８０重量％以上、好ましくは９０重量％以上、より好ましくは９５重量％以上であるときに製造されるアクリルゴムベールの強度特性に優れ且つ単量体臭も無く好適である。重合停止に当たっては、重合停止剤を使用してもよい。 The polymerization conversion rate of the emulsion polymerization reaction is not particularly limited, but is excellent in the strength characteristics of the acrylic rubber bale 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.
　（凝固工程）
　本発明のアクリルゴムシートの製造方法における凝固工程としては、上記得られた乳化重合液を撹拌している凝固液（凝固剤含有水溶液）に添加して含水クラムを生成させることを特徴とする。 (Coagulation process)
The coagulation step in the method for producing an acrylic rubber sheet of the present invention is characterized in that the obtained emulsion polymerization solution is added to a stirring coagulation solution (coagulant-containing aqueous solution) to generate a hydrous crumb.
　凝固工程で使用される乳化重合液の固形分濃度は、格別な限定はないが、通常５～５０重量％、好ましくは１０～４５重量％、より好ましくは２０～４０重量％の範囲に調整される。 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.
　使用される凝固剤としては、特に限定されないが、通常は金属塩が用いられる。金属塩としては、例えば、アルカリ金属、周期表第２族金属塩、その他の金属塩などが挙げられ、好ましくはアルカリ金属塩、周期表第２族金属塩、より好ましくは周期表第２族金属塩、特に好ましくはマグネシウム塩である。 The coagulant used is not particularly limited, but usually a metal salt is used. Examples of 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 Metals of the Periodic Table. A salt, particularly preferably a magnesium salt.
　アルカリ金属塩としては、例えば、塩化ナトリウム、硝酸ナトリウム、硫酸ナトリウムなどのナトリウム塩；塩化カリウム、硝酸カリウム、硫酸カリウムなどのカリウム塩；塩化リチウム、硝酸リチウム、硫酸リチウムなどのリチウム塩などが挙げられ、これらの中でもナトリウム塩が好ましく、塩化ナトリウム、硫酸ナトリウムが特に好ましい。 Examples of the alkali metal salt 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. Among these, sodium salts are preferable, and sodium chloride and sodium sulfate are particularly preferable.
　周期表第２族金属塩としては、例えば、塩化マグネシウム、塩化カルシウム、硝酸マグネシウム、硝酸カルシウム、硫酸マグネシウム、硫酸カルシウムなどが挙げられ、好ましくは塩化カルシウム、硫酸マグネシウム、より好ましくは硫酸マグネシウムである。 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, preferably calcium chloride, magnesium sulfate, and more preferably magnesium sulfate.
　その他の金属塩としては、例えば、塩化亜鉛、塩化チタン、塩化マンガン、塩化鉄、塩化コバルト、塩化ニッケル、塩化アルミニウム、塩化スズ、硝酸亜鉛、硝酸チタン、硝酸マンガン、硝酸鉄、硝酸コバルト、硝酸ニッケル、硝酸アルミニウム、硝酸スズ、硫酸亜鉛、硫酸チタン、硫酸マンガン、硫酸鉄、硫酸コバルト、硫酸ニッケル、硫酸アルミニウム、硫酸スズなどが挙げられる。 Other 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.
　これらの凝固剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができ、その使用量は、単量体成分１００重量部に対し、通常０．０１～１００重量部、好ましくは０．１～５０重量部、より好ましくは１～３０重量部の範囲である。凝固剤がこの範囲にあるときに、アクリルゴムの凝固を充分なものとしながら、アクリルゴムベールを架橋した場合の耐圧縮永久歪み特性や耐水性を高度に向上させることができるので好適である。 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, the acrylic rubber can be sufficiently solidified, and the compression-resistant permanent strain resistance and water resistance when the acrylic rubber veil is crosslinked can be highly improved, which is preferable.
　凝固液の凝固剤濃度は、通常０．１～２０重量％、好ましくは０．５～１５重量％、より好ましくは１～１０重量％、特に好ましくは１．５～５重量％の範囲であるときに生成する含水クラムの粒径を特定の領域に且つ均一に集束でき好適である。 The coagulant concentration of the coagulant 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 suitable because the particle size of the hydrous crumb that is sometimes generated can be uniformly focused in a specific region.
　凝固液の温度は、格別限定はないが、通常４０℃以上、好ましくは４０～９０℃、より好ましくは５０～８０℃の範囲であるときに均一な含水クラムが生成され好適である。 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.
　撹拌されている凝固液の撹拌数（回転数）は、すなわち、撹拌装置の撹拌翼の回転数で、格別な限定はないが、通常１００ｒｐｍ以上、好ましくは２００～１，０００ｒｐｍ、より好ましくは３００～９００ｒｐｍ、特に好ましくは４００～８００ｒｐｍの範囲である。回転数はある程度激しく撹拌される回転数である方が、生成する含水クラム粒径を小さく且つ均一にでき好適であり、前記下限以上とすることにより、クラム粒径が過度に大きいものと小さいものとが生成するのを抑制でき、前記上限以下とすることにより、凝固反応の制御をより容易にできる。 The stirring speed (rotation speed) of the coagulated liquid being stirred is, that is, the rotation speed of the stirring blade of the stirring device, and is not particularly limited, but is usually 100 rpm or more, preferably 200 to 1,000 rpm, and more preferably 300. It is in the range of ~ 900 rpm, particularly preferably 400 to 800 rpm. It is preferable that the rotation speed is a rotation speed that is vigorously agitated to some extent so that the hydrous crumb particle size to be generated can be made small and uniform. By setting the rotation speed to the above lower limit or more, the crumb particle size is excessively large or small. The formation of and can be suppressed, and the solidification reaction can be more easily controlled by setting the content to the upper limit or less.
　撹拌されている凝固液の周速は、すなわち、撹拌装置の撹拌翼の外周の速度は、格別な限定はないが、一定程度まで激しく撹拌されている方が生成する含水クラム粒径を小さく且つ均一にでき好適で、通常０．５ｍ／ｓ以上、好ましくは１ｍ／ｓ以上、より好ましくは１．５ｍ／ｓ以上、特に好ましくは２ｍ／ｓ以上最も好ましくは２．５ｍ／ｓ以上である。一方周速の上限値は、格別限定されるものではないが、通常５０ｍ／ｓ以下、好ましくは３０ｍ／ｓ以下、より好ましくは２５ｍ／ｓ以下、最も好ましくは２０ｍ／ｓ以下であるときに凝固反応の制御が容易になり好適である。 The peripheral speed of the coagulated liquid being agitated, that is, the speed of the outer circumference of the stirring blade of the agitating device is not particularly limited, but the water-containing crumb particle size generated by vigorously agitating to a certain degree is smaller and It can be made uniform and is preferable, 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. On the other hand, 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.
　凝固工程における凝固反応の上記条件（接触方法、乳化重合液の固形分濃度、凝固液の濃度及び温度、凝固液の撹拌時の回転数及び周速、など）を特定範囲にすることで、生成する含水クラムの形状及びクラム径が均一で且つ集束化され、洗浄及び脱水時の乳化剤や凝固剤の除去が格段に向上し好適である。 It is produced by setting the above conditions of the coagulation reaction in the coagulation step (contact method, solid content concentration of emulsion polymerization solution, concentration and temperature of coagulation solution, rotation speed and peripheral speed of coagulation solution during stirring, etc.) within a specific range. The shape and crumb diameter of the hydrous crumb are uniform and focused, and the removal of emulsifiers and coagulants during washing and dehydration is remarkably improved, which is suitable.
　（洗浄工程）
　本発明のアクリルゴムベールの製造方法における洗浄工程は、上記生成した含水クラムを水で洗浄する工程である。 (Washing process)
The cleaning step in the method for producing an acrylic rubber veil of the present invention is a step of cleaning the produced hydrous crumb with water.
　洗浄方法としては、格別限定されるものでなく常法に従えばよく、例えば、生成した含水クラムを多量の水と混合して行うことができる。 The cleaning method is not particularly limited and may follow a conventional method. For example, the produced hydrous crumb can be mixed with a large amount of water.
　使用する水の量としては、特に限定されないが、前記単量体成分１００重量部に対して、水洗１回当たりの量が、通常５０重量部以上、好ましくは５０～１５，０００重量部、より好ましくは１００～１０，０００重量部、特に好ましくは１５０～５，０００重量部の範囲であるときに、アクリルゴム中の灰分量を効果的に低減することができ好適である。 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.
　水洗する水の温度としては、格別限定されるものではないが、温水を使うのが好ましく、通常４０℃以上、好ましくは４０～１００℃、より好ましくは５０～９０℃、最も好ましくは６０～８０℃のときに洗浄効率を格段に上げることができ好適である。 The temperature of the water to be washed with water is not particularly limited, but it is preferable to use warm water, 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 the cleaning efficiency can be significantly increased at ℃.
　洗浄水の温度を前記下限以上とすることにより、乳化剤や凝固剤が含水クラムから遊離して洗浄効率がより向上する。 By setting the temperature of the washing water to the above lower limit or higher, the emulsifier and coagulant are released from the hydrous crumb to further improve the washing efficiency.
　洗浄時間としては、格別な限定はないが、通常１～１２０分、好ましくは２～６０分、より好ましくは３～３０分の範囲である。 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.
　洗浄回数としては、特に限定されず、通常１～１０回、好ましくは複数回、より好ましくは２～３回である。なお、最終的に得られるアクリルゴム中の凝固剤の残留量を低減するという観点からは、水洗回数が多い方が望ましいが、前記含水クラムの形状及び含水クラム径を特定にすること及び／又は洗浄温度を前記範囲にすることで洗浄回数を格段に低減できる。 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, 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 / or By setting the cleaning temperature within the above range, the number of cleanings can be significantly reduced.
　（脱水・乾燥・成形工程）
　本発明のアクリルゴムベールの製造方法における脱水・乾燥・成形工程は、上記洗浄した含水クラムを、脱水スリットを有する脱水バレルと減圧下の乾燥バレルと先端部にダイを有するスクリュー型押出機を用いて脱水バレルで含水量１～４０重量％まで脱水した後に乾燥バレルで１重量％未満まで乾燥してシート状乾燥ゴムをダイから押し出すことを特徴とする。 (Dehydration / drying / molding process)
In the dehydration / drying / molding step in the method for producing an acrylic rubber bale of the present invention, the above-cleaned 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.
　本発明においては、スクリュー型押出機に供給される含水クラムは、洗浄後に遊離水を除去（水切り）したものであることが好ましい。 In the present invention, the water-containing crumb supplied to the screw type extruder is preferably one in which free water is removed (drained) after washing.
　水切り工程
　本発明のアクリルゴムベールの製造方法において、上記水洗工程の後及び脱水・乾燥工程の前に、洗浄後の含水クラムから水切り機で遊離水を分離する水切り工程を設けることが脱水効率を上げる上で好適である。 Draining step In the method for producing an acrylic rubber bale of the present invention, providing 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 step improves the dehydration efficiency. It is suitable for raising.
　水切り機としては、公知のものを格別な限定なく用いることができ、例えば、金網、スクリーン、電動篩機などが挙げられ、好ましくは金網、スクリーンである。 As the drainer, 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.
　水切り機目開きは、格別限定はないが、通常０．０１～５ｍｍ、好ましくは０．１～１ｍｍ、より好ましくは０．２～０．６ｍｍの範囲であるときに、含水クラム損出が少なく且つ水切りが効率的にでき好適である。 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.
　水切り後の含水クラムの含水量、すなわち脱水・乾燥工程に投入される含水クラムの含水量は、格別限定されるものではないが、通常５０～８０重量％、好ましくは５０～７０重量％、より好ましくは５０～６０重量％の範囲である。 The water content of the water-containing crumb after draining, that is, the water content of the water-containing crumb put into the dehydration / drying step is not particularly limited, but is usually 50 to 80% by weight, preferably 50 to 70% by weight, and more. It is preferably in the range of 50 to 60% by weight.
　水切り後の含水クラムの温度、すなわち脱水・乾燥工程に投入される含水クラムの温度は、格別限定されるものではないが、通常４０℃以上、好ましくは４０～１００℃、より好ましくは５０～９０℃、特に好ましくは５５～８５℃、最も好ましくは６０～８０℃の範囲であるときに、本発明のアクリルゴムのように比熱が１．５～２．５ＫＪ／ｋｇ・Ｋと高く温度を上げにくい含水クラムをスクリュー型押出機を用いて効率よく脱水・乾燥でき好適である。 The temperature of the hydrous crumb after draining, that is, the temperature of the hydrous crumb put into the dehydration / drying step is not particularly limited, but is usually 40 ° C. or higher, preferably 40 to 100 ° C., more preferably 50 to 90 ° C. When the temperature is in the range of ° C., particularly preferably 55 to 85 ° C., most preferably 60 to 80 ° C., the temperature is raised as high as 1.5 to 2.5 KJ / kg · K as in the acrylic rubber of the present invention. It is suitable because difficult water-containing crumbs can be efficiently dehydrated and dried using a screw type extruder.
　含水クラムの脱水（脱水バレル部）
　含水クラムの脱水は、脱水スリットを有する脱水バレルで行われる。脱水スリットの目開きは、使用条件に応じて適宜選択されればよいが、通常０．０１～５ｍｍ、好ましくは０．１～１ｍｍ、より好ましくは０．２～０．６ｍｍの範囲であるときに、含水クラム損出が少なく且つ含水クラムの脱水が効率的にでき好適である。 Dehydration of hydrous crumbs (dehydration barrel)
Dehydration of the hydrous crumb is carried out in a dehydration barrel having a dehydration slit. 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. In addition, it is suitable because the loss of the hydrous crumb is small and the hydrous crumb can be efficiently dehydrated.
　スクリュー型押出機における脱水バレルの数は、格別限定されるものではないが、通常複数個、好ましくは２～１０個、より好ましくは３～６個であるときに粘着性のアクリルゴムの脱水を効率よく行う上で好適である。 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.
　脱水バレルにおける含水クラムからの水の除去は、脱水スリットから液状で除去するもの（排水）、蒸気状で除去するもの（排蒸気）の二通りがあるが、本発明においては、排水は脱水、排蒸気は予備乾燥と定義して区別する。 There are two ways to remove water from the water-containing crumb in the dehydration barrel: one that removes water from the dehydration slit in liquid form (drainage) and one that removes water in the form of steam (exhaust vapor). Exhaust steam is defined as pre-drying to distinguish it.
　脱水バレルを複数個備えるスクリュー型押出機を用いて行う場合は、排水及び排蒸気を組み合わせることで粘着性アクリルゴムの排水（脱水）と含水量低下が効率よくでき好適である。脱水バレルを３個以上備えるスクリュー型押出機の排水型脱水バレルか排蒸気型脱水バレルかの選択は、使用目的に応じて適宜行えばよいが、通常製造されるアクリルゴム中の灰分量を少なくする場合は排水型バレルを多くし、例えば脱水バレルが３個ある場合は排水型バレルを２個、脱水バレルが４個ある場合は排水型バレルを３個などと適宜選択する。 When using a screw type extruder equipped with multiple dehydration barrels, it is preferable to combine drainage and exhaust steam to efficiently drain (dehydrate) the adhesive acrylic rubber and reduce the water content. The selection of the drainage type dehydration barrel or the exhaust steam type dehydration barrel of the screw type extruder equipped with three or more dehydration barrels may be appropriately performed according to the purpose of use, but the amount of ash in the acrylic rubber usually produced is small. In this case, the number of drainage barrels is increased. For example, when there are three dehydration barrels, two drainage barrels are selected, and when there are four dehydration barrels, three drainage barrels are appropriately selected.
　脱水バレルの設定温度は、アクリルゴムの種類、灰分量、含水量、及び操業条件などにより適宜選択されるが、通常６０～１５０℃、好ましくは７０～１４０℃、より好ましくは８０～１３０℃の範囲である。排水状態で脱水する脱水バレルの設定温度は、通常６０℃～１２０℃、好ましくは７０～１１０℃、より好ましくは８０～１００℃である。排蒸気状態で乾燥する脱水バレルの設定温度は、通常１００～１５０℃、好ましくは１０５～１４０℃、より好ましくは１１０～１３０℃の範囲である。 The set temperature of the dehydration barrel is appropriately selected depending on the type of acrylic rubber, ash content, water content, operating conditions, etc., but is usually 60 to 150 ° C., preferably 70 to 140 ° C., more preferably 80 to 130 ° C. The range. 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 dries 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.
　含水クラムから水分を絞り出す排水型の脱水後の含水量としては、格別な限定はないが、通常１～４５重量％、好ましくは１～４０重量％、より好ましくは５～３５重量％、特に好ましくは１０～３５重量％であるときに生産性と灰分除去効率とが高度にバランスされ好適である。 The water content after dehydration of the drainage type that squeezes water from the water-containing crumb 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, and particularly preferably. Is suitable because the productivity and the ash removal efficiency are highly balanced when the content is 10 to 35% by weight.
　粘着性のアクリルゴムの脱水は、遠心分離機などを用いて行うと脱水スリット部にアクリルゴムが付着してしまい殆ど脱水できないが（含水量は約４５～５５重量％程度まで）、本発明において、脱水スリットを有しスクリューで強制的に絞られるスクリュー型押出機を用いることによりここまで含水量を低減できるようになった。 When dehydration of adhesive acrylic rubber is performed using a centrifuge or the like, the acrylic rubber adheres to the dehydration slit portion and can hardly be dehydrated (water content is up to about 45 to 55% by weight), but in the present invention. By using a screw type extruder that has a dehydration slit and is forcibly squeezed with a screw, the water content can be reduced to this extent.
　排水型脱水バレルと排蒸気型脱水バレルとを備える場合の含水クラムの脱水は、排水型脱水バレル部における排水後の含水量が通常５～４５重量％、好ましくは１０～４０重量％、より好ましくは１５～３５重量％、排蒸気型脱水バレル部における予備乾燥後の含水量が、通常１～３０重量％、好ましくは３～２０重量％、より好ましくは５～１５重量％である。 In the dehydration of the water-containing crumb when the drainage type dehydration barrel and the exhaust steam type dehydration barrel are provided, the water content after drainage in the drainage type dehydration barrel portion is usually 5 to 45% by weight, preferably 10 to 40% by weight, more preferably. Is 15 to 35% by weight, and the water content after pre-drying in the exhaust steam type dehydration barrel portion is usually 1 to 30% by weight, preferably 3 to 20% by weight, and more preferably 5 to 15% by weight.
　脱水後の含水量を前記下限以上とすることにより、脱水時間を短縮できてアクリルゴムの変質を抑制でき、前記上限以下とすることにより灰分量を十分に低減することができる。 By setting the water content after dehydration to be equal to or higher than the lower limit, 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.
　含水クラムの乾燥（乾燥バレル部）
　上記脱水後の含水クラムの乾燥は、減圧下の乾燥バレル部で行うことを特徴とする。 Drying of hydrous crumb (dry barrel)
The hydrous crumb after dehydration is dried in a drying barrel portion under reduced pressure.
　乾燥バレルの減圧度は、適宜選択されればよいが、通常１～５０ｋＰａ，好ましくは２～３０ｋＰａ、より好ましくは３～２０ｋＰａであるときに効率よく含水クラムを乾燥でき好適である。 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.
　乾燥バレルの設定温度は、適宜選択されればよいが、通常１００～２５０℃、好ましくは１１０～２００℃、より好ましくは１２０～１８０℃の範囲であるときに、アクリルゴムのヤケや変質がなく効率よく乾燥ができ且つアクリルゴムのメチルエチルケトン不溶解分のゲル量を低減でき好適である。 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 of the methyl ethyl ketone insoluble component of acrylic rubber can be reduced.
　スクリュー型押出機における乾燥バレルの数は、格別限定されるものではないが、通常複数個、好ましくは２～１０個、より好ましくは３～８個である。乾燥バレルが複数個有する場合の減圧度は、全ての乾燥バレルで近似した減圧度にしてもよいし、変えてもよい。乾燥バレルが複数個有する場合の設定温度は、全ての乾燥バレルで近似した温度にしてもよいし変えてもよいが、導入部（脱水バレルに近い方）の温度よりも排出部（ダイに近い方）の温度の方が高くするのが乾燥効率を上げることができ好適である。 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. When there are a plurality of dry barrels, the decompression degree may be an approximate decompression degree for all the dry barrels, or may be changed. When there are multiple drying barrels, 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.
　乾燥後の乾燥ゴムの含水量は、通常１重量％未満、好ましくは０．８重量％以下、より好ましくは０．６重量％以下である。本発明においては、特にスクリュー型押出機内で乾燥ゴムの含水量がこの値（殆ど水が除去された状態）にして溶融押出しされることがアクリルゴムベールのメチルエチルケトン不溶解分のゲル量を低減でき好適である。 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. In the present invention, the gel amount of the methyl ethyl ketone insoluble portion of the acrylic rubber veil can be reduced by melt-extruding the dry rubber with the water content of the dry rubber set to this value (in a state where most of the water is removed), particularly in the screw type extruder. Suitable.
　アクリルゴムの形状（ダイ部）
　上記脱水バレル及び乾燥バレルのスクリュー部で脱水・乾燥されたアクリルゴムは、スクリューの無い整流のダイ部に送られる。スクリュー部とダイ部の間には、ブレーカープレートや金網を設けてもよいし、設けなくてもよい。 Acrylic rubber shape (die part)
The acrylic 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.
　押出される乾燥ゴムは、ダイ形状を略長方形状にしてシート状に出すことにより空気の巻き込みが少なく比重の大きい保存安定性に優れる乾燥ゴムが得られ好適である。 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.
　ダイ部における樹脂圧は、格別限定されないが、通常０．１～１０ＭＰａ、好ましくは０．５～５ＭＰａ、より好ましくは１～３ＭＰａの範囲としたときに、空気の巻き込みが少なく（比重が高く）且つ生産性に優れ好適である。 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.
　スクリュー型押出機及び操業条件
　使用されるスクリュー型押出機のスクリュー長（Ｌ）は、使用目的に応じて適宜選択されればよいが、通常３，０００～１５，０００ｍｍ、好ましくは４，０００～１０，０００ｍｍ、より好ましくは４，５００～８，０００ｍｍの範囲である。 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.
　使用されるスクリュー型押出機のスクリュー径（Ｄ）は、使用目的に応じて適宜選択されればよいが、通常５０～２５０ｍｍ、好ましくは１００～２００ｍｍ、より好ましくは１２０～１６０ｍｍの範囲である。 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.
　使用されるスクリュー型押出機のスクリュー長（Ｌ）とスクリュー径（Ｄ）との比（Ｌ／Ｄ）は、格別限定されるものではないが、通常１０～１００、好ましくは２０～８０、より好ましくは３０～６０の範囲であるときに乾燥ゴムの分子量低下や焼けを起こさずに含水量を１重量％未満に出来好適である。 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.
　使用されるスクリュー型押出機の回転数（Ｎ）は、諸条件に応じて適宜選択されればよいが、通常１０～１，０００ｒｐｍ、好ましくは５０～７５０ｒｐｍ、より好ましくは１００～５００ｒｐｍ、最も好ましくは１２０～３００ｒｐｍであるときに、アクリルゴムの含水量とゲル量を効率よく低減でき好適である。 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.
　使用されるスクリュー型押出機の押出量（Ｑ）は、格別限定されないが、通常１００～１，５００ｋｇ／ｈｒ、好ましくは３００～１，２００ｋｇ／ｈｒ、より好ましくは４００～１，０００ｋｇ／ｈｒ、最も好ましくは５００～８００ｋｇ／ｈｒの範囲である。 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.
　使用されるスクリュー型押出機の押出量（Ｑ）と回転数（Ｎ）の比（Ｑ／Ｎ）は、格別限定されるものではないが、通常２～１０、好ましくは３～８、より好ましくは４～６の範囲である。 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.
　シート状乾燥ゴム
　スクリュー型押出機から押し出される乾燥ゴムの形状は、シート状であり、この時に空気の巻き込きこまず比重を大きくでき保存安定性が高度に改善され好適である。スクリュー型押出機から押し出されるシート状乾燥ゴムは、通常、冷却され切断されてアクリルゴムシートとして使用される。 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 usually cooled and cut to be used as an acrylic rubber sheet.
　スクリュー型押出機から押し出されるシート状乾燥ゴムの厚さは、格別な限定はないが、通常１～４０ｍｍ、好ましくは２～３５ｍｍ、より好ましくは３～３０ｍｍ、最も好ましくは５～２５ｍｍの範囲であるときに作業性、生産性に優れ好適である。特にシート状乾燥ゴムの熱伝導度が０．１５～０．３５Ｗ／ｍＫと低いために冷却効率を上げ生産性を格段に向上させる場合のシート状乾燥ゴムの厚さは、通常１～３０ｍｍ、好ましくは２～２５ｍｍ、より好ましくは３～１５ｍｍ、特に好ましくは４～１２ｍｍの範囲である。 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.
　スクリュー型押出機から押し出されるシート状乾燥ゴムの幅は、使用目的に応じて適宜選択されるが、通常３００～１，２００ｍｍ、好ましくは４００～１，０００ｍｍ、より好ましくは５００～８００ｍｍの範囲である。 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.
　スクリュー型押出機から押し出される乾燥ゴムの温度は、格別限定されるものではないが、通常１００～２００℃、好ましくは１１０～１８０℃、より好ましくは１２０～１６０℃の範囲である。 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.
　スクリュー型押出機から押し出される乾燥ゴムの含水量は、１重量％未満、好ましくは０．８重量％以下、より好ましくは０．６重量％以下である。 The water content of the dry rubber extruded from the screw type extruder is less than 1% by weight, preferably 0.8% by weight or less, and more preferably 0.6% by weight or less.
　スクリュー型押出機から押し出されるシート状乾燥ゴムの１００℃における複素粘性率（［η］１００℃）は、格別限定されるものではないが、通常１，５００～６，０００Ｐａ・ｓ、好ましくは２，０００～５，０００Ｐａ・ｓ、より好ましくは２，５００～４，０００Ｐａ・ｓ、最も好ましくは２，５００～３，５００Ｐａ・ｓの範囲であるときに、シートとしての押出性と形状保持性とが高度にバランスされ好適である。すなわち、下限以上とすることにより押出性により優れるものとでき、上限以下とすることによりシート状乾燥ゴムの形状の崩れや破断を抑制できる。 The complex viscosity ([η] 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.
　本発明においては、スクリュー型押出機から押し出されたシート状乾燥ゴムは、切断後に積層してベール化するのが巻き込む空気量も少なく保存安定性に優れ好適である。シート状乾燥ゴムの切断は、格別な限定はないが、本発明のアクリルゴムベールのアクリルゴムは粘着性が強いことから、空気を巻き込まずに連続的に切断するために、シート状乾燥ゴムを冷却してから行うのが好ましい。 In the present invention, the sheet-shaped dry rubber extruded from the screw type extruder is suitable because it is laminated after cutting and veiled because the amount of air involved is small and the storage stability is excellent. The cutting of the sheet-shaped dry rubber is not particularly limited, but since the acrylic rubber of the acrylic rubber veil of the present invention has strong adhesiveness, the sheet-shaped dry rubber is used for continuous cutting without entraining air. It is preferable to cool it down.
　シート状乾燥ゴムの切断温度は、格別な限定はないが、通常６０℃以下、好ましくは５５℃以下、より好ましくは５０℃以下であるときに、切断性と生産性とが高度にバランスされ好適である。 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.
　シート状乾燥ゴムの６０℃における複素粘性率（［η］６０℃）は、格別限定されるものではないが、通常１５，０００Ｐａ・ｓ以下、好ましくは２，０００～１０，０００Ｐａ・ｓ、より好ましくは２，５００～７，０００Ｐａ・ｓ、最も好ましくは２，７００～５，５００Ｐａ・ｓの範囲にあるときに空気を巻き込まずに且つ連続的に切断ができ好適である。 The complex viscosity ([η] 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.
　シート状乾燥ゴムの１００℃における複素粘性率（［η］１００℃）と６０℃における複素粘性率（［η］６０℃）との比（［η］１００℃／［η］６０℃）は、格別限定はないが、通常０．５以上、好ましくは０．５～０．９８、より好ましくは０．６～０．９５、最も好ましくは０．７５～０．９３の範囲であるときに空気巻き込み性が少なく、且つ切断と生産性が高度にバランスされ好適である。 The ratio ([η] 100 ° C./[η] 60 ° C.) of the complex viscosity ([η] 100 ° C.) of the sheet-shaped dried rubber at 100 ° C. to the complex viscosity ([η] 60 ° C.) at 60 ° C. is Although there is no particular limitation, air is usually in the range of 0.5 or more, preferably 0.5 to 0.98, more preferably 0.6 to 0.95, and most preferably 0.75 to 0.93. It is suitable because it has low entanglement and has a high balance between cutting and productivity.
　シート状乾燥ゴムの冷却方法としては、格別限定はなく室温に放置してもよいが、シート状乾燥ゴムの熱伝導度が０．１５～０．３５Ｗ／ｍＫと非常に小さいために、送風あるいは冷房下での空冷方式、水を吹き付ける水かけ方式、水中に浸漬する浸漬方式などの強制冷却が生産性を上げるために好ましく、特に送風あるいは冷下での空冷方式が好適である。 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.
　シート状乾燥ゴムの空冷方式では、例えば、スクリュー型押出機からベルトコンベアなどの搬送機上にシート状乾燥ゴムを押し出し、冷風を吹き付ける中で搬送し冷却することができる。冷風の温度は、格別限定されるものではないが、通常０～２５℃、好ましくは５～２５℃、より好ましくは１０～２０℃の範囲である。冷却される長さは、格別限定はないが、通常５～５００ｍ、好ましくは１０～２００ｍ、より好ましくは２０～１００ｍの範囲である。シート状乾燥ゴムの冷却速度は、格別限定されるものではないが、通常５０℃／ｈｒ以上、より好ましくは１００℃／ｈｒ以上、より好ましくは１５０℃／ｈｒ以上であるときに切断が特に容易になり好適である。 In the air-cooling method of sheet-shaped dry rubber, for example, 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.
　シート状乾燥ゴムの切断長さは、格別な限定はなく製造するアクリルゴムベールの大きさに合わせて適宜選択すればよいが、通常１００～８００ｍｍ、好ましくは２００～５００ｍｍ、より好ましくは２５０～４５０ｍｍの範囲である。 The cutting length of the sheet-shaped dry rubber is not particularly limited and may be appropriately selected according to the size of the acrylic rubber bale to be manufactured, but is usually 100 to 800 mm, preferably 200 to 500 mm, more preferably 250 to 450 mm. Is the range of.
　（ベール化工程）
　本発明のアクリルゴムベールの製造方法におけるベール化工程は、上記シート状乾燥ゴムを積層してベール化するものである。 (Veiling process)
The bale step in the method for producing an acrylic rubber veil of the present invention is to laminate the above sheet-shaped dry rubber to make a veil.
　シート状乾燥ゴムの積層温度は、格別限定はないが、通常３０℃以上、好ましくは３５℃以上、より好ましくは４０℃以上であるときに積層時に巻き込まれる空気を逃がすことができ好適である。積層枚数は、アクリルゴムベールの大きさあるいは重さに応じて適宜選択されればよい。 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.
　かくして得られる本発明のアクリルゴムベールは、クラム状アクリルゴムに比べ操作性や保存安定性に優れ、アクリルゴムベールをそのまま、あるいは必要量を切断してバンバリー、ロールなどの混合機に投入して用いることができる。 The acrylic rubber veil of the present invention thus obtained has excellent operability and storage stability as compared with crumb-shaped acrylic rubber, and the acrylic rubber veil can be used as it is or cut into a required amount and put into a mixer such as a vanbury or roll. Can be used.
　＜ゴム混合物＞
　本発明のゴム混合物は、前記アクリルゴムベールに、充填剤、架橋剤を混合してなることを特徴とする。 <Rubber mixture>
The rubber mixture of the present invention is characterized in that the acrylic rubber veil is mixed with a filler and a cross-linking agent.
　充填剤としては、格別な限定はないが、例えば、補強性充填剤、非補強性充填剤などが挙げられ、好ましくは補強性充填剤である。 The filler is not particularly limited, but examples thereof include a reinforcing filler and a non-reinforcing filler, and a reinforcing filler is preferable.
　補強性充填剤としては、例えば、ファーネスブラック、アセチレンブラック、サーマルブラック、チャンネルブラック、及びグラファイトなどのカーボンブラック；湿式シリカ、乾式シリカ、コロイダルシリカなどのシリカ；などを挙げることができる。非補強性充填剤としては、石英粉末、ケイソウ土、亜鉛華、塩基性炭酸マグネシウム、活性炭酸カルシウム、ケイ酸マグネシウム、ケイ酸アルミニウム、二酸化チタン、タルク、硫酸アルミニウム、硫酸カルシウム、硫酸バリウムなどを挙げることができる。 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.
　これらの充填剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができ、その配合量は、本発明の効果を損ねない範囲で適宜選択され、アクリルゴムベール１００重量部に対して、通常１～２００重量部、好ましくは１０～１５０重量部、より好ましくは２０～１００重量部の範囲である。 Each of these fillers can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected within a range that does not impair the effect of the present invention, with respect to 100 parts by weight of the acrylic rubber veil. 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.
　架橋剤としては、アクリルゴムベールを構成するアクリルゴムに含有される反応性基の種類や用途に応じて適宜選択されればよいが、アクリルゴムベールを架橋できるものであれば格別限定はされず、例えば、ジアミン化合物などの多価アミン化合物、及びその炭酸塩；硫黄化合物；硫黄供与体；トリアジンチオール化合物；多価エポキシ化合物；有機カルボン酸アンモニウム塩；有機過酸化物；多価カルボン酸；四級オニウム塩；イミダゾール化合物；イソシアヌル酸化合物；有機過酸化物；トリアジン化合物；などの従来公知の架橋剤を用いることができる。これらの中でも、多価アミン化合物、カルボン酸アンモニウム塩、ジチオカルバミン酸金属塩及びトリアジンチオール化合物が好ましく、ヘキサメチレンジアミンカーバメート、２，２'－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパン、安息香酸アンモニウム、２，４，６－トリメルカプト－１，３，５－トリアジンが特に好ましい。 The cross-linking agent may be appropriately selected according to the type and application of the reactive group contained in the acrylic rubber constituting the acrylic rubber bale, but is not particularly limited as long as it can cross-link the acrylic rubber bale. , For example, polyvalent amine compounds such as diamine compounds, and carbonates thereof; sulfur compounds; sulfur donors; triazinethiol compounds; polyvalent epoxy compounds; ammonium organic carboxylates; organic peroxides; polyvalent carboxylic acids; Conventionally known cross-linking agents such as a secondary onium salt; an imidazole compound; an isocyanuric acid compound; an organic peroxide; and a triazine compound; can be used. Among these, 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.
　使用するアクリルゴムベールがカルボキシル基含有アクリルゴムで構成される場合は、架橋剤として、多価アミン化合物、及びその炭酸塩を用いることが好ましい。多価アミン化合物としては、例えば、ヘキサメチレンジアミン、ヘキサメチレンジアミンカーバメート、Ｎ，Ｎ'－ジシンナミリデン－１，６－ヘキサンジアミンなどの脂肪族多価アミン化合物；４，４'－メチレンジアニリン、ｐ－フェニレンジアミン、ｍ－フェニレンジアミン、４，４'－ジアミノジフェニルエーテル、３，４'－ジアミノジフェニルエーテル、４，４'－（ｍ－フェニレンジイソプロピリデン）ジアニリン、４，４'－（ｐ－フェニレンジイソプロピリデン）ジアニリン、２，２'－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパン、４，４'－ジアミノベンズアニリド、４，４'－ビス（４－アミノフェノキシ）ビフェニル、ｍ－キシリレンジアミン、ｐ－キシリレンジアミン、１，３，５－ベンゼントリアミンなどの芳香族多価アミン化合物；などが挙げられる。これらの中でも、ヘキサメチレンジアミンカーバメート、２，２'－ビス〔４－（４－アミノフェノキシ）フェニル〕プロパンなどが好ましい。 When the acrylic rubber veil to be used is composed of a carboxyl group-containing acrylic rubber, it is preferable to use a polyvalent amine compound and a carbonate thereof as a cross-linking agent. Examples of 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. -Phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-(m-phenylenediisopropyridene) dianiline, 4,4'-(p-phenylenedi) Isopropylidene) dianiline, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diaminobenzanilide, 4,4'-bis (4-aminophenoxy) biphenyl, m-xyli Aromatic polyvalent amine compounds such as rangeamine, p-xylylenediamine, 1,3,5-benzenetriamine; and the like. Among these, hexamethylenediamine carbamate, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane and the like are preferable.
　使用するアクリルゴムベールがエポキシ基含有アクリルゴムで構成される場合は、架橋剤として、ヘキサメチレンジアミン、ヘキサメチレンジアミンカーバメートなどの脂肪族多価アミン化合物、及びその炭酸塩；４，４'－メチレンジアニリンなどの芳香族多価アミン化合物；安息香酸アンモニウム、アジピン酸アンモニウムなそのカルボン酸アンモニウム塩；ジメチルジチオカルバミン酸亜鉛などのジチオカルバミン酸金属塩；テトラデカン二酸などの多価カルボン酸；セチルトリメチルアンモニウムブロマイドなどの四級オニウム塩；２－メチルイミダゾールなどのイミダゾール化合物；イソシアヌル酸アンモニウムなどのイソシアヌル酸化合物；などを用いることができ、これらの中でもカルボン酸アンモニウム塩及びジチオカルバミン酸金属塩が好ましく、安息香酸アンモニウムがより好ましい。 When the acrylic rubber veil to be used is composed of an epoxy group-containing acrylic rubber, the cross-linking agent is an aliphatic polyvalent amine compound such as hexamethylenediamine or hexamethylenediamine carbamate, and a carbonate thereof; 4,4'-methylene. Aromatic polyvalent amine compounds such as dianiline; ammonium carboxylic acid salts such as ammonium benzoate and ammonium adipate; metal dithiocarbamic acid salts such as zinc dimethyldithiocarbamate; polyvalent carboxylic acids such as tetradecanodic acid; cetyltrimethylammonium bromide Tertiary onium salts such as; imidazole compounds such as 2-methylimidazole; isocyanuric acid compounds such as ammonium isocyanurate; among these, ammonium carboxylic acid salt and metal dithiocarbamate salt are preferable, and ammonium benzoate is preferable. Is more preferable.
　使用するアクリルゴムベールがハロゲン原子含有アクリルゴムで構成される場合は、架橋剤として、硫黄、硫黄供与体、トリアジンチオール化合物を用いることが好ましい。硫黄供与体としては、例えば、ジペンタメチレンチウラムヘキササルファイド、トリエチルチウラムジサルファイドなどが挙げられる。トリアジン化合物としては、例えば、６－トリメルカプト－ｓ－トリアジン、２－アニリノ－４，６－ジチオール－ｓ－トリアジン、１－ジブチルアミノ－３，５－ジメルカプトトリアジン、２－ジブチルアミノ－４，６－ジチオール－ｓ－トリアジン、１－フェニルアミノ－３，５－ジメルカプトトリアジン、２，４，６－トリメルカプト－１，３，５－トリアジン、１－ヘキシルアミノ－３，５－ジメルカプトトリアジンなどが挙げられ、これらの中でも、２，４，６－トリメルカプト－１，３，５－トリアジンが好ましい。 When the acrylic rubber veil to be used is composed of halogen atom-containing acrylic rubber, it is preferable to use sulfur, a sulfur donor, or a triazine thiol compound as a cross-linking agent. Examples of the sulfur donor include dipentamethylene thiuram hexasulfide and triethyl thiuram disulfide. Examples of the triazine compound 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.
　これらの架橋剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができ、その配合量は、アクリルゴムベール１００重量部に対し、通常０．００１～２０重量部、好ましくは０．１～１０重量部、より好ましくは０．１～５重量部である。架橋剤の配合量をこの範囲とすることにより、ゴム弾性を充分なものとしながら、ゴム架橋物としての機械的強度を優れたものとすることができ好適である。 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 0.1, based on 100 parts by weight of the acrylic rubber veil. It is ~ 10 parts by weight, more preferably 0.1 ~ 5 parts by weight. By setting the blending amount of the cross-linking agent within this range, it is possible to make the mechanical strength of the rubber cross-linked product excellent while making the rubber elasticity sufficient, which is preferable.
　本発明のゴム混合物は、必要に応じて前記アクリルゴムベール以外のその他のゴム成分を用いることができる。 In the rubber mixture of the present invention, other rubber components other than the acrylic rubber veil can be used if necessary.
　必要に応じて使用されるその他のゴム成分としては、格別な限定はなく、例えば、天然ゴム、ポリブタジエンゴム、ポリイソプレンゴム、スチレン－ブタジエンゴム、アクリロニトリル－ブタジエンゴム、シリコンゴム、フッ素ゴム、オレフィン系エラストマー、スチレン系エラストマー、塩化ビニル系エラストマー、ポリエステル系エラストマー、ポリアミド系エラストマー、ポリウレタン系エラストマー、ポリシロキサン系エラストマーなどを挙げることができる。その他のゴム成分の形状は、格別限定されるものではなく、例えば、クラム状、シート状、ベール状などいずれでもよい。 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 crumb shape, a sheet shape, a veil shape, or the like.
　これらのその他のゴム成分は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができる。これらのその他のゴム成分の使用量は、本発明の効果を損ねない範囲で適宜選択される。 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.
　本発明のゴム混合物は、必要に応じて老化防止剤を配合することができる。老化防止剤としては、特に限定されないが、２，６－ジ－ｔ－ブチル－４－メチルフェノール、２，６－ジ－ｔ－ブチルフェノール、ブチルヒドロキシアニソール、２，６－ジ－ｔ－ブチル－α－ジメチルアミノ－ｐ－クレゾール、オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、スチレン化フェノール、２，２'－メチレン－ビス（６－α－メチル－ベンジル－ｐ－クレゾール）、４，４'－メチレンビス（２，６－ジ－ｔ－ブチルフェノール）、２，２'－メチレン－ビス（４－メチル－６－ｔ－ブチルフェノール）、２，４－ビス［（オクチルチオ）メチル］－６－メチルフェノール、２，２'－チオビス－（４－メチル－６－ｔ－ブチルフェノール）、４，４'－チオビス－（６－ｔ－ブチル－ｏ－クレゾール）、２，６－ジ－ｔ－ブチル－４－（４，６－ビス（オクチルチオ）－１，３，５－トリアジン－２－イルアミノ）フェノールなどのその他のフェノール系老化防止剤；トリス（ノニルフェニル）ホスファイト、ジフェニルイソデシルホスファイト、テトラフェニルジプロピレングリコール・ジホスファイトなどの亜燐酸エステル系老化防止剤；チオジプロピオン酸ジラウリルなどの硫黄エステル系老化防止剤；フェニル－α－ナフチルアミン、フェニル－β－ナフチルアミン、ｐ－（ｐ－トルエンスルホニルアミド）－ジフェニルアミン、４，４'―（α，α－ジメチルベンジル）ジフェニルアミン、Ｎ，Ｎ－ジフェニル－ｐ－フェニレンジアミン、Ｎ－イソプロピル－Ｎ'－フェニル－ｐ－フェニレンジアミン、ブチルアルデヒド－アニリン縮合物などのアミン系老化防止剤；２－メルカプトベンズイミダゾールなどのイミダゾール系老化防止剤；６－エトキシ－２，２，４－トリメチル－１，２－ジヒドロキノリンなどのキノリン系老化防止剤；２，５－ジ－（ｔ－アミル）ハイドロキノンなどのハイドロキノン系老化防止剤；などが挙げられる。これらの中でも特に、アミン系老化防止剤が好ましい。 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, butylhydroxyanisole, 2,6-di-t-butyl-. α-Dimethylamino-p-cresol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, styrenated phenol, 2,2'-methylene-bis (6-α-methyl-) Benzyl-p-cresol), 4,4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2,4-bis [(Octylthio) Methyl] -6-methylphenol, 2,2'-thiobis- (4-methyl-6-t-butylphenol), 4,4'-thiobis- (6-t-butyl-o-cresol), Other phenolic anti-aging agents such as 2,6-di-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine-2-ylamino) phenol; tris (nonylphenyl) Phenolic acid ester anti-aging agents such as phosphite, diphenylisodecylphosphite, tetraphenyldipropylene glycol diphosphite; sulfur ester anti-aging agents such as dilauryl thiodipropionate; phenyl-α-naphthylamine, phenyl-β- Naftylamine, p- (p-toluenesulfonylamide) -diphenylamine, 4,4'-(α, α-dimethylbenzyl) diphenylamine, N, N-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p -Amine-based antioxidants such as phenylenediamine, butylaldehyde-aniline condensate; imidazole-based antioxidants such as 2-mercaptobenzimidazole; 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinolin, etc. 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.
　これらの老化防止剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができ、その配合量は、アクリルゴムベール１００重量部に対して、０．０１～１５重量部、好ましくは０．１～１０重量部、より好ましくは１～５重量部の範囲である。 These 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, preferably 0.% by weight, based on 100 parts by weight of the acrylic rubber veil. It is in the range of 1 to 10 parts by weight, more preferably 1 to 5 parts by weight.
　本発明のゴム混合物は、上記本発明のアクリルゴムベール、充填剤、架橋剤及び必要に応じてその他のゴム成分や老化防止剤を含み、更に、必要に応じて当該技術分野で通常使用される他の添加剤、例えば、架橋助剤、架橋促進剤、架橋遅延剤、シランカップリング剤、可塑剤、加工助剤、滑材、顔料、着色剤、帯電防止剤、発泡剤などを任意に配合できる。これらのその他の配合剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができ、その配合量は、本発明の効果を損ねない範囲で適宜選択される。 The rubber mixture of the present invention contains the 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 is usually used in the art as necessary. Optional blending of other additives such as cross-linking aids, cross-linking accelerators, cross-linking retarders, silane coupling agents, plasticizers, processing aids, rubbers, pigments, colorants, antistatic agents, foaming agents, etc. it can. 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.
　＜ゴム混合物の製造方法＞
　本発明のゴム混合物の製造方法としては、本発明のアクリルゴムベールに、前記充填剤、架橋剤及び必要に応じて含有できる前記その他のゴム成分、老化防止剤及びその他の配合剤を混合する方法が挙げられ、混合には、従来ゴム加工分野において利用されている任意の手段、例えば、オープンロール、バンバリーミキサー、各種ニーダー類などを利用することができる。すなわち、これらの混合機を用いて、アクリルゴムベールと、前記充填剤、架橋剤などを直接混合、好ましくは直接混錬することにより混合できる。 <Manufacturing method of rubber mixture>
As a method for producing a rubber mixture of the present invention, the acrylic rubber veil of the present invention is mixed with the filler, a cross-linking agent and other rubber components, an antiaging agent and other compounding agents which can be contained if necessary. For the mixing, any means conventionally used in the rubber processing field, for example, an open roll, a Banbury mixer, various kneaders and the like can be used. That is, using these mixers, the acrylic rubber veil can be mixed by directly mixing the filler, the cross-linking agent and the like, preferably by directly kneading.
　その場合において、アクリルゴムベールは、得られたベールをそのままでも、分割（切断など）して用いてもよい。 In that case, the acrylic rubber bale may be used as it is or divided (cut, etc.).
　各成分の混合手順は、格別な限定はないが、例えば、熱で反応や分解しにくい成分を充分に混合した後、熱で反応や分解しやすい成分である架橋剤などを反応や分解が起こらない温度で短時間に混合する二段階混合が好ましい。具体的には、１段目にアクリルゴムベールと充填剤を混合した後に、２段目で架橋剤を混合することが好ましい。その他のゴム成分と老化防止剤は通常１段目に混合され、架橋促進剤は２段目、その他の配合剤は適宜選択されればよい。 The mixing procedure of 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 veil and the filler in the first step and then mix the cross-linking agent in the second step. 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.
　かくして得られる本発明のゴム混合物のムーニー粘度（ＭＬ１＋４，１００℃；コンパンドムーニー）は、格別限定されるものではないが、通常１０～１５０、好ましくは２０～１００、より好ましくは２５～８０の範囲である。 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.
　＜ゴム架橋物＞
　本発明のゴム架橋物は、上記ゴム混合物を架橋してなるものである。 <Rubber crosslinked product>
The rubber crosslinked product of the present invention is obtained by cross-linking the above rubber mixture.
　本発明のゴム架橋物は、本発明のゴム混合物を用い、所望の形状に対応した成形機、例えば、押出機、射出成形機、圧縮機、及びロールなどにより成形を行い、加熱することにより架橋反応を行い、ゴム架橋物として形状を固定化することにより製造することができる。この場合においては、予め成形した後に架橋しても、成形と同時に架橋を行ってもよい。成形温度は、通常１０～２００℃、好ましくは２５～１５０℃である。架橋温度は、通常１００～２５０℃、好ましくは１３０～２２０℃、より好ましくは１５０～２００℃であり、架橋時間は、通常０．１分～１０時間、好ましくは１分～５時間である。加熱方法としては、プレス加熱、蒸気加熱、オーブン加熱、及び熱風加熱などのゴムの架橋に用いられる方法を適宜選択すればよい。 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., and the crosslinking time is usually 0.1 minutes to 10 hours, preferably 1 minute to 5 hours. As the heating method, a method used for cross-linking rubber such as press heating, steam heating, oven heating, and hot air heating may be appropriately selected.
　本発明のゴム架橋物は、ゴム架橋物の形状、大きさなどによっては、更に加熱して二次架橋を行ってもよい。二次架橋は、加熱方法、架橋温度、形状などにより異なるが、好ましくは１～４８時間行う。加熱方法、加熱温度は適宜選択すればよい。 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.
　本発明のゴム架橋物は、例えば、Ｏ－リング、パッキン、ダイアフラム、オイルシール、シャフトシール、ベアリングシース、メカニカルシール、ウエルヘッドシール、電気・電子機器用シール、空気圧縮機器用シールなどのシール材；シリンダブロックとシリンダヘッドとの連結部に装着されるロッカーカバーガスケット、オイルパンとシリンダヘッドあるいはトランスミッションケースとの連結部に装着されるオイルパンガスケット、正極、電解質板及び負極を備えた単位セルを挟み込む一対のハウジング間に装着された燃料電池セパレーター用ガスケット、ハードディスクドライブのトップカバー用ガスケットなどの各種ガスケット；緩衝材、防振材；電線被覆材；工業用ベルト類；チューブ・ホース類；シート類；などとして好適に用いられる。 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 unit cell equipped with a rocker cover gasket attached to the connecting portion between the cylinder block and the cylinder head, an oil pan gasket attached to the connecting portion between the oil pan and the cylinder head or the transmission case, a positive electrode, an electrolyte plate and a negative electrode. Various 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;
　本発明のゴム架橋物は、また、自動車用途に用いられる押し出し成形型品及び型架橋製品として、例えば、燃料ホース、フィラーネックホース、ベントホース、ペーパーホース、オイルホースなどの燃料タンクなどの燃料油系ホース、ターボエアーホース、ミッションコントロールホースなどのエアー系ホース、ラジエターホース、ヒーターホース、ブレーキホース、エアコンホースなどの各種ホース類に好適に用いられる。 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.
　＜アクリルゴムベールの製造に用いられる装置構成＞
　次に、本発明の一実施形態に係るアクリルゴムベールの製造に用いられる装置構成について説明する。図１は、本発明の一実施形態に係るアクリルゴムベールの製造に用いられる装置構成を有するアクリルゴム製造システムの一例を模式的に示す図である。本発明に係るアクリルゴムの製造には、例えば、図１に示すアクリルゴム製造システム１を使用することができる。 <Device configuration used for manufacturing acrylic rubber veils>
Next, an apparatus configuration used for manufacturing an acrylic rubber veil according to an embodiment of the present invention will be described. 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 veil according to an embodiment of the present invention. For the production of the acrylic rubber according to the present invention, for example, the acrylic rubber production system 1 shown in FIG. 1 can be used.
　図１に示すアクリルゴム製造システム１は、不図示の乳化重合反応器、凝固装置３、洗浄装置４、水切り機４３、スクリュー型押出機５、冷却装置６、ベール化装置７により構成されている。 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. ..
　乳化重合反応器は、上述した乳化重合工程に係る処理を行うように構成されている。図１には不図示であるが、この乳化重合反応器は、例えば重合反応槽、反応温度を制御する温度制御部、モータ及び撹拌翼を備えた撹拌装置を有する。乳化重合反応器では、アクリルゴムを形成するための単量体成分に水と乳化剤とを混合して撹拌機で適切に撹拌しながらエマルジョン化し、重合触媒存在下において乳化重合することで乳化重合液を得ることができる。乳化重合反応器は、回分式、半回分式、連続式のいずれであってもよく、槽型反応器、管型反応器のいずれであってもよい。 The emulsion polymerization reactor is configured to perform the treatment related to the emulsion polymerization step described above. Although not shown in FIG. 1, 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. In the emulsion polymerization reactor, 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 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.
　図１に示す凝固装置３は、上述した凝固工程に係る処理を行うように構成されている。図１に模式的に図示されているように、凝固装置３は、例えば撹拌槽３０、撹拌槽３０内を加熱する加熱部３１、撹拌槽３０内の温度を制御する不図示の温度制御部、モータ３２及び撹拌翼３３を備えた撹拌装置３４、撹拌翼３３の回転数及び回転速度を制御する不図示の駆動制御部を有する。凝固装置３では、乳化重合反応器で得られた乳化重合液を、凝固剤としての凝固液と接触させて凝固させることにより含水クラムを生成することができる。 The coagulation device 3 shown in FIG. 1 is configured to perform the process related to the coagulation step described above. As schematically shown in FIG. 1, 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. In the coagulation apparatus 3, a hydrous crumb can be produced by bringing the emulsion polymerization solution obtained by the emulsion polymerization reactor into contact with the coagulation solution as a coagulant and coagulating it.
　凝固装置３では、例えば、乳化重合液と凝固液との接触は、乳化重合液を撹拌している凝固液中に添加する方法が採用される。すなわち、凝固装置３の撹拌槽３０に凝固液を充填しておき、この凝固液に乳化重合液を添加及び接触させて乳化重合液を凝固させることによって含水クラムが生成される。 In the coagulation device 3, for example, 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.
　凝固装置３の加熱部３１は、撹拌槽３０に充填された凝固液を加熱するよう構成されている。また、凝固装置３の温度制御部は、温度計で計測された撹拌槽３０内の温度を監視しながら加熱部３１による加熱動作を制御することで、撹拌槽３０内の温度を制御するように構成されている。撹拌槽３０内の凝固液の温度は、温度制御部によって、通常４０℃以上、好ましくは４０～９０℃、より好ましくは５０～８０℃の範囲となるよう制御される。 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.
　凝固装置３の撹拌装置３４は、撹拌槽３０に充填された凝固液を撹拌するように構成されている。具体的には、撹拌装置３４は、回転動力を生み出すモータ３２と、モータ３２の回転軸に対して垂直方向に広がる撹拌翼３３を備えている。撹拌翼３３は、撹拌槽３０に充填された凝固液内で、モータ３２の回転動力により回転軸を中心として回転することで凝固液を流動させることができる。撹拌翼３３の形状や大きさ、設置数などは特に限定されない。 The stirring device 34 of the coagulating device 3 is configured to stir the coagulating liquid filled in the stirring tank 30. Specifically, 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.
　凝固装置３の駆動制御部は、撹拌装置３４のモータ３２の回転駆動を制御して、撹拌装置３４の撹拌翼３３の回転数及び回転速度を所定値に設定するように構成されている。凝固液の撹拌数が、例えば、通常１００ｒｐｍ以上、好ましくは２００～１，０００ｒｐｍ、より好ましくは３００～９００ｒｐｍ、特に好ましくは４００～８００ｒｐｍの範囲となるように、駆動制御部によって撹拌翼３３の回転が制御される。凝固液の周速が、通常０．５ｍ／ｓ以上、好ましくは１ｍ／ｓ以上、より好ましくは１．５ｍ／ｓ以上、特に好ましくは２ｍ／ｓ以上、最も好ましくは２．５ｍ／ｓ以上となるように、駆動制御部によって撹拌翼３３の回転が制御される。さらに、凝固液の周速の上限値が、通常５０ｍ／ｓ以下、好ましくは３０ｍ／ｓ以下、より好ましくは２５ｍ／ｓ以下、最も好ましくは２０ｍ／ｓ以下となるように、駆動制御部によって撹拌翼３３の回転が制御される。 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.
　図１に示す洗浄装置４は、上述した洗浄工程に係る処理を行うように構成されている。図１に模式的に図示されているように、洗浄装置４は、例えば洗浄槽４０、洗浄槽４０内を加熱する加熱部４１、洗浄槽４０内の温度を制御する不図示の温度制御部を有する。洗浄装置４では、凝固装置３で生成された含水クラムを多量の水と混合して洗浄することにより、最終的に得られるアクリルゴムベール中の灰分量を効果的に低減することができる。 The cleaning device 4 shown in FIG. 1 is configured to perform the processing related to the cleaning process described above. As schematically shown in FIG. 1, 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. Have. In the cleaning device 4, the amount of ash in the finally obtained acrylic rubber veil can be effectively reduced by mixing the hydrous crumb generated by the coagulation device 3 with a large amount of water and cleaning.
　洗浄装置４の加熱部４１は、洗浄槽４０内を加熱するよう構成されている。また、洗浄装置４の温度制御部は、温度計で計測された洗浄槽４０内の温度を監視しながら加熱部４１による加熱動作を制御することで、洗浄槽４０内の温度を制御するように構成されている。上述したように、洗浄槽４０内の洗浄水の温度は、通常４０℃以上、好ましくは４０～１００℃、より好ましくは５０～９０℃、最も好ましくは６０～８０℃の範囲となるよう制御される。 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.
　洗浄装置４で洗浄された含水クラムは、脱水工程及び乾燥工程を行うスクリュー型押出機５に供給される。このとき、洗浄後の含水クラムは、遊離水を分離することが可能な水切り機４３を通ってスクリュー型押出機５に供給されることが好ましい。水切り機４３には、例えば金網、スクリーン、電動篩機などを用いることができる。 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. For the drainer 43, for example, a wire mesh, a screen, an electric sieve, or the like can be used.
　また、洗浄後の含水クラムがスクリュー型押出機５に供給される際、含水クラムの温度は４０℃以上、更に６０℃以上であることが好ましい。例えば、洗浄装置４における水洗に用いられる水の温度を６０℃以上（例えば７０℃）とすることで、スクリュー型押出機５に供給された際の含水クラムの温度を６０℃以上に維持することができるようにしてもよく、洗浄装置４からスクリュー型押出機５に搬送する際に含水クラムの温度が４０℃以上、好ましくは６０℃以上となるよう加温してもよい。これにより、後工程である脱水工程及び乾燥工程を効果的に行うことが可能となり、最終的に得られる乾燥ゴムの含水率を大幅に低減させることが可能となる。 Further, when the water-containing crumb after cleaning is supplied to the screw type extruder 5, the temperature of the water-containing crumb is preferably 40 ° C. or higher, more preferably 60 ° C. or higher. For example, by setting the temperature of the water used for washing in the washing device 4 to 60 ° C. or higher (for example, 70 ° C.), 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. As a result, the dehydration step and the drying step, which are the subsequent steps, can be effectively performed, and the water content of the finally obtained dried rubber can be significantly reduced.
　図１に示すスクリュー型押出機５は、上述した脱水工程及び乾燥工程に係る処理を行うように構成されている。なお、図１には好適な例としてスクリュー型押出機５が図示されているが、脱水工程に係る処理を行う脱水機として遠心分離機やスクイザーなどを用いてもよく、乾燥工程に係る処理を行う乾燥機として熱風乾燥機、減圧乾燥機、エキスパンダー乾燥機、ニーダー型乾燥機などを用いてもよい。 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. Although the screw type extruder 5 is shown as a suitable example in FIG. 1, 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.
　スクリュー型押出機５は、脱水工程及び乾燥工程を経て得られる乾燥ゴムを所定の形状に成形して排出するように構成されている。具体的には、スクリュー型押出機５は、洗浄装置４で洗浄された含水クラムを脱水する脱水機としての機能を有する脱水バレル部５３と、含水クラムを乾燥する乾燥機としての機能を有する乾燥バレル部５４とを備えており、さらにスクリュー型押出機５の下流側に含水クラムを成形する成形機能を有するダイ５９を備えて構成されている。 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. Specifically, 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.
　以下、図２を参照しながら、スクリュー型押出機５の構成について説明する。図２は、図１で示したスクリュー型押出機５として好適な一具体例の構成を示している。このスクリュー型押出機５により、上述した脱水・乾燥工程を好適に行うことができる。 Hereinafter, the configuration of the screw type extruder 5 will be described with reference to FIG. FIG. 2 shows a configuration of a specific example suitable for the screw type extruder 5 shown in FIG. With this screw type extruder 5, the above-mentioned dehydration / drying step can be suitably performed.
　図２に示すスクリュー型押出機５は、バレルユニット５１内に不図示の一対のスクリューを備えてなる二軸スクリュー型の押出乾燥機である。スクリュー型押出機５は、バレルユニット５１内の一対のスクリューを回転駆動する駆動ユニット５０を有する。駆動ユニット５０は、バレルユニット５１の上流端（図２で左端）に取り付けられている。また、スクリュー型押出機５は、バレルユニット５１の下流端（図２で右端）にダイ５９を有する。 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. Further, the screw type extruder 5 has a die 59 at the downstream end (right end in FIG. 2) of the barrel unit 51.
　バレルユニット５１は、上流側から下流側（図２で左側から右側）にわたり、供給バレル部５２、脱水バレル部５３、乾燥バレル部５４を有する。 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).
　供給バレル部５２は、２つの供給バレル、すなわち、第１の供給バレル５２ａ及び第２の供給バレル５２ｂにより構成されている。 The supply barrel portion 52 is composed of two supply barrels, that is, a first supply barrel 52a and a second supply barrel 52b.
　また、脱水バレル部５３は、３つの脱水バレル、すなわち、第１の脱水バレル５３ａ、第２の脱水バレル５３ｂ及び第３の脱水バレル５３ｃにより構成されている。 Further, 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.
　また、乾燥バレル部５４は、８個の乾燥バレル、すなわち、第１の乾燥バレル５４ａ、第２の乾燥バレル５４ｂ、第３の乾燥バレル５４ｃ、第４の乾燥バレル５４ｄ、第５の乾燥バレル５４ｅ、第６の乾燥バレル５４ｆ、第７の乾燥バレル５４ｇ、第８の乾燥バレル５４ｈにより構成されている。 Further, 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.
　このようにバレルユニット５１は、分割された１３個の各バレル５２ａ～５２ｂ，５３ａ～５３ｃ，５４ａ～５４ｈが上流側から下流側にわたり連結されて構成されている。 As described above, 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.
　また、スクリュー型押出機５は、上記各バレル５２ａ～５２ｂ，５３ａ～５３ｃ，５４ａ～５４ｈを個別に加熱して、各バレル５２ａ～５２ｂ，５３ａ～５３ｃ，５４ａ～５４ｈ内の含水クラムをそれぞれ所定温度に加熱する不図示の加熱手段を有する。加熱手段は、各バレル５２ａ～５２ｂ，５３ａ～５３ｃ，５４ａ～５４ｈに対応する数を備える。そのような加熱手段としては、例えば、各バレル５２ａ～５２ｂ，５３ａ～５３ｃ，５４ａ～５４ｈ内に形成されたスチーム流通ジャケットにスチーム供給手段から高温スチームを供給するなどの構成が採用されるが、これに限定はされない。また、スクリュー型押出機５は、各バレル５２ａ～５２ｂ，５３ａ～５３ｃ，５４ａ～５４ｈに対応する各加熱手段の設定温度を制御する不図示の温度制御手段を有する。 Further, 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. As such 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. Further, 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.
　なお、バレルユニット５１における各バレル部５２、５３、５４をそれぞれ構成する供給バレル、脱水バレル及び乾燥バレルの設置数は、図２に示す態様に限定されるものではなく、乾燥処理するアクリルゴムの含水クラムの含水量などに応じた数に設定することができる。 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.
　例えば、供給バレル部５２の供給バレルの設置数は例えば１～３個とされる。また、脱水バレル部５３の脱水バレルの設置数は、例えば２～１０個が好ましく、３～６個とすると、粘着性のアクリルゴムの含水クラムの脱水を効率よく行うことができるのでより好ましい。また、乾燥バレル部５４の乾燥バレルの設置数は、例えば２～１０個が好ましく、３～８個であるとより好ましい。 For example, the number of supply barrels installed in the supply barrel portion 52 is, for example, 1 to 3. Further, 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. Further, 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.
　バレルユニット５１内の一対のスクリューは、駆動ユニット５０に格納されたモータなどの駆動手段によって回転駆動される。一対のスクリューはバレルユニット５１内の上流側から下流側にわたって延在しており、回転駆動されることで、供給バレル部５２に供給された含水クラムを混合しながら下流側に搬送することができるようになっている。一対のスクリューとしては、互いに山部と谷部とが噛み合わされる状態とされた二軸噛合型であることが好ましく、これにより、含水クラムの脱水効率及び乾燥効率を高めることができる。 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.
　また、一対のスクリューの回転方向は、同方向でも異方向でもよいが、セルフクリーニングの性能面からは同方向に回転する形式のものが好ましい。一対のスクリューのスクリュー形状としては、特に限定されず、各バレル部５２、５３、５４において必要とされる形状であればよく、特に限定されない。 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.
　供給バレル部５２は、含水クラムをバレルユニット５１内に供給する領域である。供給バレル部５２の第１の供給バレル５２ａは、バレルユニット５１内に含水クラムを供給するフィード口５５を有する。 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.
　脱水バレル部５３は、含水クラムから、凝固剤などが含まれる液体（セラム水）を分離し排出する領域である。 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.
　脱水バレル部５３を構成する第１～第３の脱水バレル５３ａ～５３ｃは、含水クラムの水分を外部に排出する脱水スリット５６ａ、５６ｂ、５６ｃをそれぞれ有する。各脱水スリット５６ａ、５６ｂ、５６ｃは、各脱水バレル５３ａ～５３ｃにそれぞれ複数形成されている。 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.
　各脱水スリット５６ａ、５６ｂ、５６ｃのスリット幅すなわち目開きは、使用条件に応じて適宜選択されればよく、通常で０．０１～５ｍｍとされ、含水クラムの損出が少なく、且つ含水クラムの脱水が効率的にできる点から、好ましくは０．１～１ｍｍであり、０．２～０．６ｍｍであればより好ましい。 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.
　脱水バレル部５３の各脱水バレル５３ａ～５３ｃにおける含水クラムからの水分の除去は、それぞれの脱水スリット５６ａ、５６ｂ、５６ｃから液状で除去する場合と、蒸気状で除去する場合との二通りがある。本実施形態の脱水バレル部５３においては、水分を液状で除去する場合を排水と定義し、蒸気状で除去する場合を排蒸気と定義して区別する。 There are two ways to remove water from the water-containing crumbs in each of the dehydration barrels 53a to 53c of the dehydration barrel portion 53: a liquid removal from the dehydration slits 56a, 56b, 56c, and a vapor removal. .. In the dehydration barrel portion 53 of the present embodiment, the case where water is removed in liquid form is defined as wastewater, and the case where water is removed in vapor form is defined as exhaust steam.
　脱水バレル部５３においては、排水及び排蒸気を組み合わせることで、粘着性アクリルゴムの含水率を低下させることが効率よくできるので好適である。脱水バレル部５３では、第１～第３の脱水バレル５３ａ～５３ｃのうち、どの脱水バレルで排水又は排蒸気を行うかは、使用目的に応じて適宜に設定すればよいが、通常製造されるアクリルゴム中の灰分量を少なくする場合は、排水を行う脱水バレルを多くするとよい。その場合、例えば図２に示すように、上流側の第１及び第２の脱水バレル５３ａ、５３ｂで排水を行い、下流側の第３の脱水バレル５３ｃで排蒸気を行う。また、例えば脱水バレル部５３が４つの脱水バレルを有する場合には、例えば上流側の３つの脱水バレルで排水を行い、下流側の１つの脱水バレルで排蒸気を行うといった態様が考えられる。一方、含水量を低減する場合には、排蒸気を行う脱水バレルを多くするとよい。 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. In the dehydration barrel portion 53, 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. When reducing the amount of ash in the acrylic rubber, it is advisable to increase the number of dehydration barrels for draining. In that case, for example, as shown in FIG. 2, drainage is performed in the first and second dehydration barrels 53a and 53b on the upstream side, and steam is discharged in the third dehydration barrel 53c on the downstream side. Further, for example, when the dehydration barrel portion 53 has four dehydration barrels, for example, 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. On the other hand, when reducing the water content, it is preferable to increase the number of dehydration barrels for exhausting steam.
　脱水バレル部５３の設定温度は、上述の脱水・乾燥工程で述べたように、通常６０～１５０℃、好ましくは７０～１４０℃、より好ましくは８０～１３０℃の範囲であり、排水状態で脱水する脱水バレルの設定温度は、通常６０℃～１２０℃、好ましくは７０～１１０℃、より好ましくは８０～１００℃であり、排蒸気状態で脱水する脱水バレルの設定温度は、通常１００～１５０℃、好ましくは１０５～１４０℃、より好ましくは１１０～１３０℃の範囲である。 As described in the above-mentioned dehydration / drying step, 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., and 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.
　乾燥バレル部５４は、脱水後の含水クラムを減圧下で乾燥させる領域である。乾燥バレル部５４を構成する第１～第８の乾燥バレル５４ａ～５４ｈのうち、第２の乾燥バレル５４ｂ、第４の乾燥バレル５４ｄ、第６の乾燥バレル５４ｆ及び第８の乾燥バレル５４ｈは、脱気のためのベント口５８ａ、５８ｂ、５８ｃ、５８ｄをそれぞれ有する。各ベント口５８ａ、５８ｂ、５８ｃ、５８ｄには、不図示のベント配管がそれぞれ接続されている。 The drying barrel portion 54 is a region where the hydrous crumb after dehydration is dried under reduced pressure. Of the first to eighth dry barrels 54a to 54h constituting the dry barrel portion 54, 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.
　各ベント配管の末端には不図示の真空ポンプがそれぞれ接続されており、それら真空ポンプの作動により、乾燥バレル部５４内が所定圧力に減圧されるようになっている。スクリュー型押出機５は、それら真空ポンプの作動を制御して乾燥バレル部５４内の減圧度を制御する図示せぬ圧力制御手段を有する。 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.
　乾燥バレル部５４での減圧度は適宜選択されればよいが、上述したように、通常１～５０ｋＰａ、好ましくは２～３０ｋＰａ、より好ましくは３～２０ｋＰａに設定される。 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.
　また、乾燥バレル部５４内の設定温度は適宜選択されればよいが、上述したように、通常１００～２５０℃、好ましくは１１０～２００℃、より好ましくは１２０～１８０℃に設定される。 Further, 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.
　乾燥バレル部５４を構成する各乾燥バレル５４ａ～５４ｈにおいては、全ての乾燥バレル５４ａ～５４ｈ内の設定温度を近似した値にしてもよいし、異ならせてもよいが、上流側（脱水バレル部５３側）の温度よりも下流側（ダイ５９側）の温度の方を高温に設定すると、乾燥効率が向上するので好ましい。 In each of the dry barrels 54a to 54h constituting the dry barrel portion 54, 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.
　ダイ５９は、バレルユニット５１の下流端に配置される金型であり、所定のノズル形状の吐出口を有する。乾燥バレル部５４で乾燥処理されたアクリルゴムは、ダイ５９の吐出口を通過することで、所定のノズル形状に応じた形状に押出成形される。ダイ５９を通過するアクリルゴムは、ダイ５９のノズル形状に応じて、粒状、柱状、丸棒状、シート状など、種々の形状に成形される。例えば、ダイ５９の吐出口を略長方形状とすることで、アクリルゴムをシート状に押出成形することができる。スクリューとダイ５９との間には、ブレーカープレートや金網を設けてもよいし、設けなくてもよい。 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 acrylic rubber that passes through the die 59 is formed into various shapes such as granular, columnar, round bar, and sheet depending on the nozzle shape of the die 59. For example, by making the discharge port of the die 59 substantially rectangular, the acrylic rubber can be extruded into a sheet shape. A breaker plate or wire mesh may or may not be provided between the screw and the die 59.
　本実施形態に係るスクリュー型押出機５によれば、以下のようにして、原料のアクリルゴムの含水クラムがシート状の乾燥ゴムに押出成形される。 According to the screw type extruder 5 according to the present embodiment, the water-containing crumb of the raw material acrylic rubber is extruded into a sheet-shaped dry rubber as follows.
　洗浄工程を経て得られたアクリルゴムの含水クラムは、フィード口５５から供給バレル部５２に供給される。供給バレル部５２に供給された含水クラムは、バレルユニット５１内の一対のスクリューの回転により、供給バレル部５２から脱水バレル部５３に送られる。脱水バレル部５３では、前述したように第１～第３の脱水バレル５３ａ～５３ｃにそれぞれ設けられた脱水スリット５６ａ、５６ｂ、５６ｃから、含水クラムに含まれる水分の排水や排蒸気が行われて、含水クラムが脱水処理される。 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. In 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.
　脱水バレル部５３で脱水された含水クラムは、バレルユニット５１内の一対のスクリューの回転により乾燥バレル部５４に送られる。乾燥バレル部５４に送られた含水クラムは可塑化混合されて融体となり、発熱して昇温しながら下流側へ運ばれる。そして、このアクリルゴムの融体中に含まれる水分が気化し、その水分（蒸気）が各ベント口５８ａ、５８ｂ、５８ｃ、５８ｄにそれぞれ接続された不図示のベント配管を通じて外部へ排出される。 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.
　上記のように乾燥バレル部５４を通過することで含水クラムは乾燥処理されてアクリルゴムの融体となり、そのアクリルゴムはバレルユニット５１内の一対のスクリューの回転によりダイ５９に供給され、シート状の乾燥ゴムとしてダイ５９から押し出される。 By passing through the dry barrel portion 54 as described above, 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.
　ここで、本実施形態に係るスクリュー型押出機５の操業条件の一例を挙げる。 Here, an example of the operating conditions of the screw type extruder 5 according to the present embodiment will be given.
　バレルユニット５１内の一対のスクリューの回転数（Ｎ）は、諸条件に応じて適宜選択されればよく、通常で１０～１，０００ｒｐｍとされ、アクリルゴムベールの含水量とゲル量を効率よく低減できる点から、好ましくは５０～７５０ｒｐｍ、より好ましくは１００～５００ｒｐｍであり、１２０～３００ｒｐｍが最も好ましい。 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 veil 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.
　また、アクリルゴムの押出量（Ｑ）は、格別限定されないが、通常で１００～１，５００ｋｇ／ｈｒとされ、好ましくは３００～１，２００ｋｇ／ｈｒ、より好ましくは４００～１，０００ｋｇ／ｈｒであり、５００～８００ｋｇ／ｈｒが最も好ましい。 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.
　また、アクリルゴムの押出量（Ｑ）とスクリューの回転数（Ｎ）との比（Ｑ／Ｎ）は、格別限定されないが、通常で１～２０とされ、好ましくは２～１０、より好ましくは３～８であり、４～６が特に好ましい。 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.
　図１に示す冷却装置６は、脱水機による脱水工程及び乾燥機による乾燥工程を経て得られた乾燥ゴムを冷却するように構成されている。冷却装置６による冷却方式としては、送風あるいは冷房下での空冷方式、水を吹き付ける水かけ方式、水中に浸漬する浸漬方式などを含む様々な方式を採用することが可能である。また、室温下に放置することで、乾燥ゴムを冷却するようにしてもよい。 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. As 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.
　上述したように、ダイ５９のノズル形状に応じて、スクリュー型押出機５から排出された乾燥ゴムは、粒状、柱状、丸棒状、シート状など、種々の形状に押出成形される。以下、図３を参照しながら、冷却装置６の一例として、シート状に成形されたシート状乾燥ゴム１０を冷却する搬送式冷却装置６０について説明する。 As described above, the dried rubber discharged from the screw type extruder 5 is extruded into various shapes such as granular, columnar, round bar, and sheet according to the nozzle shape of the die 59. Hereinafter, as an example of the cooling device 6, 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.
　図３は、図１で示した冷却装置６として好適な搬送式冷却装置６０の構成を示している。図３に示す搬送式冷却装置６０は、スクリュー型押出機５のダイ５９の吐出口から排出されたシート状乾燥ゴム１０を搬送しながら、空冷方式によって冷却するよう構成されている。この搬送式冷却装置６０を用いることで、スクリュー型押出機５から排出されたシート状乾燥ゴムを好適に冷却することができる。 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. By using this transport type cooling device 60, the sheet-shaped dry rubber discharged from the screw type extruder 5 can be suitably cooled.
　図３に示す搬送式冷却装置６０は、例えば、図２に示したスクリュー型押出機５のダイ５９に直結するか、又はダイ５９の近傍に設置して使用される。 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.
　搬送式冷却装置６０は、スクリュー型押出機５のダイ５９から排出されるシート状乾燥ゴム１０を図３中矢印Ａ方向に搬送するコンベア６１と、コンベア６１上のシート状乾燥ゴム１０に冷風を吹き付ける冷却手段６５とを有する。 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.
　コンベア６１は、ローラ６２、６３と、これらローラ６２、６３に巻架され、シート状乾燥ゴム１０がその上に載せられるコンベアベルト６４とを有する。コンベア６１は、コンベアベルト６４上にスクリュー型押出機５のダイ５９から排出されたシート状乾燥ゴム１０を連続して下流側（図３で右側）に搬送するよう構成されている。 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.
　冷却手段６５は、特に限定されないが、例えば、不図示の冷却風発生手段から送られてくる冷却風をコンベアベルト６４上のシート状乾燥ゴム１０の表面に吹き付けることができるような構成を有するものなどが挙げられる。 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.
　搬送式冷却装置６０のコンベア６１及び冷却手段６５の長さ（冷却風の吹き付けが可能な部分の長さ）Ｌ１は、特に限定されないが、例えば１０～１００ｍであり、好ましくは２０～５０ｍである。また、搬送式冷却装置６０におけるシート状乾燥ゴム１０の搬送速度は、コンベア６１及び冷却手段６５の長さＬ１、スクリュー型押出機５のダイ５９から排出されるシート状乾燥ゴム１０の排出速度、目標とする冷却速度や冷却時間などに応じて適宜調整すればよいが、例えば１０～１００ｍ／ｈｒであり、より好ましくは１５～７０ｍ／ｈｒである。 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. .. Further, 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.
　図３に示す搬送式冷却装置６０によれば、スクリュー型押出機５のダイ５９から排出されるシート状乾燥ゴム１０をコンベア６１にて搬送しつつ、シート状乾燥ゴム１０に対し冷却手段６５から冷却風を吹き付けることにより、シート状乾燥ゴム１０の冷却が行われる。 According to the transport type cooling device 60 shown in FIG. 3, 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.
　なお、搬送式冷却装置６０としては、図３に示すような１つのコンベア６１及び１つの冷却手段６５を備える構成に特に限定されず、２つ以上のコンベア６１と、これに対応する２つ以上の冷却手段６５とを備えるような構成としてもよい。その場合には、２つ以上のコンベア６１及び冷却手段６５のそれぞれの総合長さを上記範囲とすればよい。 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.
　図１に示すベール化装置７は、スクリュー型押出機５から押出成形され、さらに冷却装置６で冷却された乾燥ゴムを加工して、一塊のブロックであるベールを製造するよう構成されている。上述したように、スクリュー型押出機５は、乾燥ゴムを粒状、柱状、丸棒状、シート状など、種々の形状に押出成形することが可能であり、ベール化装置７は、このように種々の形状に成形された乾燥ゴムをベール化するように構成されている。ベール化装置７によって製造されるアクリルゴムベールの重さや形状などは特に限定されないが、例えば約２０ｋｇの略直方体形状のアクリルゴムベールが製造される。 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. As described above, the screw type extruder 5 can extrude the dried rubber into various shapes such as granular, columnar, round bar, and sheet, and the bale device 7 has various shapes as described above. It is configured to veil dry rubber molded into a shape. 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.
　ベール化装置７は、例えばベーラーを備え、冷却された乾燥ゴムをベーラーにより圧縮することでアクリルゴムベールを製造してもよい。 The bale device 7 may include, for example, a baler, and may manufacture an acrylic rubber bale by compressing the cooled dry rubber with the baler.
　また、スクリュー型押出機５によってシート状乾燥ゴム１０を製造した場合には、シート状乾燥ゴム１０を積層したアクリルゴムベールを製造してもよい。例えば、図３に示す搬送式冷却装置６０の下流側に配置されるベール化装置７に、シート状乾燥ゴム１０を切断するカッティング機構が設けられていてもよい。具体的には、ベール化装置７のカッティング機構は、例えば、冷却されたシート状乾燥ゴム１０を連続的に所定の間隔で切断して、所定の大きさのカットシート状乾燥ゴム１６に加工するように構成されている。カッティング機構により所定の大きさに切断されたカットシート状乾燥ゴム１６を複数枚積層することで、カットシート状乾燥ゴム１６を積層したアクリルゴムベールを製造することができる。 Further, when the sheet-shaped dry rubber 10 is manufactured by the screw type extruder 5, an acrylic rubber veil in which the sheet-shaped dry rubber 10 is laminated may be manufactured. For example, 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. Specifically, 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.
　カットシート状乾燥ゴム１６を積層したアクリルゴムベールを製造する場合には、例えば４０℃以上のカットシート状乾燥ゴム１６を積層することが好ましい。４０℃以上のカットシート状乾燥ゴム１６を積層することで、更なる冷却及び自重による圧縮によって良好な空気抜けが実現される。 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.
　以下に、実施例及び比較例を挙げて、本発明についてより具体的に説明する。なお、各例中の「部」、「％」及び「比」は、特に断りのない限り、重量基準である。
　各種の物性については、以下の方法に従って評価した。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, "part", "%" and "ratio" in each example are weight-based unless otherwise specified.
Various physical properties were evaluated according to the following methods.
　［単量体組成］
　アクリルゴムにおける単量体組成に関して、アクリルゴム中の各単量体単位の単量体構成はＨ－ＮＭＲで確認し、アクリルゴム中に反応性基の活性が残存していること及びその各反応性基含有量は下記試験法で確認した。 [Monomer composition]
Regarding the monomer composition in acrylic rubber, the monomer composition of each monomer unit in acrylic rubber was confirmed by 1 H-NMR, and the activity of the reactive group remained in acrylic rubber and each reaction thereof. The reactive group content was confirmed by the following test method.
　また、各単量体単位のアクリルゴム中の含有割合は、各単量体の重合反応に用いた使用量及び重合転化率から算出した。具体的には、重合反応は乳化重合反応でその重合転化率は、未反応の単量体がいずれも確認できない略１００％であったことから、各単量体単位の含有割合を各単量体の使用量と同一とした。 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.
［反応性基含有量］
　アクリルゴムの反応性基の含有量は、下記方法によりアクリルゴムベール中の含有量を測定した。
　（１）カルボキシル基量は、アクリルゴムベールをアセトンに溶解し水酸化カリウム溶液で電位差滴定を行うことにより算出した。
　（２）エポキシ基量は、アクリルゴムベールをメチルエチルケトンに溶解し、それに規定量の塩酸を加えてエポキシ基と反応させ、残留した塩酸量を水酸化カリウムで滴定することにより算出した。
　（３）塩素量は、アクリルゴムベールを燃焼フラスコ中で完全燃焼させ、発生する塩素を水に吸収させ硝酸銀で滴定することにより算出した。 [Reactive group content]
The content of the reactive group of the acrylic rubber was measured in the acrylic rubber veil by the following method.
(1) The amount of carboxyl groups was calculated by dissolving an acrylic rubber veil in acetone and performing potentiometric titration with a potassium hydroxide solution.
(2) The amount of epoxy group was calculated by dissolving an 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.
(3) The amount of chlorine was calculated by completely burning an acrylic rubber veil in a combustion flask, absorbing the generated chlorine in water, and titrating with silver nitrate.
［灰分量］
　アクリルゴムベール中に含まれる灰分量（％）は、ＪＩＳ　Ｋ６２２８　Ａ法に準じて測定した。 [Ash content]
The amount of ash (%) contained in the acrylic rubber veil was measured according to the JIS K6228 A method.
［灰分成分量］
　アクリルゴムベール灰分中の各成分量（ｐｐｍ）は、上記の灰分量測定の際に採取した灰分をΦ２０ｍｍの滴定濾紙に圧着し、ＺＳＸ　Ｐｒｉｍｕｓ（Ｒｉｇａｋｕ社製）を用いてＸＲＦ測定した。 [Amount of ash component]
The amount of each component (ppm) in the acrylic rubber veil ash content was measured by XRF using ZSX Primus (manufactured by Rigaku) by pressing the ash content collected at the time of the above ash content measurement onto a Φ20 mm titration filter paper.
［ゲル量］
　アクリルゴムベールのゲル量（％）は、メチルエチルケトンに対する不溶解分の量であり、以下の方法により求めた。 [Gel amount]
The gel amount (%) of the acrylic rubber veil was the amount of the insoluble matter in methyl ethyl ketone, and was determined by the following method.
　アクリルゴムベール０．２ｇ程度を秤量（Ｘｇ）し、１００ｍｌメチルエチルケトンに浸漬させて室温で２４時間放置後、８０メッシュ金網を用いてメチルエチルケトンに対する不溶解分を濾別した濾液、すなわち、メチルエチルケトンに溶解するゴム成分のみが溶解した濾液を蒸発乾燥固化させた乾燥固形分（Ｙｇ）を秤量し、下式により算出した。
　ゲル量（％）＝１００×（Ｘ－Ｙ）／Ｘ About 0.2 g of acrylic rubber veil is weighed (Xg), immersed in 100 ml methyl ethyl ketone, left at room temperature for 24 hours, and then dissolved in a filtrate obtained by filtering out the insoluble matter in methyl ethyl ketone using an 80 mesh wire mesh, that is, methyl ethyl ketone. The dry solid content (Yg) obtained by evaporating and solidifying the filtrate in which only the rubber component was dissolved was weighed and calculated by the following formula.
Gel amount (%) = 100 × (XY) / X
［比重］
　アクリルゴムベールの比重は、ＪＩＳ　Ｋ６２６８架橋ゴム－密度測定のＡ法に準じて測定した。 [specific gravity]
The specific gravity of the acrylic rubber veil was measured according to the method A of JIS K6268 crosslinked rubber-density measurement.
［ガラス転移温度（Ｔｇ）］
　アクリルゴムのガラス転移温度（Ｔｇ）は、示差走査型熱量計（ＤＳＣ、製品名「Ｘ－ＤＳＣ７０００」、日立ハイテクサイエンス社製）を用いて測定した。 [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.).
［ｐＨ］
　アクリルゴムベールのｐＨは、６ｇ（±０．０５ｇ）のアクリルゴムベールをテトラヒドロフラン１００ｇで溶解後、蒸留水２．０ｍｌを添加し完全に溶解したことを確認後にｐＨ電極で測定した。 [PH]
The pH of the acrylic rubber veil was measured with a pH electrode after confirming that 6 g (± 0.05 g) of the acrylic rubber veil was dissolved in 100 g of tetrahydrofuran, and 2.0 ml of distilled water was added to completely dissolve the acrylic rubber veil.
［含水量］
　アクリルゴムベールの含水量（％）は、ＪＩＳ　Ｋ６２３８－１：オーブンＡ（揮発分測定）法に準じて測定した。 [Water content]
The water content (%) of the acrylic rubber veil was measured according to JIS K6238-1: Oven A (volatile content measurement) method.
［分子量及び分子量分布］
　アクリルゴムの重量平均分子量（Ｍｗ）及び分子量分布（Ｍｚ／Ｍｗ）は、溶媒としてジメチルホルムアミドに塩化リチウムが０．０５ｍｏｌ／Ｌ、３７％濃塩酸が０．０１％の濃度でそれぞれ添加された溶液を用いた、ＧＰＣ－ＭＡＬＳ法により測定される絶対分子量及び絶対分子量分布である。具体的には、ＧＰＣ（Ｇｅｌ　Ｐｅｒｍｅａｔｉｏｎ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙ）装置に多角度レーザ光散乱光度計（ＭＡＬＳ）及び示差屈折率計（ＲＩ）を組み入れ、ＧＰＣ装置でサイズ分別された分子鎖溶液の光散乱強度及び屈折率差を、溶出時間を追って測定することにより、溶質の分子量とその含有率を順次計算し求めた。ＧＰＣ装置による測定条件及び測定方法は、以下のとおりである。
　カラム：ＴＳＫｇｅｌ　α－Ｍ　２本（φ７．８ｍｍ×３０ｃｍ、東ソー社製）
　カラム温度：４０℃
　流速：０．８ｍｌ／ｍｍ
　試料調整：試料１０ｍｇに溶媒５ｍｌを加え、室温で緩やかに撹拌した（溶解を視認）。その後０．５μｍフィルターを用いてろ過を行った。 [Molecular weight and molecular weight distribution]
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. Specifically, 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.
Column: 2 TSKgel α-M (φ7.8 mm x 30 cm, manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Flow velocity: 0.8 ml / mm
Sample preparation: 5 ml of solvent was added to 10 mg of sample, and the mixture was gently stirred at room temperature (dissolution was visually observed). Then, filtration was performed using a 0.5 μm filter.
［複素粘性率］
　アクリルゴムベールの複素粘性率ηは、動的粘弾性測定装置「ラバープロセスアナライザＲＰＡ－２０００」（アルファテクノロジー社製）を用いて、歪み４７３％、１Ｈｚにて温度分散（４０～１２０℃）を測定し、各温度における複素粘性率ηを求めた。ここでは、上述の動的粘弾性のうち６０℃における動的粘弾性を複素粘性率η（６０℃）とし、１００℃における動的粘弾性を複素粘性率η（１００℃）として、η（１００℃）／η（６０℃）、η（６０℃）／η（１００℃）の値を算出した。 [Complex viscosity]
The complex viscosity η of the acrylic rubber bale is subjected to temperature dispersion (40 to 120 ° C.) at a strain of 473% and 1 Hz using a dynamic viscoelasticity measuring device “Rubber Process Analyzer RPA-2000” (manufactured by Alpha Technology). The measurement was performed to determine the complex viscoelasticity η at each temperature. Here, among the above-mentioned dynamic viscoelasticities, the dynamic viscoelasticity at 60 ° C. is defined as the complex viscoelasticity η (60 ° C.), and the dynamic viscoelasticity at 100 ° C. is defined as the complex viscoelasticity η (100 ° C.). The values of ° C.) / η (60 ° C.) and η (60 ° C.) / η (100 ° C.) were calculated.
［ムーニー粘度（ＭＬ１＋４，１００℃）］
　アクリルゴムベールのムーニー粘度（ＭＬ１＋４，１００℃）は、ＪＩＳ　Ｋ６３００の未架橋ゴム物理試験法に従って測定した。 [Moony Viscosity (ML1 + 4,100 ° C)]
The Mooney viscosity (ML1 + 4,100 ° C.) of the acrylic rubber veil was measured according to the uncrosslinked rubber physical test method of JIS K6300.
［ゲル量のバラツキ性評価］
　ゴム試料のゲル量のバラツキ評価は、ゴム試料２０部（２０ｋｇ）から任意に選択した２０点のゲル量を測定し、下記基準に基づき評価した。
　◎：測定した２０点のゲル量の平均値を算出し、平均値±３の範囲内に測定した２０点全てが入っているもの
　〇：測定した２０点のゲル量の平均値を算出し、平均値±５の範囲内に測定した２０点全てが入っていたもの（平均値±３の範囲では測定した２０点のうち１点でも外れてしまうが、平均値±５の範囲内には２０点全てが入るもの）
　×：測定した２０点のゲル量の平均値を算出し、平均値±５の範囲から測定した２０点のうち１点でも外れたもの [Evaluation of variation in gel amount]
The variation in the gel amount of the rubber sample was evaluated by measuring the gel amount of 20 points arbitrarily selected from 20 parts (20 kg) of the rubber sample and evaluating based on the following criteria.
⊚: The average value of the measured 20-point gel amount was calculated, and all the measured 20 points were within the range of the average value ± 3. 〇: The average value of the measured 20-point gel amount was calculated. All 20 points measured within the range of mean ± 5 were included (in the range of mean ± 3, even one of the 20 points measured would be off, but within the range of mean ± 5 20 (Those that contain all the points)
X: The average value of the gel amount of the measured 20 points was calculated, and even one of the 20 points measured from the range of the average value ± 5 deviated.
［保存安定性］
　ゴム試料の保存安定性は、ゴム試料を４５℃×８０％ＲＨの恒温恒湿度槽（ＥＳＰＥＣ社製ＳＨ－２２２）に投入し、７日間試験前後のゴム試料を使用してゴム混合物のムーニースコーチ最低粘度（Ｖｍ）をＪＩＳ　Ｋ６３００－１：２０１３に準じてＬロータを用いて１２５℃で測定し試験損後の変化率を算出した。Ｖｍ変化率は、比較例２の変化率を１００とする指数で評価した（指数が小さいほど保存安定性に優れる）。 [Storage stability]
For the storage stability of the rubber sample, the rubber sample is placed in a constant temperature and humidity chamber (SH-222 manufactured by ESPEC) at 45 ° C. × 80% RH, and the rubber sample before and after the test for 7 days is used as a Mooney scorch of the rubber mixture. The minimum viscosity (Vm) was measured at 125 ° C. using an L rotor according to JIS K6300-1: 2013, and the rate of change after the test loss was calculated. The Vm change rate was evaluated by an index with the change rate of Comparative Example 2 as 100 (the smaller the index, the better the storage stability).
［加工性評価］
　ゴム試料の加工性は、ゴム試料を５０℃に加温されたバンバリーミキサーに投入し１分間素練り後、表１記載のゴム混合物配合の配合剤Ａを投入して１段目のゴム混合物が一体化して最大トルク値を示すまでの時間、すなわちＢＩＴ（Ｂｌａｃｋ　Ｉｎｃｏｒｐｏｒａｔｉｏｎ　Ｔｉｍｅ）を測定し、比較例２を１００とする指数で評価した（指数が小さいほど加工性に優れる）。 [Evaluation of workability]
Regarding the processability of the rubber sample, the rubber sample was put into a Banbury mixer heated to 50 ° C. and kneaded for 1 minute, and then the compounding agent A containing the rubber mixture shown in Table 1 was added to obtain the rubber mixture in the first stage. The time required to integrate and show the maximum torque value, that is, BIT (Black Incorporation Time) was measured and evaluated with an index of Comparative Example 2 as 100 (the smaller the index, the better the workability).
［耐水性評価］
　ゴム試料の耐水性は、ＪＩＳ　Ｋ６２５８に準拠してゴム試料の架橋物を温度８５℃蒸留水中に１００時間浸漬させて浸漬試験を行い、浸漬前後の体積変化率を下記式に従って算出し、比較例２を１００とする指数で評価した（指数が小さいほど耐水性に優れる）。 [Water resistance evaluation]
The water resistance of the rubber sample is determined by immersing the crosslinked product of the rubber sample in distilled water at a temperature of 85 ° C. for 100 hours in accordance with JIS K6258, performing a dipping test, and calculating the volume change rate before and after dipping according to the following formula. It was evaluated by an index with 2 as 100 (the smaller the index, the better the water resistance).
　浸漬前後の体積変化率（％）＝（（浸漬後の試験片体積―浸漬前の試験片体積）／浸漬前の試験片体積）×１００ Volume change rate before and after immersion (%) = ((Test piece volume after immersion-Test piece volume before immersion) / Test piece volume before immersion) x 100
［常態物性評価］
　ゴム試料の常態物性は、ＪＩＳ　Ｋ６２５１に従いゴム試料のゴム架橋物を破断強度、１００％引張応力及び破断伸びを測定し以下の基準で評価した。
（１）破断強度は、１０ＭＰａ以上を◎、１０ＭＰａ未満を×として評価した。
（２）１００％引張応力は、５ＭＰａ以上を◎、５ＭＰａ未満を×として評価した。
（３）破断伸びは、１５０％以上を◎、１５０％未満を×として評価した。 [Evaluation of normal physical properties]
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%.
［実施例１］
　ホモミキサーを備えた混合容器に、純水４６部、アクリル酸エチル２８部、アクリル酸ｎ－ブチル３８部、アクリル酸メトキシエチル２７部、アクリロニトリル５部及びアリルグリシジルエーテル２部、及び乳化剤としてノニルフェニルオキシヘキサオキシエチレンリン酸エステルナトリウム塩１．８部を仕込み撹拌して単量体エマルジョンを得た。 [Example 1]
In a mixing container equipped with a homomixer, 46 parts of pure water, 28 parts of ethyl acrylate, 38 parts of n-butyl acrylate, 27 parts of methoxyethyl acrylate, 5 parts of acrylonitrile and 2 parts of allyl glycidyl ether, and nonylphenyl as an emulsifier. 1.8 parts of oxyhexaoxyethylene phosphate sodium salt was charged and stirred to obtain a monomeric emulsion.
　次に、温度計、撹拌装置を備えた重合反応槽に、純水１７０部及び上記で得られた単量体エマルジョン３部を投入し、窒素気流下で１２℃まで冷却した。次に、重合反応槽中に、単量体エマルジョンの残部、硫酸第一鉄０．０００３３部、アスコルビン酸ナトリウム０．２６４部、及び過硫酸カリウム０．２２部を３時間かけて連続的に滴下した。その後、重合反応内の温度を２３℃に保った状態にて反応を継続し、重合転化率が略１００％に達したことを確認し、重合停止剤としてのハイドロキノンを添加して重合反応を停止し乳化重合液を得た。 Next, 170 parts of pure water and 3 parts of the monomer emulsion obtained above were put into a polymerization reaction tank equipped with a thermometer and a stirrer, and cooled to 12 ° C. under a nitrogen stream. Next, the balance of the monomer emulsion, 0.00033 parts of ferrous sulfate, 0.264 parts of sodium ascorbate, and 0.22 parts of potassium persulfate were continuously added dropwise to the polymerization reaction tank over 3 hours. did. After that, the reaction was continued while the temperature in the polymerization reaction was maintained at 23 ° C., it was confirmed that the polymerization conversion rate reached approximately 100%, and hydroquinone as a polymerization terminator was added to stop the polymerization reaction. An emulsion polymerization solution was obtained.
　温度計と撹拌装置を備えた凝固槽で、８０℃に加温した激しく撹拌（６００回転：周速３．１ｍ／ｓ）した２％硫酸マグネシウム水溶液（凝固液）中に、得られた乳化重合液を８０℃に加温して連続的に添加して重合体を凝固させ濾別して含水クラムを得た。 Emulsion polymerization obtained in a 2% magnesium sulfate aqueous solution (coagulant) heated to 80 ° C. and vigorously stirred (600 rpm: peripheral speed 3.1 m / s) in a coagulation tank equipped with a thermometer and a stirrer. The liquid was heated to 80 ° C. and continuously added to solidify the polymer and filtered off to obtain a hydrous crumb.
　次に、凝固槽内に１９４部の温水（７０℃）を添加して１５分間撹拌した後に水分を排出させ、再度１９４部の温水（７０℃）を添加して１５分間撹拌して含水クラムの洗浄を行った。洗浄した含水クラム（含水クラム温度６５℃）を、スクリュー型押出機１５に供給し、脱水・乾燥して幅３００ｍｍで厚さ１０ｍｍのシート状乾燥ゴムを押し出した。次に、スクリュー型押出機１５に直結して設けた搬送式冷却装置を用いて、シート状乾燥ゴムを冷却速度２００℃／ｈｒで冷却した。 Next, 194 parts of warm water (70 ° C.) was added to the coagulation tank and stirred for 15 minutes, then the water was discharged, and 194 parts of warm water (70 ° C.) was added again and stirred for 15 minutes to form a water-containing crumb. Cleaning was performed. The washed hydrous crumb (moisture content crumb temperature 65 ° C.) was supplied to the screw type extruder 15, dehydrated and dried, and a sheet-shaped dry rubber having a width of 300 mm and a thickness of 10 mm was extruded. Next, the sheet-shaped dry rubber was cooled at a cooling rate of 200 ° C./hr by using a transport type cooling device directly connected to the screw type extruder 15.
　なお、本実施例１で用いたスクリュー型押出機は、１つの供給バレル、３つの脱水バレル（第１～第３の脱水バレル）、５つの乾燥バレル（第１～第５の乾燥バレル）で構成されている。第１及び第２の脱水バレルは排水を行い、第３の脱水バレルは排蒸気を行うようになっている。スクリュー型押出機の操業条件は、以下のとおりとした。 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.
含水量：
　・第２の脱水バレルでの排水後の含水クラムの含水量：２０％
　・第３の脱水バレルでの排蒸気後の含水クラムの含水量：１０％
　・第５の乾燥バレルでの乾燥後の含水クラムの含水量：０．４％ 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%
ゴム温度：
　・第１の供給バレルに供給する含水クラムの温度：６５℃
　・スクリュー型押出機から排出されるゴムの温度：１４０℃ Rubber temperature:
-The temperature of the hydrous crumb supplied to the first supply barrel: 65 ° C.
・ Temperature of rubber discharged from screw type extruder: 140 ℃
脱水バレル部の設定温度：
　・第１の脱水バレル：９０℃
　・第２の脱水バレル：１００℃
　・第３の脱水バレル：１２０℃
　・第１の乾燥バレル：１２０℃
　・第２の乾燥バレル：１３０℃
　・第３の乾燥バレル：１４０℃
　・第４の乾燥バレル：１６０℃
　・第５の乾燥バレル：１８０℃ Set temperature of dehydration barrel:
-First dehydration barrel: 90 ° C
-Second dehydration barrel: 100 ° C
-Third dehydration barrel: 120 ° C
-First drying barrel: 120 ° C
-Second drying barrel: 130 ° C
-Third drying barrel: 140 ° C
・ Fourth drying barrel: 160 ° C
・ Fifth drying barrel: 180 ° C
運転条件：
　・バレルユニット内のスクリューの直径（Ｄ）：１３２ｍｍ
　・バレルユニット内のスクリューの全長（Ｌ）：４６２０ｍｍ
　・Ｌ／Ｄ：３５
　・バレルユニット内のスクリューの回転数：１３５ｒｐｍ
　・ダイからのゴムの押出量：７００ｋｇ／ｈｒ
　・ダイの樹脂圧：２ＭＰａ Operating conditions:
-Screw diameter (D) in the barrel unit: 132 mm
-Overall length (L) of the screw in the barrel unit: 4620 mm
・ L / D: 35
-Rotation speed of the screw in the barrel unit: 135 rpm
-Rubber extrusion amount from die: 700 kg / hr
・ Die resin pressure: 2MPa
　押し出されたシート状乾燥ゴムを、５０℃まで冷却してからカッターで切断して、４０℃以下にならない内に２０部（２０ｋｇ）になるように積層してアクリルゴムベール（Ａ）を得た。得られたアクリルゴムベール（Ａ）の反応性基含有量、灰分量、灰分成分量、比重、ゲル量、ｐＨ、ガラス転移温度（Ｔｇ）、含水量、分子量、分子量分布、複素粘性率及びムーニー粘度（ＭＬ１＋４，１００℃）を測定しそれらの結果を表２に示した。また、アクリルゴムベール（Ａ）のゲル量のバラツキ性を評価しその結果を表２に示した。 The extruded sheet-shaped dry rubber was cooled to 50 ° C., cut with a cutter, and laminated to 20 parts (20 kg) before the temperature fell below 40 ° C. to obtain an acrylic rubber veil (A). .. Reactive group content, ash content, ash component content, specific gravity, gel amount, pH, glass transition temperature (Tg), water content, molecular weight, molecular weight distribution, complex viscosity and Moony of the obtained acrylic rubber veil (A) The viscosities (ML1 + 4,100 ° C.) were measured and the results are shown in Table 2. In addition, the variation in the gel amount of the acrylic rubber veil (A) was evaluated, and the results are shown in Table 2.
　次に、バンバリーミキサーを用いて、アクリルゴムベール（Ａ）１００部と表１記載の「配合１」の配合剤Ａを投入して、５０℃で５分間混合した。このときのＢＩＴを測定してアクリルゴムベールの加工性を評価しその結果を表２に示した。 Next, using a Bunbury mixer, 100 parts of the acrylic rubber veil (A) and the compounding agent A of "Formulation 1" shown in Table 1 were added and mixed at 50 ° C. for 5 minutes. The BIT at this time was measured to evaluate the processability of the acrylic rubber bale, and the results are shown in Table 2.
　次に、得られた混合物を５０℃のロールに移して、表１記載の「配合１」の配合剤Ｂを混合してゴム混合物を得た。得られたゴム混合物及び保存安定性試験後のアクリルゴムベール（Ａ）を用いて同様に作製したゴム混合物のムーニースコーチ最低粘度（Ｖｍ）を測定しその変化率を表２に示した。 Next, the obtained mixture was transferred to a roll at 50 ° C., and the compounding agent B of "Formulation 1" shown in Table 1 was mixed to obtain a rubber mixture. The Mooney Scorch minimum viscosity (Vm) of the rubber mixture thus prepared using the obtained rubber mixture and the acrylic rubber veil (A) after the storage stability test was measured, and the rate of change is shown in Table 2.
Figure JPOXMLDOC01-appb-T000001
  
Figure JPOXMLDOC01-appb-T000001
  
　得られたゴム混合物を、縦１５ｃｍ、横１５ｃｍ、深さ０．２ｃｍの金型に入れ、プレス圧１０ＭＰａで加圧しながら１８０℃で１０分間プレスすることにより一次架橋し、次に、得られた一次架橋物を、ギヤー式オーブンにて、更に１８０℃、２時間の条件で加熱して二次架橋させることにより、シート状のゴム架橋物を得た。そして、得られたシート状のゴム架橋物から３ｃｍ×２ｃｍ×０．２ｃｍの試験片を切り取り耐水性評価及び常態物性を評価してそれらの結果を表２に示した。 The obtained rubber mixture was placed in a mold having a length of 15 cm, a width of 15 cm, and a depth of 0.2 cm, and was first crosslinked by pressing at 180 ° C. for 10 minutes while pressurizing at a press pressure of 10 MPa, and then obtained. The primary crosslinked product was further heated in a gear oven at 180 ° C. for 2 hours for secondary cross-linking to obtain a sheet-shaped rubber crosslinked product. Then, a 3 cm × 2 cm × 0.2 cm test piece was cut out from the obtained sheet-shaped rubber crosslinked product, and the water resistance evaluation and the normal physical properties were evaluated, and the results are shown in Table 2.
［実施例２］
　単量体成分を、アクリル酸エチル４２．２部、アクリル酸ｎ－ブチル３５部、アクリル酸メトキシエチル２０部、アクリロニトリル１．５部及びクロロ酢酸ビニル１．３部に、乳化剤をトリデシルオキシヘキサオキシエチレンリン酸エステルナトリウム塩に変更する以外は実施例１と同様に行いアクリルゴムベール（Ｂ）を得て各特性（「配合２」に変更して）を評価した。それらの結果を表２に示した。 [Example 2]
The monomer component was 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, and the emulsifier was tridecyloxyhexa. Acrylic rubber veil (B) was obtained in the same manner as in Example 1 except that the sodium salt was changed to oxyethylene phosphate sodium salt, and each characteristic (changed to "formulation 2") was evaluated. The results are shown in Table 2.
［実施例３］
　スクリュー型押出機の第１脱水バレルの温度を１００℃、第２の脱水バレルの温度を１２０℃に変えて第１の脱水バレルのみで排水を行うようにし、且つ、第１の脱水バレルでの排水後の含水クラムの含水量を３０％に変更する以外は実施例１と同様に行い、アクリルゴムベール（Ｃ）を得て各特性を評価した。それらの結果を表２に示した。 [Example 3]
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. The same procedure as in Example 1 was carried out except that the water content of the water-containing crumb after drainage was changed to 30%, and an acrylic rubber bale (C) was obtained and each characteristic was evaluated. The results are shown in Table 2.
［実施例４］
　スクリュー型押出機の第１脱水バレルの温度を１００℃、第２の脱水バレルの温度を１２０℃に変えて第１の脱水バレルのみで排水を行うようにし、且つ、第１の脱水バレルでの排水後の含水クラムの含水量を３０％に変更する以外は実施例２と同様に行い、アクリルゴムベール（Ｄ）を得て各特性を評価した。それらの結果を表２に示した。 [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. The same procedure as in Example 2 was carried out except that the water content of the water-containing crumb after drainage was changed to 30%, and acrylic rubber barrels (D) were obtained and each characteristic was evaluated. The results are shown in Table 2.
［比較例１］
　実施例２と同様に乳化重合を行った乳化重合液（回転数１００ｒｐｍ、周速０．５ｍ／ｓ）に８０℃に加温した０．７％硫酸マグネシウム水溶液（凝固液）を連続的に添加して重合体を凝固させ濾別して含水クラムを得た。次に、得られた含水クラムを１９４部の温水（７０℃）を添加して１５分間撹拌した後に水分を排出させ、再度１９４部の温水（７０℃）を添加して１５分間の洗浄を行った後に、１６０℃の熱風乾燥機で乾燥させて含水量０．４重量％のクラム状アクリルゴム（Ｅ）を得た。得られたクラム状アクリルゴム（Ｅ）の各特性（「配合２」）を評価して表２に示した。 [Comparative Example 1]
A 0.7% magnesium sulfate aqueous solution (coagulant) heated to 80 ° C. was continuously added to the emulsion polymer solution (rotation speed 100 rpm, peripheral speed 0.5 m / s) subjected to emulsion polymerization in the same manner as in Example 2. The polymer was coagulated and filtered off to obtain a hydrous crumb. Next, 194 parts of warm water (70 ° C.) was added to the obtained hydrous crumb and stirred for 15 minutes, then the water was discharged, and 194 parts of warm water (70 ° C.) was added again to perform washing for 15 minutes. After that, it was dried with a hot air dryer at 160 ° C. to obtain a crumb-shaped acrylic rubber (E) having a water content of 0.4% by weight. Each characteristic (“blending 2”) of the obtained crumb-shaped acrylic rubber (E) was evaluated and shown in Table 2.
［比較例２］
　ホモミキサーを備えた混合容器に、純水４６部、アクリル酸エチル４２．２部、アクリル酸ｎ－ブチル３５部、アクリル酸メトキシエチル２０部、アクリロニトリル１．５部、クロロ酢酸ビニル１．３部、乳化剤としてラウリル硫酸ナトリウム０．７０９部及びポリオキシエチレンドデシルエーテル（分子量１５００）１．８２部を仕込み撹拌して単量体エマルジョンを得た。 [Comparative Example 2]
In a mixing container equipped with a homomixer, 46 parts of pure water, 42.2 parts of ethyl acrylate, 35 parts of n-butyl acrylate, 20 parts of methoxyethyl acrylate, 1.5 parts of acrylonitrile, 1.3 parts of vinyl chloroacetate As an emulsifier, 0.709 parts of sodium lauryl sulfate and 1.82 parts of polyoxyethylene dodecyl ether (molecular weight 1500) were charged and stirred to obtain a monomer emulsion.
　次に、温度計、撹拌装置を備えた重合反応槽に、純水１７０部及び上記で得られた単量体エマルジョン３部を投入し、窒素気流下で１２℃まで冷却した。次に、重合反応槽中に、単量体エマルジョンの残部、硫酸第一鉄０．０００３３部、アスコルビン酸ナトリウム０．２６４部、及び過硫酸カリウム０．２２部を３時間かけて連続的に滴下した。その後、重合反応内の温度を２３℃に保った状態にて反応を継続し、重合転化率が略１００％に達したことを確認し、重合停止剤としてのハイドロキノンを添加して重合反応を停止し乳化重合液を得た。 Next, 170 parts of pure water and 3 parts of the monomer emulsion obtained above were put into a polymerization reaction tank equipped with a thermometer and a stirrer, and cooled to 12 ° C. under a nitrogen stream. Next, the balance of the monomer emulsion, 0.00033 parts of ferrous sulfate, 0.264 parts of sodium ascorbate, and 0.22 parts of potassium persulfate were continuously added dropwise to the polymerization reaction tank over 3 hours. did. After that, the reaction was continued while the temperature in the polymerization reaction was maintained at 23 ° C., it was confirmed that the polymerization conversion rate reached approximately 100%, and hydroquinone as a polymerization terminator was added to stop the polymerization reaction. An emulsion polymerization solution was obtained.
　次に、乳化重合液を８０℃に加温した後に０．７％硫酸ナトリウム水溶液（凝固液）連続的に添加して重合体を凝固させ濾別して含水クラムを得た。得られた含水クラム１００部に対し、工業用水１９４部を添加し、２５℃、５分間撹拌した後、凝固槽から水分を排出する含水クラムの洗浄を４回行い、次に、ｐＨ３の硫酸水溶液１９４部を添加して２５℃で５分間撹拌した後、凝固槽から水分を排出させて酸洗浄を１回行った後、純水１９４部添加して純水洗浄を１回行った後に、１６０℃の熱風乾燥機で乾燥させて含水量０．４重量％のクラム状アクリルゴム（Ｆ）を得た。得られたクラム状アクリルゴム（Ｆ）の各特性（「配合２」）を評価して表２に示した。 Next, after heating the emulsion polymerization solution to 80 ° C., 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. To 100 parts of the obtained water-containing crumb, 194 parts of industrial water was added, and after stirring at 25 ° C. for 5 minutes, the water-containing crumb for discharging water from the coagulation tank was washed four times, and then a sulfuric acid aqueous solution having a pH of 3 was washed. After adding 194 parts and stirring at 25 ° C. for 5 minutes, water is discharged from the coagulation tank to perform acid cleaning once, then 194 parts of pure water is added and pure water cleaning is performed once, and then 160. A crumb-shaped acrylic rubber (F) having a water content of 0.4% by weight was obtained by drying with a hot air dryer at ° C. Each characteristic (“blending 2”) of the obtained crumb-shaped acrylic rubber (F) was evaluated and shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000002
  
　表２から、本発明の反応性基を有する重量平均分子量（Ｍｗ）が１００，０００～５，０００，０００でアクリルゴムからなり、メチルエチルケトン不溶解なゲル量が５０重量％以下で比重が０．９以上であるアクリルゴムベール（Ａ）～（Ｄ）は、保存安定性とバンバリー混錬時の加工性が高度に優れていること、しかもゲル量のバラツキ（結果として下記加工性のバラツキ、架橋物性のバラツキ）と耐水性と強度特性を含めた常態物性にも優れていることがわかる（実施例１～４）。 From Table 2, the weight average molecular weight (Mw) having the reactive group of the present invention is 100,000 to 5,000,000, and it is made of acrylic rubber. The amount of gel insoluble in methyl ethyl ketone is 50% by weight or less, and the specific gravity is 0. Acrylic rubber veils (A) to (D) having a value of 9 or more are highly excellent in storage stability and processability during Banbury kneading, and also have variations in gel amount (as a result, variations in processability and cross-linking described below). It can be seen that it is also excellent in normal physical properties including water resistance and strength characteristics (variations in physical properties) (Examples 1 to 4).
　強度特性含めた常態物性については、本発明のアクリルゴムベールの強度を維持させ作業性を向上させるために本願実施例及び比較例の条件で製造したアクリルゴムベール（Ａ）～（Ｄ）及びクラム状アクリルゴム（Ｅ）～（Ｆ）は、ＧＰＣ－ＭＡＬＳで測定された絶対分子量の重量平均分子量（Ｍｗ）が１０万を超え、しかも、ＧＰＣ－ＭＡＬＳで測定された高分子量領域を重視した絶対分子量分布のｚ平均分子量（Ｍｚ）と重量平均分子量（Ｍｗ）との比（Ｍｚ／Ｍｗ）が１．３を遥かに超えて大きいため、常態物性のいずれの特性にも優れていることがわかる（実施例１～６及び比較例１～２）。しかしながら、比較例１のクラム状アクリルゴム（Ｅ）は、常態物性には優れるが、ゲル量がバラツキ、加工性及び耐水性が大きく劣り、比較例２のクラム状アクリルゴム（Ｆ）は、ゲル量のバラツキ性、保存安定性、加工性及び耐水性のいずれの特性も十分でないことがわかる。 Regarding the normal physical properties including the strength characteristics, the acrylic rubber veils (A) to (D) and crumbs produced under the conditions of the Examples and Comparative Examples of the present application in order to maintain the strength of the acrylic rubber bale of the present invention and improve the workability. The acrylic rubbers (E) to (F) have a weight average molecular weight (Mw) of the absolute molecular weight measured by GPC-MALS exceeding 100,000, and an absolute emphasis on the high molecular weight region measured by GPC-MALS. Since the ratio (Mz / Mw) of the z average molecular weight (Mz) and the weight average molecular weight (Mw) of the molecular weight distribution is much larger than 1.3, it can be seen that it is excellent in all the characteristics of normal physical properties. (Examples 1 to 6 and Comparative Examples 1 to 2). However, although the crumb-shaped acrylic rubber (E) of Comparative Example 1 is excellent in normal physical properties, the gel amount varies, the processability and water resistance are significantly inferior, and the crumb-shaped acrylic rubber (F) of Comparative Example 2 is a gel. It can be seen that none of the characteristics of quantity variation, storage stability, processability and water resistance is sufficient.
　保存安定性については、４５℃×８０％ＲＨの恒温恒湿槽投入前後のムーニースコーチ最低粘度（Ｖｍ）の変化率を評価しているが、本発明のアクリルゴムベール（Ａ）～（Ｄ）は、クラム状アクリルゴム（Ｅ）及び（Ｆ）と比べて圧倒的に優れていることがわかる（実施例１～４と比較例１～２との比較）。これは、アクリルゴムベール（Ａ）～（Ｄ）の比重がクラム状アクリルゴム（Ｅ）及び（Ｆ）と比べると格段に高く、殆ど空気を含まない状態になっているために保存安定性が向上していると思われる。保存安定性の差は、本発明のアクリルゴムベール（Ａ）～（Ｄ）と比較例のクラム状アクリルゴム（Ｅ）～（Ｆ）の比重（空気の巻き込み量）の差であるが、本発明のアクリルゴムベール（Ａ）～（Ｅ）の空気の巻き込み量（含有量）が少ないのは、表２にはそれら条件を示していないが本願アクリルゴムベールの製造方法の詳細説明及び本願実施例で示しているように、特定なスクリュー型押出機を用いて、ダイ部の温度と樹脂圧を特定にして特定含水量のシート状乾燥ゴムを押し出すこと、そして押し出されたシート状乾燥ゴムを特定温度まで冷却してから切断し且つ特定温度で積層することで達成できていることがわかる。 Regarding the storage stability, the rate of change in the minimum viscosity (Vm) of the Mooney scorch before and after putting it in the constant temperature and humidity chamber of 45 ° C. × 80% RH is evaluated. The acrylic rubber veils (A) to (D) of the present invention are evaluated. Is overwhelmingly superior to the crumb-shaped acrylic rubbers (E) and (F) (comparison between Examples 1 to 4 and Comparative Examples 1 and 2). This is because the specific gravities of the acrylic rubber veils (A) to (D) are much higher than those of the crumb-shaped acrylic rubbers (E) and (F), and the storage stability is high because they contain almost no air. It seems to be improving. The difference in storage stability is the difference in specific gravity (amount of air entrainment) between the acrylic rubber veils (A) to (D) of the present invention and the crumb-shaped acrylic rubbers (E) to (F) of the comparative example. Table 2 does not show these conditions for the small amount (content) of air entrained in the acrylic rubber veils (A) to (E) of the present invention, but a detailed description of the method for producing the acrylic rubber bale of the present application and the implementation of the present application. As shown in the example, using a specific screw type extruder, the temperature and resin pressure of the die part are specified to extrude the sheet-shaped dry rubber with a specific water content, and the extruded sheet-shaped dry rubber is extruded. It can be seen that this can be achieved by cooling to a specific temperature, cutting, and laminating at a specific temperature.
　メチルエチルケトン不溶解分のゲル量のバラツキ性については、任意に選択した２０点のゲル量を測定し、平均値±３の範囲内に測定した２０点全ての測定値が入っているか否か、あるいは平均値±５の範囲内に２０点全ての測定値が入っているか否かで判断したが、本発明のアクリルゴムベール（Ａ）～（Ｄ）は、クラム状アクリルゴム（Ｅ）及び（Ｆ）と比べて圧倒的にバラツキ性に優れ、ベール内でのメチルエチルケトン不溶解分のゲル量のバラツキが少ないことがわかる（実施例１～４と比較例１との比較）。メチルエチルケトン不溶解分のゲル量は、バンバリーなどの加工性に直接影響して、これが変化するとゴム混合物及びゴム架橋物の諸物性がバラツキ結果として諸物性を悪化させてしまうので好ましくない。それに対して、本発明のアクリルゴムベール（Ａ）～（Ｄ）は、メチルエチルケトン不溶解分のゲル量のバラツキがなく、安定したゴム混合物やゴム架橋物を与えることができる。 Regarding the variation in the amount of gel of the insoluble methyl ethyl ketone, the amount of gel at 20 points arbitrarily selected was measured, and whether or not all the measured values of all 20 points measured within the range of the mean value ± 3 were included, or It was judged whether or not all the measured values of 20 points were within the range of the average value ± 5, but the acrylic rubber veils (A) to (D) of the present invention were crumb-shaped acrylic rubbers (E) and (F). ) Is overwhelmingly excellent in variation, and it can be seen that there is little variation in the amount of gel of the methyl ethyl ketone insoluble matter in the veil (comparison between Examples 1 to 4 and Comparative Example 1). The amount of gel of the insoluble methyl ethyl ketone directly affects the processability of Banbury and the like, and if this is changed, the physical properties of the rubber mixture and the crosslinked rubber will vary, resulting in deterioration of the physical properties, which is not preferable. On the other hand, the acrylic rubber veils (A) to (D) of the present invention have no variation in the gel amount of the methyl ethyl ketone insoluble matter, and can provide a stable rubber mixture or rubber crosslinked product.
　加工性については、本発明では強度特性を上げるために乳化重合の重合転化率を高めているが、重合転化率を上げていくと急激にメチルエチルケトン不溶解分のゲル量が増加しアクリルゴムの加工性を悪化させてしまったが、スクリュー型押出機内で実質的に水分が無い状態（含水量１％未満）まで乾燥させ溶融混錬されることで急増したメチルエチルケトン不溶解分のゲルが消失し、アクリルゴムベールの加工性と強度を高度にバランスされていることがわかる（実施例１～４と比較例１との比較）。 Regarding processability, in the present invention, the polymerization conversion rate of emulsion polymerization is increased in order to improve the strength characteristics, but as the polymerization conversion rate is increased, the gel amount of the insoluble methyl ethyl ketone rapidly increases and the processing of acrylic rubber Although the properties were deteriorated, the rapidly increased amount of methyl ethyl ketone insoluble gel disappeared when it was dried and melt-kneaded in a screw-type extruder to a state where there was virtually no water content (water content less than 1%). It can be seen that the processability and strength of the acrylic rubber bale are highly balanced (comparison between Examples 1 to 4 and Comparative Example 1).
　耐水性については、本願課題の保存安定性とバンバリー等混錬時の加工性に優れるアクリルゴムベールを作り出す中での副次効果である。すなわち、本願課題を達成するためには比熱の大きなアクリルゴムを短いスクリュー型押出機の中で含水量を１重量％未満まですることが重要で、そのためには、凝固反応で脱水しやすいクラム形状を作り、温水で含水クラムを洗浄しそのままの温度でスクリュー型押出機に投入し且つスクリュー型押出機内での脱水効率を向上させることで乾燥バレル部で実質的に水分を含まない状態で溶融混錬を可能にしメチルエチルケトン不溶解分のゲル量を消失し、且つ、ダイ部の樹脂圧を低減しシート状の押し出しを可能にしアクリルゴムベールの比重を高めることで課題を達成している。これらの作業条件を行う結果として、表２からわかるように、アクリルゴムベールの灰分量が画期的に低減され耐水性が大幅に改良されていることがわかる。 Water resistance is a secondary effect in producing an acrylic rubber veil that has excellent storage stability and workability during kneading such as Banbury. That is, in order to achieve the subject of the present application, it is important to reduce the water content of acrylic rubber having a large specific gravity to less than 1% by weight in a short screw type extruder, and for that purpose, a crumb shape that is easily dehydrated by a solidification reaction. Is made, and the hydrous crumb is washed with warm water and put into the screw type extruder at the same temperature, and the dehydration efficiency in the screw type extruder is improved, so that the dry barrel part is melt-mixed in a state of substantially no moisture. The problem is achieved by enabling smelting, eliminating the gel amount of the insoluble methyl ethyl ketone, reducing the resin pressure of the die portion, enabling sheet-like extrusion, and increasing the specific gravity of the acrylic rubber bale. As a result of performing these working conditions, as can be seen from Table 2, it can be seen that the ash content of the acrylic rubber veil is dramatically reduced and the water resistance is significantly improved.
　表２から、また、反応性基量、比重、ゲル量、ガラス転移温度（Ｔｇ）、ｐＨ、含水量、重量平均分子量（Ｍｗ）、ｚ平均分子量（Ｍｚ）と重量平均分子量（Ｍｗ）との比（Ｍｚ／Ｍｗ）、１００℃における複素粘性率η（１００℃）、６０℃における複素粘性率η（６０℃）、１００℃と６０℃における複素粘性率の比（η１００℃／η６０℃）及びムーニー粘度（１＋４，１００℃）が特定範囲にあるアクリルゴムベール（Ａ）～（Ｄ）は、保存安定性と加工性が格段に優れるとともにメチルエチルケトン不溶解分のゲル量バラツキ、耐水性及び常態物性（強度特性）にも優れていることがわかる（実施例１～４）。 From Table 2, also, the reactive group weight, specific gravity, gel weight, glass transition temperature (Tg), pH, water content, weight average molecular weight (Mw), z average molecular weight (Mz) and weight average molecular weight (Mw). Ratio (Mz / Mw), complex viscosity at 100 ° C. η (100 ° C.), complex viscosity at 60 ° C. η (60 ° C.), ratio of complex viscosity at 100 ° C. and 60 ° C. (η100 ° C./η60 ° C.) and Acrylic rubber veils (A) to (D) having a Mooney viscosity (1 + 4,100 ° C.) in a specific range are remarkably excellent in storage stability and processability, as well as variations in the amount of gel in which methyl ethyl ketone is insoluble, water resistance, and normal physical characteristics. It can be seen that it is also excellent in (strength characteristics) (Examples 1 to 4).
［実施例５］
　単量体成分を、アクリル酸エチル４．５部、アクリル酸ｎ－ブチル６４．５部、アクリル酸メトキシエチル２９．５部、フマル酸モノｎ－ブチル１．５部に変更する以外は実施例１と同様に行いアクリルゴムベール（Ｇ）を得た。得られたアクリルゴムベール（Ｇ）の各特性を測定及び評価（ゴム混合物の配合剤Ｂはヘキサメチレンジアミンカーバメート０．５部及びレノグランＸＬＡ－６０（活性アミンと遅延剤合成混合物：ランクセス社製）２部に変更）すると、反応性基含有量「０．３１％」、灰分量「０．１１０％」、比重「１．１４２」、メチルエチルケトン不溶解分のゲル量「１．８％」、Ｔｇ「－３９℃」、ｐＨ「５」、含水量「０．４％」、Ｍｗ／１０００「１３８０」、Ｍｚ／Ｍｗ「１．６９」、η（１００℃）「３１２４Ｐａ・ｓ」、η（６０℃）「３３６０Ｐａ・ｓ」、η（１００℃）／η（６０℃）「０．９３」、メチルエチルケトン不溶解分のゲル量バラツキ「◎」、保存安定性「６」、加工性「２１」、耐水性「２」、破断強度「◎」、１００％引張応力「◎」、破断伸び「◎」であり、保存安定性と加工性が格段に優れ、且つ、強度特性含めた常態物性、ゲル量バラツキ及び耐水性にも優れていた。 [Example 5]
Examples except that the monomer component was changed to 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. Acrylic rubber bale (G) was obtained in the same manner as in 1. Measurement and evaluation of each characteristic of the obtained acrylic rubber veil (G) (Compounding agent B of the rubber mixture is 0.5 part of hexamethylenediamine carbamate and Lenogran XLA-60 (active amine and retarder synthetic mixture: manufactured by Rankses). (Changed to 2 parts), reactive group content "0.31%", ash content "0.110%", specific gravity "1.142", methyl ethyl ketone insoluble gel amount "1.8%", Tg "-39 ° C", pH "5", water content "0.4%", Mw / 1000 "1380", Mz / Mw "1.69", η (100 ° C) "3124Pa · s", η (60) ° C.) "3360 Pa · s", η (100 ° C.) / η (60 ° C.) "0.93", gel amount variation of methyl ethyl ketone insoluble content "◎", storage stability "6", processability "21", Water resistance "2", breaking strength "◎", 100% tensile stress "◎", breaking elongation "◎", excellent storage stability and workability, normal physical properties including strength characteristics, gel amount It was also excellent in variation and water resistance.
［実施例６］
　単量体成分をアクリル酸エチル４８．２５部、アクリル酸ｎ－ブチル５０部、フマル酸モノｎ－ブチル１．７５部ゴムに変更する以外は実施例２と同様に行いアクリルゴムベール（Ｈ）を得た。得られたアクリルゴムベール（Ｈ）の各特性を測定及び評価（ゴム混合物の配合剤Ｂをヘキサメチレンジアミンカーバメート０．６部及びレノグランＸＬＡ－６０（活性アミンと遅延剤合成混合物：ランクセス社製）２部に変更）すると、反応性基含有量「０．３５％」、灰分量「０．０９２％」、比重「１．１７８」、メチルエチルケトン不溶解分のゲル量「２．１％」、Ｔｇ「－２８℃」、ｐＨ「４．５」、含水量「０．４％」、Ｍｗ／１０００「１４５０」、Ｍｚ／Ｍｗ「１．７９」、η（１００℃）「３１５０Ｐａ・ｓ」、η（６０℃）「３６２０Ｐａ・ｓ」、η（１００℃）／η（６０℃）「０．８７」、メチルエチルケトン不溶解分のゲル量バラツキ「◎」、保存安定性「６」、加工性「２３」、耐水性「２」、破断強度「◎」、１００％引張応力「◎」、破断伸び「◎」であり、保存安定性と加工性が格段に優れ、且つ、強度特性含めた常態物性、ゲル量バラツキ及び耐水性にも優れていた。 [Example 6]
Acrylic rubber veil (H) was carried out in the same manner as in Example 2 except that the monomer component was changed to 48.25 parts of ethyl acrylate, 50 parts of n-butyl acrylate, and 1.75 parts of mono-n-butyl fumarate. Got Measurement and evaluation of each characteristic of the obtained acrylic rubber veil (H) (0.6 parts of hexamethylenediamine carbamate and Lenogran XLA-60 (composite mixture of active amine and retarder: manufactured by Rankses) (Changed to 2 parts), reactive group content "0.35%", ash content "0.092%", specific gravity "1.178", methyl ethyl ketone insoluble gel amount "2.1%", Tg "-28 ° C", pH "4.5", water content "0.4%", Mw / 1000 "1450", Mz / Mw "1.79", η (100 ° C) "3150 Pa · s", η (60 ° C) "3620 Pa · s", η (100 ° C) / η (60 ° C) "0.87", gel amount variation of methyl ethyl ketone insoluble content "◎", storage stability "6", processability "23" , Water resistance "2", breaking strength "◎", 100% tensile stress "◎", breaking elongation "◎", excellent storage stability and workability, and normal physical properties including strength characteristics. It was also excellent in gel amount variation and water resistance.
　１　アクリルゴム製造システム
　３　凝固装置
　４　洗浄装置
　５　スクリュー型押出機
　６　冷却装置
　７　ベール化装置
  1 Acrylic rubber manufacturing system 3 Coagulation equipment 4 Cleaning equipment 5 Screw type extruder 6 Cooling equipment 7 Veiling equipment

Claims (14)

  1. 　反応性基を有する重量平均分子量（Ｍｗ）が１００，０００～５，０００，０００でアクリルゴムからなり、メチルエチルケトン不溶解なゲル量が５０重量％以下で比重が０．８以上であるアクリルゴムベール。 Acrylic rubber veil having a reactive group, having a weight average molecular weight (Mw) of 100,000 to 5,000,000 and made of acrylic rubber, having a gel amount insoluble in methyl ethyl ketone of 50% by weight or less and a specific gravity of 0.8 or more. ..
  2. 　メチルエチルケトン不溶解分のゲル量が、２０重量％以下である請求項１に記載のアクリルゴムベール。 The acrylic rubber veil according to claim 1, wherein the amount of gel of the insoluble methyl ethyl ketone is 20% by weight or less.
  3. 　アクリルゴムベールのメチルエチルケトン不溶解分のゲル量を任意に２０点測定したときの値が、（平均値－５）～（平均値＋５）重量％の範囲内に測定した２０点全てが入る請求項１又は２に記載のアクリルゴムベール。 Claim that the value when the gel amount of the methyl ethyl ketone insoluble portion of the acrylic rubber veil is arbitrarily measured at 20 points falls within the range of (mean value -5) to (mean value + 5)% by weight. The acrylic rubber bale according to 1 or 2.
  4. 　重量平均分子量（Ｍｗ）が、１，０００，０００～５，０００，０００の範囲である請求項１～３のいずれか１項に記載のアクリルゴムベール。 The acrylic rubber veil according to any one of claims 1 to 3, wherein the weight average molecular weight (Mw) is in the range of 1,000,000 to 5,000,000.
  5. 　ｚ平均分子量（Ｍｚ）と重量平均分子量（Ｍｗ）との比（Ｍｚ／Ｍｗ）が、１．３以上である請求項１～４のいずれか１項に記載のアクリルゴムベール。 The acrylic rubber veil according to any one of claims 1 to 4, wherein the ratio (Mz / Mw) of the z average molecular weight (Mz) to the weight average molecular weight (Mw) is 1.3 or more.
  6. 　１００℃における複素粘性率（［η］１００℃）が、１，５００～６，０００Ｐａ・ｓの範囲である請求項１～５のいずれか１項に記載のアクリルゴムベール。 The acrylic rubber veil according to any one of claims 1 to 5, wherein the complex viscosity ([η] 100 ° C.) at 100 ° C. is in the range of 1,500 to 6,000 Pa · s.
  7. 　１００℃における複素粘性率（［η］１００℃）と６０℃における複素粘性率（［η］６０℃）との比（［η］１００℃／［η］６０℃）が、０．５以上である請求項１～６のいずれか１項に記載のアクリルゴムベール。 When the ratio ([η] 100 ° C / [η] 60 ° C) of the complex viscosity at 100 ° C ([η] 100 ° C) to the complex viscosity at 60 ° C ([η] 60 ° C) is 0.5 or more. The acrylic rubber bale according to any one of claims 1 to 6.
  8. 　１００℃における複素粘性率（［η］１００℃）と６０℃における複素粘性率（［η］６０℃）との比（［η］１００℃／［η］６０℃）が、０．８以上である請求項１～７のいずれか１項に記載のアクリルゴムベール。 When the ratio ([η] 100 ° C / [η] 60 ° C) of the complex viscosity at 100 ° C ([η] 100 ° C) to the complex viscosity at 60 ° C ([η] 60 ° C) is 0.8 or more. The acrylic rubber bale according to any one of claims 1 to 7.
  9. 　ｐＨが、６以下である請求項１～８のいずれか１項に記載のアクリルゴムベール。 The acrylic rubber veil according to any one of claims 1 to 8, which has a pH of 6 or less.
  10. 　灰分が、０．５重量％以下である請求項１～９のいずれか１項に記載のアクリルゴムベール。 The acrylic rubber veil according to any one of claims 1 to 9, wherein the ash content is 0.5% by weight or less.
  11. 　灰分中のナトリウム、イオウ、カルシウム、マグネシウム及びリンからなる群から選ばれる少なくとも１種の元素の含有量が、８０重量％以上である請求項１～１０のいずれか１項に記載のアクリルゴムベール。 The acrylic rubber veil according to any one of claims 1 to 10, wherein the content of at least one element selected from the group consisting of sodium, sulfur, calcium, magnesium and phosphorus in the ash is 80% by weight or more. ..
  12. 　（メタ）アクリル酸エステルと反応性基含有単量体とを含む単量体成分を水と乳化剤とでエマルジョン化し重合触媒存在下に乳化重合し乳化重合液を得る乳化重合工程と、
    　得られた乳化重合液と凝固液を接触させて含水クラムを生成する凝固工程と、
    　生成した含水クラムを洗浄する洗浄工程と、
    　洗浄した含水クラムを、脱水スリットを有する脱水バレルと減圧下の乾燥バレルと先端部にダイを有するスクリュー型押出機を用いて脱水バレルで含水量１～４０重量％まで脱水した後に乾燥バレルで含水量１重量％未満まで乾燥してシート状乾燥ゴムをダイから押し出す脱水・乾燥・成形工程と、
    　押し出されたシート状乾燥ゴムを積層してベール化するベール化工程と、を含む請求項１～１１のいずれか１項に記載のアクリルゴムベールの製造方法。     An emulsion polymerization step in which a monomer component containing a (meth) acrylic acid ester and a reactive group-containing monomer is emulsified with water and an emulsifier and emulsion-polymerized in the presence of a polymerization catalyst to obtain an emulsion polymerization solution.
    A coagulation step in which the obtained emulsion polymerization solution and the coagulation solution are brought into contact with each other to form a hydrous crumb,
    A cleaning process to clean the generated hydrous crumbs,
    The washed water-containing crumb is dehydrated to a water content of 1 to 40% by weight in a dehydration barrel using a dehydration barrel having a dehydration slit, a drying barrel under reduced pressure, and a screw type extruder having a die at the tip, and then contained in the drying barrel. Dehydration / drying / molding process that dries to less than 1% by weight of water and extrudes sheet-shaped dry rubber from the die.
    The method for producing an acrylic rubber veil according to any one of claims 1 to 11, further comprising a bale-forming step of laminating extruded sheet-shaped dry rubber to form a veil.
  13. 　請求項１～１１のいずれか１項に記載のアクリルゴムベールに、充填剤及び架橋剤を混合してなるゴム混合物。 A rubber mixture obtained by mixing a filler and a cross-linking agent with the acrylic rubber veil according to any one of claims 1 to 11.
  14. 　請求項１３に記載のゴム混合物を架橋してなるゴム架橋物。
          A rubber crosslinked product obtained by cross-linking the rubber mixture according to claim 13.
PCT/JP2020/022320 2019-07-19 2020-06-05 Acrylic-rubber bale with excellent storage stability and processability WO2021014797A1 (en)

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US17/626,633 US20220315683A1 (en) 2019-07-19 2020-06-05 Acrylic rubber bale excellent in storage stability and processability
EP20844898.5A EP4001316A4 (en) 2019-07-19 2020-06-05 Acrylic-rubber bale with excellent storage stability and processability
CN202080049000.4A CN114072431A (en) 2019-07-19 2020-06-05 Acrylic rubber bale with excellent storage stability and processability
KR1020227000567A KR20220038334A (en) 2019-07-19 2020-06-05 Acrylic rubber veil with excellent storage stability and processability
EP20844247.5A EP4001315A4 (en) 2019-07-19 2020-07-17 Acrylic rubber bale having excellent storage stability and workability
PCT/JP2020/027947 WO2021015143A1 (en) 2019-07-19 2020-07-17 Acrylic rubber bale having excellent storage stability and workability
KR1020217042526A KR20220038295A (en) 2019-07-19 2020-07-17 Acrylic rubber veil with excellent storage stability and processability
CN202080047949.0A CN114051505B (en) 2019-07-19 2020-07-17 Acrylic rubber bag excellent in storage stability and processability
US17/626,067 US20220259345A1 (en) 2019-07-19 2020-07-17 Acrylic rubber bale excellent in storage stability and processability

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