WO2021014795A1 - 耐水性に優れるアクリルゴム - Google Patents

耐水性に優れるアクリルゴム Download PDF

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Publication number
WO2021014795A1
WO2021014795A1 PCT/JP2020/022318 JP2020022318W WO2021014795A1 WO 2021014795 A1 WO2021014795 A1 WO 2021014795A1 JP 2020022318 W JP2020022318 W JP 2020022318W WO 2021014795 A1 WO2021014795 A1 WO 2021014795A1
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Prior art keywords
weight
acrylic rubber
rubber
meth
acrylic
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Ceased
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PCT/JP2020/022318
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English (en)
French (fr)
Japanese (ja)
Inventor
増田　浩文
信宏 常國
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Zeon Corp
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Zeon Corp
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Application filed by Zeon Corp filed Critical Zeon Corp
Priority to US17/626,613 priority Critical patent/US20220389141A1/en
Priority to CN202080049236.8A priority patent/CN114080402B/zh
Priority to KR1020227000539A priority patent/KR102779954B1/ko
Priority to JP2021534588A priority patent/JP7424381B2/ja
Priority to EP20842946.4A priority patent/EP4001317A4/en
Publication of WO2021014795A1 publication Critical patent/WO2021014795A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
    • B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
    • B29B7/12—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with single shaft
    • B29B7/16—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with single shaft with paddles or arms
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    • 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
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    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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Definitions

  • the present invention relates to acrylic rubber and its production method, rubber composition and rubber crosslinked product. More specifically, acrylic rubber having excellent water resistance and a highly balanced strength property and processability, and the acrylic rubber.
  • the present invention relates to a rubber composition containing rubber and a rubber cross-linked product obtained by cross-linking the rubber composition.
  • 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.
  • Patent Document 1 International Publication No. 2018/079783 pamphlet
  • a monomer component composed of ethyl acrylate, n-butyl acrylate, and mono n-butyl fumarate is contained in pure water, sodium lauryl sulfate, and polyoxy.
  • Emulsified using an emulsifier composed of ethylene dodecyl ether, and emulsion polymerization is carried out in the presence of a polymerization initiator to a polymerization conversion rate of 95% by weight to obtain an emulsion polymerization solution, and sodium sulfate is continuously added thereto to obtain a hydrous crumb.
  • the produced hydrous crumb is washed with industrial water four times, acid washing at pH 3 once, and pure water washing once, and then dried at 110 ° C. for 1 hour in a hot air dryer. Therefore, a method for producing an acrylic rubber having an excellent water resistance (volume change after immersion in 80 ° C. distilled water for 70 hours) with a small residual amount of an emulsifier or a coagulant is disclosed.
  • acrylic rubber which is required to have a high degree of water resistance under a harsher environment and also has excellent strength characteristics and workability, is required.
  • the present invention has been made in view of the actual conditions of the prior art, and is an acrylic rubber having a high degree of water resistance and a balance between strength characteristics and processability, a method for producing the same, and a rubber composition containing the acrylic rubber. , As well as a rubber crosslinked product obtained by cross-linking the same.
  • the present inventors have a specific monomer composition, the ash content and the ash component ratio satisfy specific conditions, and the molecular weight distribution and weight average molecular weight in the high molecular weight region are in a specific range.
  • the acrylic rubber in the above has excellent water resistance and a high balance between strength characteristics and workability. We have found that these characteristics can be improved.
  • the present inventors also, in such acrylic rubber, emulsify a monomer component having a specific composition with a specific emulsifier, and a specific coagulation liquid in which an emulsion polymerization solution obtained by emulsion polymerization to a high polymerization conversion rate is vigorously stirred to some extent. It was found that it can be easily produced by adding it to the inside and solidifying it, then washing the produced hydrous crumb with warm water, and then dehydrating and drying it using a special screw type extruder.
  • the present inventors have completed the present invention based on these findings.
  • a binding unit of at least one (meth) acrylic acid ester derived from the group consisting of a (meth) acrylic acid alkyl ester and a (meth) acrylic acid alkoxyalkyl ester is 70-99.9 weight by weight. %, 0.1 to 10% by weight of the binding unit derived from the reactive group-containing monomer, and 0 to 20% by weight of the binding unit derived from the other monomer, and the ash content is 0.15% by weight. % Or less, the total amount of sodium and sulfur in the ash is 60% by weight or more with respect to the total ash content, and the ratio of sodium to sulfur ([Na] / [S]) is 0.5 to 2.5 by weight.
  • Acrylic acid having a ratio of z average molecular weight (Mz) and weight average molecular weight (Mw) of 1.3 or more and a weight average molecular weight (Mw) in the range of 1,000,000 to 5,000,000. Rubber is provided.
  • the ratio of sodium to sulfur in the ash ([Na] / [S]) is preferably in the range of 0.7 to 1.
  • the amount of gel of the insoluble methyl ethyl ketone in the rubber is 50% by weight or less.
  • the gel amount of the insoluble methyl ethyl ketone is 10% by weight or less.
  • the pH is preferably 6 or less.
  • the ratio of the complex viscosity at 100 ° C. ([ ⁇ ] 100 ° C.) to the complex viscosity at 60 ° C. ([ ⁇ ] 60 ° C.) ([ ⁇ ] 100 ° C./[ ⁇ ] 60 ° C.) is preferably 0.8 or more.
  • the acrylic rubber of the present invention is in the form of a sheet or a veil.
  • the acrylic rubber of the present invention described above preferably has a specific gravity of 0.8 or more.
  • At least one (meth) acrylic acid ester selected from the group consisting of (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester, a reactive group-containing monomer, and a reactive group-containing monomer, and If necessary, a monomer component composed of other copolymerizable monomers is emulsionized with water and a sulfuric acid-based emulsifier, and the polymerization conversion rate is emulsion-polymerized to 90% by weight or more in the presence of a polymerization catalyst to obtain an emulsion polymerization solution.
  • the washing step of washing and the washed water-containing crumb are 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, and the water content in the dehydration barrel is 1 to 40% by weight.
  • a method for producing acrylic rubber which comprises a dehydration / drying step of extruding the dried rubber from the die by drying to less than 1% by weight in the drying barrel after dehydration to.
  • the peripheral speed is preferably 1.5 m / s or more.
  • the sodium salt aqueous solution is preferably a sodium sulfate aqueous solution.
  • the temperature of the hydrous crumb supplied to the screw type extruder is preferably 40 ° C. or higher.
  • a rubber composition containing the above-mentioned rubber component containing acrylic rubber, a reinforcing agent and a cross-linking agent.
  • a rubber crosslinked product obtained by crosslinking the above rubber composition is further provided.
  • an acrylic rubber having excellent water resistance and a balance of strength characteristics and processability is provided, and a method for producing the acrylic rubber, a rubber composition containing the acrylic rubber, and a rubber obtained by cross-linking the acrylic rubber. Crosslinked products are provided.
  • the acrylic rubber of the present invention has a binding unit of 70 to 99.9% by weight derived from at least one (meth) acrylic acid ester selected from the group consisting of (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester. , 0.1 to 10% by weight of the bonding unit derived from the reactive group-containing monomer, and 0 to 20% by weight of the bonding unit derived from the other monomer, and the ash content is 0.15% by weight.
  • the total amount of sodium and sulfur in the ash content is 60% by weight or more with respect to the total ash content, and the ratio of sodium to sulfur ([Na] / [S]) is 0.5 to 2.5 by weight.
  • the ratio of z average molecular weight (Mz) to weight average molecular weight (Mw) is 1.3 or more, and the weight average molecular weight (Mw) is in the range of 1,000,000 to 5,000,000. It is characterized by.
  • the acrylic rubber of the present invention has at least one (meth) acrylic acid ester selected from the group consisting of (meth) acrylic acid alkyl esters and (meth) acrylic acid alkoxyalkyl esters as the monomer components constituting the same. It consists substantially of a reactive group-containing monomer and, optionally, other copolymerizable monomers.
  • (meth) acrylic acid ester is used as a general term for esters of acrylic acid and / or methacrylic acid.
  • 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 (meth). ) Acrylic acid alkyl ester, more preferably a (meth) acrylic acid alkyl ester having an alkyl group having 2 to 6 carbon atoms is used. Specific examples of such (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.
  • the (meth) alkoxyalkyl ester is not particularly limited, but usually has a (meth) alkoxyalkyl ester having 2 to 12 alkoxyalkyl groups, preferably a (meth) having 2 to 8 alkoxyalkyl groups.
  • Acrylic acid alkoxyalkyl esters more preferably (meth) acrylic acid alkoxy esters having an alkoxyalkyl group having 2 to 6 carbon atoms are used.
  • Specific examples of such (meth) acrylic acid alkoxyalkyl ester include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, methoxybutyl (meth) acrylate, and (meth).
  • Examples thereof include ethoxymethyl acrylate, 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 these (meth) acrylic acid alkyl esters and (meth) acrylic acid alkoxyalkyl esters is used alone or in combination of two or more.
  • the proportion of the binding unit (hereinafter sometimes referred to as “monomer component”) derived from these monomers in the acrylic rubber is 70 to 99.9% by weight, preferably 85 to 99.5% by weight, and more. It is preferably 92 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 above-mentioned reactive group-containing monomer is appropriately selected according to the purpose of use thereof, but is usually a single having at least one functional group selected from the group consisting of a carboxyl group, an epoxy group and a halogen group.
  • a monomer having at least one functional group selected from the group consisting of a metric, preferably a carboxyl group, an epoxy group and a chlorine atom can highly improve the compression set resistance and water resistance of the obtained acrylic rubber. Therefore, it is suitable.
  • the halogen group is not particularly limited, but the chlorine atom is suitable for enhancing the compression set resistance and oil resistance.
  • an ethylenically unsaturated carboxylic acid can be preferably used as the monomer having a carboxyl group.
  • 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 is preferable because it can further enhance the compression-resistant permanent strain characteristics when acrylic rubber is used as a rubber cross-linked 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.
  • an ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms is preferable, and examples thereof include butenedioic acid such as fumaric acid and maleic acid, itaconic acid, and citraconic acid.
  • the ethylenically unsaturated dicarboxylic acid includes those existing as an anhydride.
  • the ethylenically unsaturated dicarboxylic acid monoester is usually an ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms and an alkyl monoester having 1 to 12 carbon atoms, preferably an ethylenically unsaturated dicarboxylic acid having 4 to 6 carbon atoms. And an alkyl monoester having 2 to 8 carbon atoms, more preferably an alkyl monoester having 2 to 6 carbon atoms of buthendioic acid having 4 carbon atoms.
  • ethylenically unsaturated dicarboxylic acid monoesters include monomethyl fumarate, monoethyl fumarate, mono n-butyl fumarate, monomethyl maleate, monoethyl maleate, mono n-butyl maleate, and monocyclopentyl fumarate.
  • Monocyclohexyl fumarate, monocyclohexenyl fumarate, monocyclopentyl maleate, monoalkyl maleate such as monocyclohexyl maleate; monomethyl itaconate, monoethyl itaconate, monon-butyl itaconate, monocyclohexyl itaconate Acid monoalkyl esters; etc. are mentioned, and 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 (haloacetyls).
  • the unsaturated alcohol ester of the halogen-containing saturated carboxylic acid include vinyl chloroacetate, vinyl 2-chloropropionate, and allyl chloroacetate.
  • Specific 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. , (Meta) acrylic acid 2-chloropropyl, (meth) acrylic acid 3-chloropropyl, (meth) acrylic acid 2,3-dichloropropyl and the like.
  • (meth) acrylic acid haloacyloxyalkyl ester examples include (meth) acrylic acid 2- (chloroacetoxy) ethyl, (meth) acrylic acid 2- (chloroacetoxy) propyl, and (meth) acrylic acid 3- (chloro). Examples thereof include acetoxy) propyl and 3- (hydroxychloroacetoxy) propyl (meth) acrylate.
  • 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.
  • Specific 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, p-chloromethyl- ⁇ -methylstyrene and the like.
  • halogen-containing unsaturated amide examples include N-chloromethyl (meth) acrylamide, and specific examples of the haloacetyl group-containing unsaturated monomer include 3- (hydroxychloroacetoxy) propylallyl ether. , P-vinylbenzylchloroacetate and the like.
  • a diene monomer having a radical-reactive carbon-carbon double bond group can also be used.
  • a diene monomer having a radical-reactive carbon-carbon double bond group can also be used.
  • examples of such a diene monomer include conjugated diene and non-conjugated diene, and examples of the conjugated diene include 1,3-butadiene, isoprene, and piperylene.
  • examples of the non-conjugated diene include etylidene norbornene, dicyclopentadiene, dicyclopentadienyl (meth) acrylate, and 2-dicyclopentadienyl ethyl (meth) acrylate.
  • These reactive group-containing monomers are used alone or in combination of two or more, and the proportion in the acrylic rubber is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, and more. It is preferably 1 to 3% by weight.
  • the other monomers other than the above-mentioned monomers used as necessary are not particularly limited as long as they can be copolymerized with the above-mentioned monomers.
  • aromatic vinyl, ethylenically unsaturated nitrile, acrylamide-based monomer, and other olefin-based monomers can be mentioned.
  • aromatic vinyl include styrene, ⁇ -methylstyrene, divinylbenzene and the like.
  • Examples of 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 0 to 20% by weight, preferably 0 to 10% by weight, and more preferably 0 to 5% by weight. It is in the range of%.
  • the acrylic rubber of the present invention comprises at least one (meth) acrylic acid ester selected from the group consisting of the above (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester, a reactive group-containing monomer, and a reactive group-containing monomer. It is a polymer obtained from other monomers contained as needed, and each ratio in acrylic rubber is selected from the group consisting of (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester.
  • the binding unit derived from at least one (meth) acrylic acid ester is in the range of 70 to 99.9% by weight, preferably 85 to 99.5% by weight, more preferably 92 to 99% by weight, and is a reactive group.
  • the binding unit derived from the contained monomer is in the range of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, more preferably 1 to 3% by weight, and the binding unit derived from other monomers. However, it is in the range of 0 to 20% by weight, preferably 0 to 10% by weight, and more preferably 0 to 5% by weight.
  • the ash content of the acrylic rubber of the present invention is 0.15% by weight or less, preferably 0.13% by weight or less, more preferably 0.10% by weight or less, the water resistance is highly excellent and suitable.
  • the lower limit of the ash content of the acrylic rubber of the present invention is not particularly limited, but is usually 0.0001% by weight or more, preferably 0.0005% by weight or more, more preferably 0.001% by weight or more, and particularly preferably 0. When it is 005% by weight or more, most preferably 0.01% by weight or more, the adhesiveness to the metal is reduced and the workability is improved, which is preferable.
  • the amount of ash for highly balancing both water resistance and metal adhesion is usually 0.0001 to 0.15% by weight, preferably 0.0005 to 0.14% by weight, and more preferably 0.001. It can be said that the preferable range is from 0.13% by weight, particularly preferably 0.005 to 0.12% by weight, and most preferably 0.01 to 0.1% by weight.
  • the acrylic rubber of the present invention When the total amount of sodium and sulfur in the ash content of the acrylic rubber of the present invention is 60% by weight or more, preferably 70% by weight or more, and more preferably 80% by weight or more in proportion to the total ash content, the acrylic rubber It is suitable because it has a high degree of water resistance.
  • the ratio of sodium to sulfur ([Na] / [S]) in the ash content of the acrylic rubber of the present invention is 0.5 to 2.5 by weight, preferably 0.6 to 1.5, more preferably. When it is in the range of 0.7 to 1, particularly preferably 0.75 to 0.95, and most preferably 0.8 to 0.9, the acrylic rubber having highly excellent water resistance is suitable.
  • the ratio (Mz / Mw) of the z average molecular weight (Mz) and the weight average molecular weight (Mw) of the acrylic rubber of the present invention is an absolute molecular weight distribution that emphasizes high molecular weight substances measured by GPC-MALS and is 1.3. As described above, when it is preferably in the range of 1.4 to 5, more preferably 1.5 to 2, the processability and strength characteristics of acrylic rubber are highly balanced, and changes in physical properties during storage can be alleviated. Is.
  • the weight average molecular weight (Mw) of the acrylic rubber of the present invention is an absolute molecular weight measured by GPC-MALS, which is 1,000,000 to 5,000,000, preferably 1,100,000 to 4,000,000. , More preferably 1,200,000 to 3,000,000, most preferably 1,300,000 to 2,500,000, processability, strength characteristics and compression resistance when acrylic rubber is mixed. It is suitable because the permanent strain characteristics are highly balanced.
  • the amount of gel of the acrylic rubber of the present invention may be appropriately selected according to the purpose of use of the rubber, but is not particularly limited by the insoluble content of methyl ethyl ketone, but is usually 50% by weight or less, preferably 30. When it is 0% by weight or less, more preferably 20% by weight or less, particularly preferably 10% by weight or less, and most preferably 5% by weight or less, the processability and strength characteristics of the acrylic rubber are highly balanced, which is preferable. ..
  • the glass transition temperature (Tg) of the acrylic rubber of the present invention may be appropriately selected depending on the intended use of the rubber, but is usually 20 ° C. or lower, preferably 10 ° C. or lower, more preferably 0 ° C. or lower.
  • Acrylic rubber is suitable because it has good workability and cold resistance.
  • 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 specific gravity of the acrylic rubber of the present invention is appropriately selected according to the intended use of the rubber, but is usually 0.7 to 1.5, preferably 0.8 to 1.4, and more preferably 0.9 to 1. 3. Especially preferably, when the range is 0.95 to 1.25, most preferably 1.0 to 1.2, the storage stability of the acrylic rubber is excellent, which is preferable.
  • the water content of the acrylic rubber of the present invention is appropriately selected according to the intended use of the rubber, but is usually less than 1% by weight, preferably 0.8% by weight or less, more preferably 0.6% by weight or less.
  • the vulcanization characteristics of acrylic rubber are optimized, and the heat resistance and water resistance of crosslinked rubber are highly improved, which is preferable.
  • the complex viscosity ([ ⁇ ] 60 ° C.) of the acrylic rubber of the present invention at 60 ° C. is not exceptional, but is usually 15,000 Pa ⁇ s or less, preferably 2,000 to 10,000 Pa ⁇ s. It is preferably in the range of 2,500 to 7,000 Pa ⁇ s, most preferably 2,700 to 5,500 Pa ⁇ s, and the acrylic rubber in this range has excellent workability, oil resistance and shape retention. It is suitable because it is excellent.
  • the complex viscosity ([ ⁇ ] 100 ° C.) of the acrylic rubber 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 5,000 Pa. ⁇ S, more preferably in the range of 2,500 to 4,000 Pa ⁇ s, most preferably in the range of 2,500 to 3,500 Pa ⁇ s. Acrylic rubber in this range is suitable because it is excellent in processability, oil resistance and shape retention.
  • it is usually 0.5 or more, preferably 0.6 or more, more preferably 0.75 or more, particularly preferably 0.8 or more, and most preferably 0.83 or more.
  • 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. 5 to 0.98, preferably 0.6 to 0.95, more preferably 0.75 to 0.93, particularly preferably 0.8 to 0.93, most preferably 0.83 to 0.93. In this case, the processability, oil resistance, and shape retention of acrylic rubber are highly balanced and suitable.
  • the pH of the acrylic rubber 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 most preferably 3 to 5.
  • the storage stability of acrylic rubber is highly improved, which is suitable.
  • the Mooney viscosity (ML1 + 4,100 ° C.) of the acrylic rubber of the present invention is not particularly limited, but is usually 10 to 150, preferably 20 to 100, and more preferably 25 to 70.
  • the workability and strength characteristics of rubber are highly balanced and suitable.
  • the shape of the acrylic rubber of the present invention is not particularly limited and may be appropriately selected depending on the intended use.
  • it may be crumb-shaped, powder-shaped, rod-shaped, sheet-shaped, veil-shaped, etc.
  • the veil shape is remarkably excellent in workability and storage stability and is suitable.
  • the sheet-shaped or bale-shaped acrylic rubber of the present invention is a form of the above-mentioned acrylic rubber, which is overwhelmingly superior in workability as compared with a form such as a crumb-shaped rubber, and has a small specific surface area of the acrylic rubber and is remarkably excellent in storage stability. Excellent and suitable.
  • the sheet-shaped or bale-shaped acrylic rubber of the present invention is in a raw rubber state and is uncrosslinked.
  • the specific gravity of the sheet-shaped or bale-shaped acrylic rubber of the present invention is not particularly limited, but is usually 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and particularly preferably 0.95 or more. Most preferably, it is 1.0 or more.
  • the specific gravity of the sheet-shaped or bale-shaped acrylic rubber of the present invention is also usually 0.7 to 1.5, preferably 0.8 to 1.4, more preferably 0.9 to 1.3, and particularly preferably 0. When it is in the range of .95 to 1.25, most preferably 1.0 to 1.2, storage stability and workability are highly balanced and preferable.
  • the thickness of the sheet-shaped acrylic rubber of the present invention is appropriately selected according to the intended use without any particular limitation, but is usually 1 to 40 mm, preferably 2 to 35 mm, more preferably 3 to 30 mm, and most preferably 5. When the range is in the range of ⁇ 25 mm, workability, storage stability and productivity are highly balanced and suitable.
  • the width of the sheet-shaped acrylic rubber of the present invention is appropriately selected depending on the intended use, but is usually in the range of 300 to 1,200 mm, preferably 400 to 1,000 mm, more preferably 500 to 800 mm. It has excellent handleability and is suitable.
  • the length of the sheet-shaped acrylic rubber of the present invention is not particularly limited, but is particularly handled when it is usually in the range of 300 to 1,200 mm, preferably 400 to 1,000 mm, and more preferably 500 to 800 mm. It has excellent properties and is suitable.
  • the shape of the veiled acrylic rubber of the present invention is not particularly limited and is appropriately selected according to the purpose of use, but in many cases, a rectangular parallelepiped is preferable.
  • the size of the veil-shaped acrylic rubber of the present invention is not particularly limited and is appropriately selected according to the intended use, but the width is usually in the range of 100 to 800 mm, preferably 200 to 500 mm, and more preferably 250 to 450 mm.
  • the length is usually in the range of 300 to 1,200 mm, preferably 400 to 1,000 mm, more preferably 500 to 800 mm, and the height (thickness) is usually 50 to 500 mm, preferably 100 to 300 mm, more preferably. Is suitable to be in the range of 150-250 mm.
  • Acrylic rubber having excellent properties as described above can be efficiently produced, for example, by the production method of the present invention including the following steps (1) to (5).
  • An emulsion polymerization step in which a monomer component composed of other polymerizable monomers is emulsion-polymerized with water and a sulfuric acid-based emulsifier and the polymerization conversion rate is emulsion-polymerized to 90% by weight or more in the presence of a polymerization catalyst to obtain an emulsion polymerization solution.
  • 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 dried.
  • a dehydration / drying process that dries to less than 1% by weight in a barrel and pushes the dried rubber out of the die.
  • the emulsion polymerization step in the method for producing acrylic rubber of the present invention comprises 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.
  • a monomer component consisting of the contained monomer and other copolymerizable monomers used as needed is emulsionized with water and a sulfuric acid-based emulsifier, and the polymerization conversion rate is 90% by weight in the presence of a polymerization catalyst.
  • This is the step of obtaining an emulsion polymerization solution by emulsion polymerization up to the above.
  • the monomer components used here are the same as those exemplified above and those described as a preferable range.
  • the amount of the monomer component used may be appropriately selected so as to have the above composition of the acrylic rubber of the present invention.
  • a sulfuric acid ester-type anionic emulsifier can be preferably used.
  • the sulfate ester type anionic emulsifier 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. Is.
  • sulfuric acid-based 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, based on 100 parts by weight of the monomer component. It is in the range of 1 to 5 parts by weight, more preferably 1 to 3 parts by weight.
  • emulsifiers in addition to the above sulfuric acid-based emulsifier, other emulsifiers can be used in combination, if necessary.
  • the types of emulsifiers other than the sulfuric acid-based emulsifier are not limited, and examples thereof include anionic emulsifiers other than the sulfuric acid-based emulsifier, cationic emulsifiers, and nonionic emulsifiers, and nonionic emulsifiers are particularly preferably used.
  • anionic emulsifiers other than sulfuric acid-based emulsifiers include fatty acid-based emulsifiers such as sodium octanate, sodium decanoate, sodium laurate, sodium myristate, sodium palmitate, and sodium stearate; sodium hexanesulfonate and octane sulfonic acid.
  • Examples of the cationic emulsifier include alkyltrimethylammonium chloride, dialkylammonium chloride, and benzylammonium chloride.
  • nonionic emulsifier examples include polyoxyalkylene fatty acid esters such as polyoxyethylene stearic acid ester; polyoxyalkylene alkyl ethers such as polyoxyethylene dodecyl ether; polyoxyalkylene alkyl phenol ethers such as polyoxyethylene nonylphenyl ether; and poly.
  • examples thereof include oxyethylene sorbitan alkyl ester, and polyoxyalkylene alkyl ether and polyoxyalkylene alkyl phenol ether are preferable, and polyoxyethylene alkyl ether and polyoxyethylene alkyl phenol ether are more preferable.
  • emulsifiers other than these sulfuric acid-based emulsifiers can be used alone or in combination of two or more, and the amount used can be used within a range that does not impair the effects of the present invention, and is a monomer component. It is usually in the range of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 1 to 3 parts by weight with respect to 100 parts by weight.
  • a conventional method may be followed, and a method of stirring the monomer, emulsifier and water using a stirrer such as a homogenizer or a disk turbine is adopted. ..
  • the amount of water used at this time 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 in emulsion polymerization may be one 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, which are preferably peroxides, and inorganic peroxides and organic peroxides are used.
  • Examples of the inorganic peroxide include sodium persulfate, potassium persulfate, hydrogen peroxide, ammonium persulfate, etc.
  • potassium persulfate, hydrogen peroxide, ammonium persulfate are preferable, and potassium persulfate is preferable. Especially preferable.
  • the organic peroxide is not limited as long as it is used in emulsion polymerization, and is, for example, 2,2-di (4,5-di- (t-butylperoxy) cyclohexyl) propane, 1-.
  • 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) -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.
  • 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, based on 100 parts by weight of the monomer component. It is in the range of 0005 to 1 part by weight, more preferably 0.001 to 0.5 parts by weight.
  • the reducing agent can be used without particular limitation as long as it is used in the redox catalyst of emulsion polymerization, 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 ferrous naphthenate. Among these, ferrous sulfate is included. preferable.
  • 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 0.01 with respect to 100 parts by weight of the monomer component. It is in the range of 0.00001 to 0.001 parts by weight, more preferably 0.00005 to 0.0005 parts by weight.
  • Examples of the reducing agent other than the metal ion compound in the reduced state include ascorbic acid such as ascorbic acid, sodium ascorbate and potassium ascorbate or a salt thereof; erythorbic acid such as erythorbic acid, sodium erythorbate and potassium erythorbicate.
  • sulfites such as sodium hydroxymethane sulfite; sodium sulfite, potassium sulfite, sodium hydrogen sulfite, aldehyde sodium hydrogen sulfite, potassium hydrogen sulfite sulfite; sodium pyrosulfite, potassium pyrosulfite, sodium pyrosulfite, Pyro sulfites such as potassium hydrogen pyrosulfite; thiosulfates such as sodium thiosulfite and potassium thiosulfite; phosphite, sodium bisulfite, potassium bisulfite, sodium bisulfite, potassium hydrogen sulfite phosphite or salts thereof; Pyrophosphates such as pyrophosphate, sodium pyrophosphate, potassium pyrophosphate, sodium hydrogenpyrophosphate, potassium hydrogenpyrophosphate or salts thereof; sodium formaldehyde sulfoxylate and the like can be mentioned.
  • the reducing agents other than the metal ion compounds in the reduced state can be used individually or in combination of two or more, and the amount used is usually 0.001 to 0.001 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 preferable combination of the metal ion compound in the reduced state and the other reducing agent is a combination of ferrous sulfate and ascorbic acid or a salt thereof and / or sodium formaldehyde sulfoxylate, and more preferably ferrous sulfate and ascorbin.
  • 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 step may be only the amount used at the time of emulsification of the above-mentioned monomer component, but is usually 10 to 1 with respect to 100 parts by weight of the monomer component used for polymerization. It is adjusted to be in the range of 000 parts by weight, preferably 50 to 500 parts by weight, more preferably 80 to 400 parts by weight, and most preferably 100 to 300 parts by weight.
  • the method of the emulsion polymerization reaction may be 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 depending on 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 acrylic rubber produced is excellent in strength characteristics and has no monomeric odor. is there.
  • a polymerization inhibitor may be used to terminate the polymerization.
  • the coagulation step in the method for producing acrylic rubber of the present invention is characterized in that the obtained emulsion polymerization solution is added to a sodium salt aqueous solution stirred at a peripheral speed of 0.5 m / s or more to generate a hydrous crumb. And.
  • 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 sodium salt used here is not particularly limited, and examples thereof include inorganic sodium salts such as sodium chloride, sodium nitrate and sodium sulfate, and organic sodium salts such as sodium formate and sodium acetate. Among these, an inorganic sodium salt is preferable, sodium chloride and sodium sulfate are more preferable, and sodium sulfate is particularly preferable.
  • Each of these sodium salts 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 0.1, based on 100 parts by weight of the monomer component.
  • the range is from 50 parts by weight, more preferably 1 to 30 parts by weight.
  • the amount of sodium salt is in this range, not only the acrylic rubber is sufficiently solidified, but also the compression set resistance and water resistance when the acrylic rubber is crosslinked can be highly improved, which is preferable.
  • a coagulant other than the sodium salt may be used in combination as long as the effect of the present invention is not impaired.
  • the sodium salt concentration of the aqueous sodium salt solution used is not particularly limited, but is usually in the range of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, and more preferably 1 to 5% by weight. It is suitable because the particle size of the hydrous crumb generated at a certain time can be uniformly focused in a specific region.
  • the temperature of the sodium salt-containing aqueous solution is not particularly limited, but is preferably 40 ° C. or higher, preferably 40 to 90 ° C., more preferably 50 to 80 ° C., to produce a uniform hydrous crumb.
  • the stirring number of the agitated sodium salt aqueous solution is represented by the number of rotations of the stirring blade of the stirring device provided in the coagulation bath containing the sodium salt aqueous solution, but the one in which the aqueous solution is vigorously agitated is generated.
  • the water-containing crumb particle size is preferably small and uniform, and is usually in the range of 100 rpm or more, preferably 200 to 1,000 rpm, more preferably 300 to 900 rpm, and particularly preferably 400 to 800 rpm. That is, it is preferable that the number of rotations at which the coagulating liquid is vigorously agitated to some extent is such that the generated hydrous crumb particle size can be focused to a size that is uniform and has good ash removal efficiency.
  • the peripheral speed of the agitated sodium salt aqueous solution is represented by the speed of the outer circumference of the stirring blade of the agitating device, and the water-containing crumb particle size generated when the aqueous solution is vigorously agitated to a certain degree is small and uniform.
  • the peripheral speed is 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. It is better to set it to / 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 hydrous crumb thus produced is sieved by a JIS sieve, it is preferable that all of the following conditions (a) to (e) are satisfied.
  • the JIS sieve complies with the provisions of Japanese Industrial Standards (JIS Z 8801-1).
  • JIS Z 8801-1 The proportion of hydrous crumbs that do not pass through a JIS sieve with an opening of 9.5 mm is 10% by weight or less.
  • B The proportion of hydrous crumbs that pass through a 9.5 mm mesh JIS sieve and do not pass through a 6.7 mm JIS sieve is 30% by weight or less.
  • the proportion of hydrous crumbs that do not pass through the JIS sieve having a mesh size of 9.5 mm is 10% by weight or less, preferably 5% by weight or less. It is preferably 1% by weight or less, and (b) the proportion of the hydrous crumb that passes through the 9.5 mm mesh JIS sieve and does not pass through the 6.7 mm JIS sieve is 30% by weight or less, preferably 20% by weight.
  • the proportion of the hydrous crumb that passes through the 6.7 mm mesh JIS sieve and does not pass through the 710 ⁇ m JIS sieve is 20% by weight or more, preferably 40% by weight.
  • the proportion of water-containing crumbs that pass through a JIS sieve with an opening of 710 ⁇ m and do not pass through a JIS sieve of 425 ⁇ m is 30% by weight.
  • % Or less preferably 20% by weight or less, more preferably 15% by weight or less, and (e) the proportion of hydrous crumb passing through a JIS sieve with an opening of 425 ⁇ m is 10% by weight or less, preferably 5% by weight. %, More preferably 1% by weight or less, which is preferable because the cleaning efficiency of the emulsifier and the coagulant is remarkably improved and the productivity is also increased.
  • the proportion of the produced hydrous crumb (f) that passes through the JIS sieve with a mesh size of 6.7 mm and does not pass through the JIS sieve with a mesh size of 4.75 mm is usually 40 weight. % Or less, preferably 10% by weight or less, more preferably 5% by weight or less, the cleaning efficiency of the emulsifier or coagulant is improved, which is preferable.
  • the proportion of the hydrous crumb that has passed through the (g) JIS sieve with a mesh size of 4.75 mm and does not pass through the JIS sieve with a mesh size of 710 ⁇ m is usually 40% by weight or more, preferably 60% by weight or more. More preferably, when it is 80% by weight or more, the removal efficiency of the emulsifier and coagulant during cleaning and dehydration is remarkably improved, which is preferable.
  • the proportion of the produced hydrous crumb that passes through the (h) JIS sieve having a mesh size of 3.35 mm and does not pass through the JIS sieve having a mesh size of 710 ⁇ m is usually 20% by weight or more, preferably 40% by weight or more.
  • it is more preferably 50% by weight or more, particularly preferably 60% by weight or more, and most preferably 70% by weight or more, the removal efficiency of the emulsifier and coagulant during washing and dehydration is remarkably improved.
  • the cleaning step in the method for producing acrylic rubber of the present invention is a step of cleaning the hydrous crumb produced in the solidification step with warm water.
  • the cleaning method is not particularly limited and may follow a conventional method.
  • the generated hydrous crumb can be mixed with a large amount of warm water.
  • the amount of hot 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 above-mentioned 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 hot water to be washed with water is not particularly limited, but it is preferable to use hot water because the washing efficiency is improved.
  • the temperature of the hot water is not particularly limited, but is preferably 40 ° C. or higher, preferably 40 to 100 ° C., more preferably 50 to 90 ° C., and most preferably 60 to 80 ° C., because the cleaning efficiency can be significantly increased. Is. That is, when the temperature of the washing water is set to be equal to or higher than the above lower limit, the emulsifier and the coagulant are released from the hydrous crumb, and the washing efficiency is further improved.
  • the washing 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 times of washing with water 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 washings with water is large, but the shape of the water-containing crumb and the diameter of the water-containing crumb should be specified as described above. And / or by setting the cleaning temperature within the above range, the number of cleanings can be significantly reduced.
  • the water-containing crumb washed in the above washing step is dehydrated 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. It is characterized by dehydrating to a water content of 1 to 40% by weight and then drying to less than 1% by weight in a drying barrel to extrude the dried rubber from the die.
  • the hydrous crumb supplied to the screw type extruder is one in which free water is removed (drained) after washing.
  • Draining step In the production method of the present invention, it is preferable to provide a draining step for separating free water from the water-containing crumb after washing with a drainer after the washing step and before the dehydration / drying step in order to improve the dehydration efficiency. Is.
  • 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.
  • 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, more preferably 0.2 to 0.6 mm, the water content crumb loss is small and It is suitable because it can drain water efficiently.
  • 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 to be put into the next dehydration / drying step is not particularly limited, but is usually 40 ° C. or higher, preferably 40 to 100 ° C.
  • the temperature is more preferably 50 to 90 ° C., particularly preferably 55 to 85 ° C., and most preferably 60 to 80 ° C.
  • the specific heat is 1.5 to 2.5 KJ / kg, like the acrylic rubber of the present invention.
  • a hydrous crumb with a high temperature of K which is difficult to raise the temperature, it is suitable to use a screw type extruder because it can be efficiently dehydrated and dried.
  • dehydration of hydrous crumbs is performed in a dehydration barrel portion having a dehydration slit provided in the screw type extruder.
  • the opening of the dehydration slit may be appropriately selected according to the conditions of use, but is usually in the range of 0.01 to 5 mm, preferably 0.1 to 1 mm, and more preferably 0.2 to 0.6 mm.
  • the number of dehydration barrels in the screw extruder is not particularly limited, but usually, when the number is usually a plurality, preferably 2 to 10, more preferably 3 to 6, dehydration of the adhesive acrylic rubber. It is suitable for performing the above efficiently.
  • the adhesive acrylic rubber can be efficiently dehydrated by combining drainage and exhaust steam.
  • a screw type extruder equipped with three or more dehydration barrels the selection of whether to use a drainage type dehydration barrel or a steam exhaust type dehydration barrel for each dehydration barrel may be appropriately performed according to the purpose of use, but it is manufactured.
  • To reduce the amount of ash in the acrylic rubber it is better to increase the number of drainage barrels, and to reduce the water content, it is better to increase the number of steam exhaust type barrels.
  • the set temperature of the dehydration barrel is appropriately selected depending on the monomer composition, ash content, water content, operating conditions, etc. of the acrylic rubber, but is usually 60 to 150 ° C., preferably 70 to 140 ° C., more preferably 80 to 80 to It is in the range of 130 ° C.
  • the set temperature of the dehydration barrel that dehydrates in the drained state is usually 60 ° C. to 120 ° C., preferably 70 to 110 ° C., and more preferably 80 to 100 ° C.
  • the set temperature of the dehydration barrel that dehydrates in the exhaust 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 dehydration that squeezes water from the water-containing crumb is usually 1 to 45% by weight, preferably 1 to 40% by weight, more preferably 5 to 35% by weight, and particularly preferably 10 to 35% by weight. Most preferably, when it is 15 to 35% by weight, the productivity and the efficiency of ash removal are highly balanced and preferable.
  • the acrylic rubber adheres to the dehydration slit portion and can hardly be dehydrated (water content is only about 45 to 55% by weight).
  • water content can be reduced to this extent by using a screw type extruder having a dehydration slit and forcibly squeezed with a screw.
  • the water content after dehydration in the drain type dehydration barrel portion is usually 5 to 45% by weight, preferably 10 to 40% by weight. It is preferably 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 the deterioration of the acrylic rubber can be suppressed, and by setting it below the above upper limit, the ash content of the acrylic rubber can be sufficiently reduced. It can be reduced.
  • the drying step of the hydrous crumb after dehydration is performed in the 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., the acrylic rubber is not burnt or deteriorated and is efficient. It is suitable because it can be dried well 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 degree of decompression may be an approximate degree of decompression for all the dry barrels, or may be changed for each barrel.
  • the set temperature may be an approximate temperature for all drying barrels or may be changed for each barrel, but it is higher than the temperature of the introduction part of the hydrous crumb (closer to the dehydration barrel). It is preferable to raise the temperature of the discharge part (closer to the die) 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 water content of the dry rubber is set to this value (a state in which almost all water is removed) and melt extrusion is performed to reduce the gel amount of the methyl ethyl ketone insoluble portion of the acrylic rubber. It is suitable for
  • Acrylic rubber shape (die part)
  • the acrylic rubber dehydrated and dried by the screw portions of the dehydration barrel and the drying barrel is sent to a screwless rectifying die portion provided near the tip of the screw type extruder.
  • a breaker plate or wire mesh may or may not be provided between the screw and the die portion.
  • the dried rubber to be extruded can be obtained in various shapes such as granular, pellet-shaped, columnar, round bar-shaped, and sheet-shaped depending on the nozzle shape of the die, and any of them may be used.
  • 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, more preferably 1 to 3 MPa, the amount of air entrained in the rubber is small (rubber). It is suitable because it has a high specific gravity and is also excellent in productivity.
  • 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 usually 10 to 100, preferably 20 to 80, more preferably 30 to 60, and particularly preferably. When it is in the range of 40 to 50, the water content can be reduced to less than 1% by weight without causing a decrease in the molecular weight or "burning" of the dried rubber, which is preferable.
  • 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 of acrylic rubber and the gel amount of the insoluble methyl ethyl ketone when the speed is 120 to 300 rpm.
  • the extrusion rate (Q) of the screw type extruder used is usually 100 to 1,500 kg / hr, preferably 300 to 1,200 kg / hr, more preferably 400 to 1,000 kg / hr, and most preferably 500 to 500. It is in the range of 800 kg / hr.
  • the ratio (Q / N) of the extrusion amount (Q) to the rotation speed (N) of the screw type extruder used is usually in the range of 2 to 10, preferably 3 to 8, and more preferably 4 to 6.
  • the strength characteristics, processability, and manufacturing productivity of acrylic rubber are highly balanced and suitable.
  • the acrylic rubber thus obtained is remarkably excellent in workability, strength characteristics and water resistance.
  • the shape of the obtained acrylic rubber is not particularly limited, and may be, for example, crumb-shaped, powder-shaped, rod-shaped, sheet-shaped, veil-shaped, etc., but the sheet-shaped or bale-shaped is processable and strong. It is suitable because it has excellent properties and water resistance, and also has excellent workability and storage stability.
  • Sheet-shaped or bale-shaped acrylic rubber The sheet-shaped acrylic rubber can be cut by extruding the sheet-shaped dry rubber with the die portion of the screw-type extruder having a substantially rectangular shape and cooling it if necessary.
  • the bale-shaped acrylic rubber is not particularly limited, but can be obtained by laminating the obtained sheet-shaped acrylic rubber, both of which are superior in workability and air entrainment as compared with crumb-shaped acrylic rubber and the like. It is suitable because it has a small amount (high specific gravity) and is overwhelmingly excellent in storage stability.
  • the thickness of the sheet-shaped dry rubber extruded from the screw type extruder is not particularly limited, but is usually in the range of 1 to 40 mm, preferably 2 to 35 mm, more preferably 3 to 30 mm, and most preferably 5 to 25 mm. It is suitable because it has excellent workability and productivity at some time. In particular, since the thermal conductivity of the sheet-shaped dry rubber is as low as 0.15 to 0.35 W / mK, the thickness of the sheet-shaped dry rubber is usually 1 to 30 mm when the cooling efficiency is increased and the productivity is remarkably improved.
  • the range is preferably 2 to 25 mm, more preferably 3 to 15 mm, and particularly preferably 4 to 12 mm.
  • the width of the sheet-shaped dry rubber extruded from the screw type extruder is appropriately selected according to the purpose of use, but is usually in the range of 300 to 1,200 mm, preferably 400 to 1,000 mm, and more preferably 500 to 800 mm. is there.
  • the temperature of the dry rubber extruded from the screw type extruder is not particularly limited, but is usually in the range of 100 to 200 ° C, preferably 110 to 180 ° C, and more preferably 120 to 160 ° C.
  • the water content of the dried rubber extruded from the screw type extruder is not particularly limited, but is usually less than 1% by weight, preferably 0.8% by weight or less, and more preferably 0.6% by weight or less.
  • the complex viscosity ([ ⁇ ] 100 ° C.) of the sheet-shaped dry rubber extruded from the screw type extruder at 100 ° C. is not particularly limited, but is usually 1,500 to 6,000 Pa ⁇ s, preferably 2.
  • Extrudability and shape retention as a sheet when the range is 5,000 to 5,000 Pa ⁇ s, more preferably 2,500 to 4,000 Pa ⁇ s, and most preferably 2,500 to 3,500 Pa ⁇ s. Is highly balanced and suitable. That is, when it is at least the lower limit, the extrudability can be improved, and when it is at least the upper limit, the shape of the sheet-shaped dry rubber can be suppressed from collapsing or breaking.
  • the sheet-shaped dry rubber extruded from the screw type extruder may be folded and used as it is, but usually it can be cut and used.
  • the cutting of the sheet-shaped dry rubber is not particularly limited, but since the acrylic rubber of the present invention has strong adhesiveness, the sheet-shaped dry rubber must be cooled before continuously cutting without entraining air. It is preferable to do so.
  • 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 There is no particular limitation and it may be appropriately selected according to the purpose of use, but it 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. When it is 0.85 or more and the upper limit is usually 0.98 or less, preferably 0.97 or less, more preferably 0.96 or less, particularly preferably 0.95 or less, and most preferably 0.93 or less. It is suitable because it has low air entrainment 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 is appropriately selected according to the purpose of use, but is usually in the range of 100 to 800 mm, preferably 200 to 500 mm, and more preferably 250 to 450 mm.
  • the sheet-shaped acrylic rubber thus obtained is superior in operability, storage stability, processability, strength characteristics, water resistance and compression-resistant permanent strain characteristics as compared with crumb-shaped acrylic rubber, and is veiled as it is or by laminating. Can be used.
  • the method for producing the bale-shaped acrylic rubber of the present invention is not particularly limited, but by laminating the sheet-shaped dry rubber (sheet-shaped acrylic rubber), a bale with less air entrainment and excellent storage stability. Acrylic rubber veil can be obtained and is suitable.
  • 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 veiled acrylic rubber.
  • the veil-shaped acrylic rubber of the present invention is integrated by the weight of the laminated sheet-shaped dry rubber.
  • the veil-shaped acrylic rubber of the present invention thus obtained is superior in operability and storage stability as compared with crumb-shaped acrylic rubber, and is also excellent in processability, strength characteristics, water resistance and compression set resistance, and veil-shaped acrylic rubber. Can be used as it is, or after cutting the required amount, it can be put into a mixer such as a rubber or roll.
  • the rubber composition of the present invention is characterized by containing the above-mentioned rubber component containing the acrylic rubber of the present invention, a filler, and a cross-linking agent.
  • the content of the acrylic rubber of the present invention in the rubber component may be selected according to the intended use of the rubber composition, for example, usually 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight. That is all.
  • the acrylic rubber of the present invention alone or in combination with the above acrylic rubber and other rubbers can be used.
  • acrylic rubbers used in combination with the acrylic rubber of the present invention include acrylic rubbers other than the above acrylic rubbers, natural rubbers, polybutadiene rubbers, polyisoprene rubbers, styrene-butadiene rubbers, acrylonitrile-butadiene rubbers, silicon rubbers, and fluororubbers.
  • acrylic rubbers other than the above acrylic rubbers natural rubbers, polybutadiene rubbers, polyisoprene rubbers, styrene-butadiene rubbers, acrylonitrile-butadiene rubbers, silicon rubbers, and fluororubbers.
  • examples thereof include olefin-based elastomers, styrene-based elastomers, vinyl chloride-based elastomers, polyester-based elastomers, polyamide-based elastomers, polyurethane-based elastomers, and polysiloxane-based elastomers.
  • the shape of these other rubbers may be any of a veil shape, a sheet shape, a powder and granular material shape, and the like.
  • the content of other rubbers in the rubber component is appropriately selected within a range that does not impair the effects of the present invention, and is, for example, usually 70% by weight or less, preferably 50% by weight or less, and more preferably 30% by weight or less.
  • the filler is not particularly limited, and examples thereof include a reinforcing filler and a non-reinforcing filler, and a reinforcing filler is preferably used.
  • 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 non-reinforcing property.
  • the filler include quartz powder, diatomaceous earth, zinc white, basic sodium carbonate, activated calcium carbonate, sodium silicate, aluminum silicate, titanium dioxide, talc, aluminum sulfate, calcium sulfate, barium sulfate and the like. ..
  • Each of these fillers can be used alone or in combination of two or more, and the blending amount thereof is not particularly limited, but is usually 1 to 200 parts by weight with respect to 100 parts by weight of the rubber component. It is preferably in the range of 10 to 150 parts by weight, more preferably 20 to 100 parts by weight.
  • the cross-linking agent is not particularly limited, but for example, a polyvalent amine compound such as a diamine compound and a carbonate thereof; a sulfur compound; a sulfur donor; a triazinethiol compound; a polyvalent epoxy compound; an ammonium organic carboxylate salt; Conventionally known cross-linking agents such as oxides; polyvalent carboxylic acids; quaternary onium salts; imidazole compounds; isocyanuric acid compounds; organic peroxides; triazine compounds; can be used. Among these, a polyvalent amine compound and a triazine compound are preferable, and a polyvalent amine compound is particularly preferable.
  • polyvalent amine compound examples include aliphatic polyvalent amine compounds such as hexamethylenediamine, hexamethylenediamine carbamate, and N, N'-dicinnamylidene-1,6-hexanediamine; 4,4'-methylenedianiline, p.
  • hexamethylenediamine carbamate 2,2'-bis [4- (4-aminophenoxy) phenyl] propane and the like are preferable.
  • These polyvalent amine compounds are particularly preferably used in combination with a carboxyl group-containing acrylic rubber.
  • 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 And so on.
  • These triazine compounds are particularly preferably used in combination with a halogen group-containing acrylic rubber.
  • 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 to 10 parts by weight, based on 100 parts by weight of the rubber component. It is by weight, more preferably 0.1 to 5 parts by weight.
  • the blending amount of the cross-linking agent is usually 0.001 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the rubber component. It is by weight, more preferably 0.1 to 5 parts by weight.
  • the rubber composition of the present invention can further be blended with an anti-aging agent, if necessary.
  • the anti-aging agent is not particularly limited, but is 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butylphenol, butylhydroxyaniline, 2,6-di-t-butyl-.
  • 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 0.1 to 100 parts by weight, based on 100 parts by weight of the rubber component. It is in the range of 10 parts by weight, more preferably 1 to 5 parts by weight.
  • the rubber composition of the present invention comprises the rubber component, a filler, a cross-linking agent and, if necessary, an anti-aging agent, and if necessary, other additives commonly used in the art, such as , Cross-linking aids, cross-linking accelerators, cross-linking retarders, silane coupling agents, plasticizers, processing aids, lubricants, pigments, colorants, antistatic agents, foaming agents and the like can be arbitrarily blended. These other compounding agents can be used alone or in combination of two or more, and the compounding amount thereof is appropriately selected within a range that does not impair the effects of the present invention.
  • 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.
  • a mixing procedure for example, after sufficiently mixing components that are difficult to react or decompose by heat, a cross-linking agent that is a component that easily reacts or decomposes by heat is mixed in a short time at a temperature at which reaction or decomposition does not occur. It is preferable to do so.
  • the rubber crosslinked product of the present invention is obtained by cross-linking the above rubber composition.
  • the rubber crosslinked product of the present invention is formed by using the rubber composition 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 known 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, size, etc. 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 crosslinked rubber product of the present invention has excellent workability and water resistance while maintaining the basic characteristics of rubber such as tensile strength, elongation, and hardness.
  • the rubber crosslinked product of the present invention utilizes the above characteristics, for example, O-ring, packing, diaphragm, oil seal, shaft seal, bore ring sheath, mechanical seal, well head seal, seal for electric / electronic equipment, air compression.
  • Sealing materials such as equipment seals; rocker cover gaskets attached to the connection between the cylinder block and the cylinder head, oil pan gaskets attached to the connection between the oil pan and the cylinder head or the transmission case, positive electrode, electrolyte plate and
  • Various gaskets such as gaskets for fuel cell separators and gaskets for the top cover of hard disk drives mounted between a pair of housings that sandwich a unit cell equipped with a negative electrode; cushioning material, vibration isolator; wire coating material; industrial belts; It is suitably used as tubes / hoses; sheets; etc.
  • 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 around a fuel tank such as a fuel hose, a filler neck hose, a vent hose, a paper hose, and an oil hose. 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 acrylic rubber 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, and a screw type extruder (not shown).
  • 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 a sulfuric acid-based emulsifier are mixed with a monomer component for forming acrylic rubber, emulsified while being appropriately stirred with a stirrer, and emulsified by emulsion polymerization in the presence of a polymerization catalyst.
  • a polymer 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 an aqueous sodium salt solution as a coagulant and coagulating it.
  • a method of adding the emulsion polymerization solution to the stirring magnesium salt aqueous solution is adopted. That is, a hydrous crumb is generated by filling the stirring tank 30 of the coagulation device 3 with an aqueous sodium salt solution and adding and contacting the aqueous emulsion solution with the emulsion polymerization solution to coagulate the emulsion polymerization solution.
  • the heating unit 31 of the coagulation device 3 is configured to heat the sodium salt aqueous solution 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 aqueous sodium salt solution 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 coagulation device 3 is configured to stir the sodium salt aqueous solution 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 sodium salt aqueous solution by rotating around the rotation axis by the rotational power of the motor 32 in the sodium salt aqueous solution 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 stirring blade 33 is operated by the drive control unit so that the stirring number of the sodium salt aqueous solution is usually in the range of 100 rpm or more, preferably 200 to 1,000 rpm, more preferably 300 to 900 rpm, and particularly preferably 400 to 800 rpm. Rotation is controlled.
  • the peripheral speed of the sodium salt aqueous solution 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 so as to be. Further, the drive control unit sets the upper limit of the peripheral speed of the sodium salt aqueous solution to be 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 stirring blade 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 can be effectively reduced by mixing the water-containing crumbs generated in the solidifying device 3 with a large amount of water and cleaning.
  • the heating unit 41 of the cleaning device 4 is configured to heat the inside of the cleaning tank 40. Further, the temperature control unit of the cleaning device 4 controls the temperature inside the cleaning tank 40 by controlling the heating operation by the heating unit 41 while monitoring the temperature inside the cleaning tank 40 measured by the thermometer. It is configured. As described above, the temperature of the washing water in the washing tank 40 is usually controlled to be in the range of 40 ° C. or higher, preferably 40 to 100 ° C., more preferably 50 to 90 ° C., and most preferably 60 to 80 ° C. To.
  • the water-containing crumb washed by the washing device 4 is supplied to the screw type extruder 5 that performs the dehydration step and the drying step. At this time, it is preferable that the water-containing crumb after cleaning is supplied to the screw type extruder 5 through a drainer 43 capable of separating free water.
  • a drainer 43 capable of separating free water.
  • a wire mesh, a screen, an electric sieve, or the like can be used.
  • the temperature of the water-containing crumb is preferably 40 ° C. or higher, more preferably 60 ° C. or higher.
  • the temperature of the water-containing crumb when supplied to the screw type extruder 5 is maintained at 60 ° C. or higher.
  • the temperature of the hydrous crumb may be 40 ° C. or higher, preferably 60 ° C. or higher when it is conveyed from the cleaning device 4 to the screw type extruder 5.
  • the screw type extruder 5 shown in FIG. 1 is configured to perform the processes related to the above-mentioned dehydration step and drying step.
  • a centrifuge, a squeezer, or the like may be used as the dehydrator for performing the treatment related to the dehydration step, and the treatment related to the drying step may be performed.
  • a hot air dryer, a vacuum dryer, an expander dryer, a kneader type dryer, or the like may be used as the dryer.
  • the screw type extruder 5 is configured to mold the dried rubber obtained through the dehydration step and the drying step into a predetermined shape and discharge it.
  • the screw type extruder 5 has a dehydration barrel portion 53 having a function as a dehydrator for dehydrating the hydrous crumb washed by the cleaning device 4, and a dryer having a function as a dryer for drying the hydrous crumb.
  • a barrel portion 54 is provided, and a die 59 having a molding function for forming a water-containing crumb is provided on the downstream side of the screw type extruder 5.
  • FIG. 2 shows a configuration of a specific example suitable for the screw type extruder 5 shown in FIG.
  • the above-mentioned dehydration / drying step can be suitably performed.
  • the screw type extruder 5 shown in FIG. 2 is a twin-screw type extruder / dryer provided with a pair of screws (not shown) in the barrel unit 51.
  • the screw type extruder 5 has a drive unit 50 that rotationally drives a pair of screws in the barrel unit 51.
  • the drive unit 50 is attached to the upstream end (left end in FIG. 2) of the barrel unit 51.
  • the screw type extruder 5 has a die 59 at the downstream end (right end in FIG. 2) of the barrel unit 51.
  • the barrel unit 51 has a supply barrel portion 52, a dehydration barrel portion 53, and a dry barrel portion 54 from the upstream side to the downstream side (from the left side to the right side in FIG. 2).
  • the supply barrel portion 52 is composed of two supply barrels, that is, a first supply barrel 52a and a second supply barrel 52b.
  • the dehydration barrel portion 53 is composed of three dehydration barrels, that is, a first dehydration barrel 53a, a second dehydration barrel 53b, and a third dehydration barrel 53c.
  • the drying barrel portion 54 includes eight drying barrels, that is, a first drying barrel 54a, a second drying barrel 54b, a third drying barrel 54c, a fourth drying barrel 54d, and a fifth drying barrel 54e. , A sixth dry barrel 54f, a seventh dry barrel 54g, and an eighth dry barrel 54h.
  • the barrel unit 51 is configured by connecting 13 divided barrels 52a to 52b, 53a to 53c, 54a to 54h from the upstream side to the downstream side.
  • the screw type extruder 5 individually heats the barrels 52a to 52b, 53a to 53c, 54a to 54h, and determines the water content crumbs in the barrels 52a to 52b, 53a to 53c, 54a to 54h, respectively. It has a heating means (not shown) for heating to a temperature.
  • the heating means includes a number corresponding to each barrel 52a to 52b, 53a to 53c, 54a to 54h.
  • a heating means for example, a configuration is adopted in which high-temperature steam is supplied from the steam supply means to the steam distribution jackets formed in the barrels 52a to 52b, 53a to 53c, 54a to 54h. It is not limited to this.
  • the screw type extruder 5 has a temperature control means (not shown) that controls a set temperature of each heating means corresponding to each barrel 52a to 52b, 53a to 53c, 54a to 54h.
  • the number of supply barrels, dehydration barrels, and drying barrels that constitute each barrel portion 52, 53, 54 in the barrel unit 51 is not limited to the mode shown in FIG. 2, and the acrylic rubber to be dried is used.
  • the number can be set according to the water content of the water-containing crumb.
  • the number of supply barrels installed in the supply barrel portion 52 is, for example, 1 to 3.
  • the number of dehydration barrels installed in the dehydration barrel portion 53 is preferably, for example, 2 to 10, and more preferably 3 to 6, because dehydration of the water-containing crumb of the adhesive acrylic rubber can be efficiently performed.
  • the number of dry barrels installed in the dry barrel portion 54 is preferably, for example, 2 to 10, and more preferably 3 to 8.
  • the pair of screws in the barrel unit 51 are rotationally driven by a driving means such as a motor housed in the driving unit 50.
  • the pair of screws extend from the upstream side to the downstream side in the barrel unit 51, and by being rotationally driven, the water-containing crumbs supplied to the supply barrel portion 52 can be conveyed to the downstream side while being mixed. It has become like.
  • the pair of screws is preferably a biaxial meshing type in which the peaks and valleys are meshed with each other, whereby the dehydration efficiency and the drying efficiency of the hydrous crumb can be improved.
  • the rotation direction of the pair of screws may be the same direction or different directions, but from the viewpoint of self-cleaning performance, a type that rotates in the same direction is preferable.
  • the screw shape of the pair of screws is not particularly limited as long as it is a shape required for each barrel portion 52, 53, 54, and is not particularly limited.
  • the supply barrel portion 52 is an area for supplying the hydrous crumb into the barrel unit 51.
  • the first supply barrel 52a of the supply barrel portion 52 has a feed port 55 for supplying a water-containing crumb in the barrel unit 51.
  • the dehydration barrel portion 53 is a region for separating and discharging a liquid (serum water) containing a coagulant or the like from the hydrous crumb.
  • the first to third dehydration barrels 53a to 53c constituting the dehydration barrel portion 53 have dehydration slits 56a, 56b, and 56c for discharging the water content of the hydrous crumb to the outside, respectively.
  • a plurality of the dehydration slits 56a, 56b, 56c are formed in the dehydration barrels 53a to 53c, respectively.
  • the slit widths that is, the openings of the dehydration slits 56a, 56b, and 56c may be appropriately selected according to the usage conditions, and are usually 0.01 to 5 mm, so that the water-containing crumbs are less damaged and the water-containing crumbs have little loss. From the viewpoint of efficient dehydration, it is preferably 0.1 to 1 mm, and more preferably 0.2 to 0.6 mm.
  • the dehydration barrel portion 53 is suitable because it is possible to efficiently reduce the water content of the adhesive acrylic rubber by combining drainage and exhaust steam.
  • which of the first to third dehydration barrels 53a to 53c is used for drainage or exhaust steam may be appropriately set according to the purpose of use, but is usually manufactured.
  • the dehydration barrel portion 53 has four dehydration barrels
  • drainage may be performed by three dehydration barrels on the upstream side, and steam may be exhausted by one dehydration barrel on the downstream side.
  • steam may be exhausted by one dehydration barrel on the downstream side.
  • the set temperature of the dehydration barrel portion 53 is usually in the range of 60 to 150 ° C., preferably 70 to 140 ° C., more preferably 80 to 130 ° C., and is dehydrated in the drained state.
  • the set temperature of the dehydration barrel to be dehydrated is usually 60 ° C. to 120 ° C., preferably 70 to 110 ° C., more preferably 80 to 100 ° C.
  • the set temperature of the dehydration barrel to be dehydrated in the exhausted steam state is usually 100 to 150 ° C.
  • the temperature is preferably in the range of 105 to 140 ° C, more preferably 110 to 130 ° C.
  • the drying barrel portion 54 is a region where the hydrous crumb after dehydration is dried under reduced pressure.
  • the second dry barrel 54b, the fourth dry barrel 54d, the sixth dry barrel 54f, and the eighth dry barrel 54h are It has vent ports 58a, 58b, 58c, and 58d for degassing, respectively. Vent pipes (not shown) are connected to the vent ports 58a, 58b, 58c, and 58d, respectively.
  • Vacuum pumps (not shown) are connected to the ends of each vent pipe, and the operation of these vacuum pumps reduces the pressure inside the drying barrel portion 54 to a predetermined pressure.
  • the screw type extruder 5 has a pressure control means (not shown) that controls the operation of these vacuum pumps to control the degree of decompression in the drying barrel portion 54.
  • the degree of decompression in the dry barrel portion 54 may be appropriately selected, but as described above, it is usually set to 1 to 50 kPa, preferably 2 to 30 kPa, and more preferably 3 to 20 kPa.
  • the set temperature in the drying barrel portion 54 may be appropriately selected, but as described above, it is usually set to 100 to 250 ° C, preferably 110 to 200 ° C, and more preferably 120 to 180 ° C.
  • the set temperatures in all the dry barrels 54a to 54h may be approximated or different, but on the upstream side (dehydrated barrel portion). It is preferable to set the temperature on the downstream side (die 59 side) to a higher temperature than the temperature on the downstream side (53 side) because the drying efficiency is improved.
  • the die 59 is a mold arranged at the downstream end of the barrel unit 51 and has a discharge port having a predetermined nozzle shape.
  • the acrylic rubber dried in the drying barrel portion 54 is extruded into a shape corresponding to a predetermined nozzle shape by passing through the discharge port of the die 59.
  • the 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.
  • a breaker plate or wire mesh may or may not be provided between the screw and the die 59.
  • 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 and is supplied from the die 59. Extruded.
  • 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 are efficiently reduced. From the point of view, 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 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.
  • [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.
  • the content ratio of each monomer unit in the 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 in the acrylic rubber was measured by the following method. (1) The amount of carboxyl groups was calculated by dissolving acrylic rubber in acetone and performing potentiometric titration with a potassium hydroxide solution. (2) The amount of epoxy group was calculated by dissolving acrylic rubber 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 acrylic rubber 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 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 specific gravity of the acrylic rubber was measured according to the method A of JIS K6268 crosslinked rubber-density measurement.
  • 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 was measured according to JIS K6238-1: Oven A (volatile matter measurement) method.
  • the weight average molecular weight (Mw) and molecular weight distribution (Mz / Mw) of acrylic rubber are determined by adding lithium chloride at a concentration of 0.05 mol / L and 37% concentrated hydrochloric acid at a concentration of 0.01% to dimethylformamide as a solvent. It is an absolute molecular weight and an absolute molecular weight distribution measured by the GPC-MALS method using.
  • a multi-angle laser light scattering photometric meter (MALS) and a differential refractometer (RI) are incorporated into a GPC (Gel Permeation Chromatography) device, and the light scattering intensity and refraction of the molecular chain solution size-sorted by the GPC device are incorporated.
  • the molecular weight of the solute and its content were sequentially calculated and obtained by measuring the rate difference with the elution time.
  • the measurement conditions and measurement method by the GPC device are as follows.
  • the complex viscosity ⁇ of acrylic rubber is measured at a strain of 473% and a temperature dispersion (40 to 120 ° C.) at 1 Hz using a dynamic viscoelasticity measuring device “Rubber Process Analyzer RPA-2000” (manufactured by Alpha Technology). Then, the complex viscoelasticity ⁇ at each temperature was obtained.
  • the dynamic viscoelasticity at 60 ° C. is defined as the complex viscoelasticity ⁇ (60 ° C.)
  • the dynamic viscoelasticity at 100 ° C. is defined as the complex viscoelasticity ⁇ (100 ° C.).
  • the values of ° C.) / ⁇ (60 ° C.) and ⁇ (60 ° C.) / ⁇ (100 ° C.) were calculated.
  • the normal physical characteristics of acrylic rubber were evaluated according to the following criteria by measuring the breaking strength, 100% tensile stress and breaking elongation of the crosslinked product of acrylic rubber 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, 48.5 parts of ethyl acrylate, 29 parts of n-butyl acrylate, 21 parts of methoxyethyl acrylate, 1.5 parts of vinyl chloroacetate, and lauryl sulfate as an emulsifier. 0.709 parts of sodium salt and 1.82 parts of polyoxyethylene dodecyl ether (molecular weight 1500) were charged and stirred to obtain a monomer emulsion.
  • the above-mentioned emulsion was obtained in a 2% sodium sulfate aqueous solution (coagulant) heated to 80 ° C. and vigorously stirred (600 rpm: peripheral speed 3.1 m / s).
  • the polymer solution was heated to 80 ° C. and continuously added to solidify the polymer, and the mixture was 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%
  • the rate and Mooney viscosity (ML1 + 4,100 ° C.) were measured and shown in Table 2.
  • the value of "water content (%) after dehydration (drainage)" shown in the dehydration process column of Table 2 is the water content of the water content crumb immediately after drainage by the drainage type dehydration barrel (immediately before the exhaust steam type dehydration barrel). ..
  • the obtained rubber composition 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 a water resistance test and a normal physical property evaluation were performed, and the results are shown in Table 2.
  • Example 2 The monomer component was changed to 98.5 parts of ethyl acrylate and 1.5 parts of vinyl chloroacetate, and the temperature of the first dehydration barrel of the screw type extruder was set to 100 ° C and the temperature of the second dehydration barrel was set to 120 ° C.
  • Acrylic rubber is carried out in the same manner as in Example 1 except that the water content of the water-containing crumb after draining in the first dehydration barrel is changed to 30%, and drainage is performed only in the first dehydration barrel. (B) was obtained and each characteristic was evaluated. The results are shown in Table 2.
  • Example 3 Acrylic was carried out in the same manner as in Example 2 except that the monomer component was changed to 43 parts of ethyl acrylate, 25 parts of n-butyl acrylate, 26 parts of methoxyethyl acrylate, 2 parts of acrylonitrile and 4 parts of allyl glycidyl ether.
  • the rubber (C) was obtained and each characteristic (the compounding agent was replaced with "formulation 2") was evaluated. The results are shown in Table 2.
  • Example 4 Examples except that the monomer component was changed to 4.5 parts of ethyl acrylate, 64.5 parts of n-butyl acrylate, 39.5 parts of methoxyethyl acrylate, and 1.5 parts of mono-n-butyl fumarate.
  • Acrylic rubber (D) was obtained in the same manner as in No. 2, and each characteristic (the compounding agent was changed to "formulation 3") was evaluated. The results are shown in Table 2.
  • Example 5 Example 2 except that the monomer component is changed to 42.2 parts of ethyl acrylate, 35 parts of n-butyl acrylate, 20 parts of methoxyethyl acrylate, 1.5 parts of acrylonitrile, and 1.3 parts of vinyl chloroacetate.
  • Acrylic rubber (E) was obtained and each characteristic was evaluated. The results are shown in Table 2.
  • the binding unit derived from at least one (meth) acrylic acid ester selected from the group consisting of the (meth) acrylic acid alkyl ester and the (meth) acrylic acid alkoxyalkyl ester of the present invention 70 to 99.9% by weight of the binding unit derived from at least one (meth) acrylic acid ester selected from the group consisting of the (meth) acrylic acid alkyl ester and the (meth) acrylic acid alkoxyalkyl ester of the present invention. , 0.1 to 10% by weight of the bonding unit derived from the reactive group-containing monomer, and 0 to 20% by weight of the bonding unit derived from other monomers, and the ash content is 0.15% by weight.
  • the total amount of sodium and sulfur in the ash is 60% by weight or more
  • the ratio of sodium to sulfur ([Na] / [S]) is in the range of 0.5 to 2.5 by weight
  • E) is remarkably excellent in processability and water resistance while maintaining excellent normal physical properties including breaking strength (Examples 1 to 5).
  • the acrylic rubbers (A) to (G) produced under the conditions of Examples, Comparative Examples and Reference Examples of the present application are all weight average molecular weights (Mw) of absolute molecular weights measured by GPC-MALS. ) Exceeds 1 million, and the ratio (Mz / Mw) of the z average molecular weight (Mz) and the weight average molecular weight (Mw) of the absolute molecular weight distribution that emphasizes the high molecular weight region measured by GPC-MALS is 1. Since it far exceeds 3, it can be seen that the normal physical properties including the breaking strength are excellent (Examples 1 to 5, Comparative Example 1 and Reference Example 1).
  • sodium (Na) was obtained by performing the coagulation method and the washing method by the method of Reference Example 1 as compared with Comparative Example 1. It can be seen that the total amount (Na + S) of and sulfur (S) has not changed, but the amount of sodium (Na) has decreased and the Na / S ratio has decreased. This is because the coagulant (sodium sulfate: Na 2 SO 4 : Na ratio is large) used by performing the coagulation and washing method of Reference Example 1 is almost removed, but the emulsifier (sodium lauryl sulfate: NaC 12 H 25 SO) is removed. It is presumed that sodium (Na) and sulfur (S) derived from 4 ) are contained in the hydrous crumb and cannot be sufficiently removed by washing.
  • the ash content in the acrylic rubber was 0.1% by weight or less and sodium was obtained by performing a solidification reaction in the same manner as in Reference Example 1, washing twice with warm water, and then dehydrating and drying with a screw type extruder. It can be seen that the sulfur ratio becomes acrylic rubber focused in a specific range, and the water resistance is remarkably improved while maintaining the strength characteristics (Examples 1 to 5). Further, it can be seen that the gel amount of the methyl ethyl ketone insoluble content, which was 60% by weight or more, is almost eliminated by dehydration drying with a screw type extruder, and the processability of acrylic rubber is improved (Comparative Examples with Examples 1 to 5). 1 and comparison with Reference Example 1).
  • Example 6 A water-containing crumb (water-containing crumb temperature 65 ° C.) that has been emulsion-polymerized, coagulated, and washed in the same manner as in Example 1 is supplied to a screw-type extruder having a substantially rectangular die, and dehydrated and dried under the same conditions as in Example 1.
  • a sheet-shaped dry rubber having a width of 300 mm and a thickness of 10 mm was extruded.
  • a sheet-shaped dry rubber is cooled at a cooling rate of 200 ° C./hr to obtain a sheet-shaped acrylic rubber (H) using a transport-type cooling device directly connected to a screw-type extruder, and then cooled to 50 ° C. Then, it was cut with a cutter and laminated so as to have 20 parts (20 kg) before the temperature became 40 ° C. or lower to obtain a bale-shaped acrylic rubber (H).
  • Tg glass transition temperature
  • the sheet shape and veil shape are the same and the same as the corresponding acrylic rubber (A). there were.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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US17/626,613 US20220389141A1 (en) 2019-07-19 2020-06-05 Acrylic rubber excellent in water resistance
CN202080049236.8A CN114080402B (zh) 2019-07-19 2020-06-05 耐水性优异的丙烯酸橡胶
KR1020227000539A KR102779954B1 (ko) 2019-07-19 2020-06-05 내수성이 우수한 아크릴 고무
JP2021534588A JP7424381B2 (ja) 2019-07-19 2020-06-05 耐水性に優れるアクリルゴム
EP20842946.4A EP4001317A4 (en) 2019-07-19 2020-06-05 ACRYLIC RUBBER WITH SUPERIOR WATER RESISTANCE

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WO2021261214A1 (ja) * 2020-06-23 2021-12-30 日本ゼオン株式会社 バンバリー加工性に優れるアクリルゴムベール

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WO2021261214A1 (ja) * 2020-06-23 2021-12-30 日本ゼオン株式会社 バンバリー加工性に優れるアクリルゴムベール

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CN114080402B (zh) 2024-02-27
KR102779954B1 (ko) 2025-03-10
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