WO2021246515A1 - ロール加工性とバンバリー加工性に優れるアクリルゴムベール - Google Patents

ロール加工性とバンバリー加工性に優れるアクリルゴムベール Download PDF

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WO2021246515A1
WO2021246515A1 PCT/JP2021/021347 JP2021021347W WO2021246515A1 WO 2021246515 A1 WO2021246515 A1 WO 2021246515A1 JP 2021021347 W JP2021021347 W JP 2021021347W WO 2021246515 A1 WO2021246515 A1 WO 2021246515A1
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acrylic rubber
weight
rubber
veil
acrylic
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PCT/JP2021/021347
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English (en)
French (fr)
Japanese (ja)
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浩文 増田
孝文 川中
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日本ゼオン株式会社
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Priority to JP2022528911A priority Critical patent/JPWO2021246515A1/ja
Priority to CN202180058139.XA priority patent/CN116057081A/zh
Priority to KR1020227040352A priority patent/KR20230022162A/ko
Publication of WO2021246515A1 publication Critical patent/WO2021246515A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical

Definitions

  • the present invention relates to an acrylic rubber bale, a method for producing the same, a rubber mixture, and a rubber crosslinked product.
  • the present invention relates to an excellent acrylic rubber veil, a method for producing the same, a rubber mixture containing the acrylic rubber veil, and a rubber crosslinked product obtained by cross-linking the acrylic rubber veil.
  • 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. 2019/188709 pamphlet
  • a monomer component composed of ethyl acrylate, butyl acrylate, methoxyethyl acrylate and monobutyl fumarate, water and sodium lauryl sulfate, and the pressure is reduced.
  • sodium aldehyde sulfoxylate and cumenhydroperoxide which is an organic radical generator, are added to start emulsion polymerization at normal pressure and normal temperature, and the polymerization conversion rate becomes 95% by weight.
  • the acrylic rubber obtained by this method has a problem that the roll processability and the Banbury processability are extremely inferior, and the storage stability and the water resistance are also inferior. Further, Patent Document 1 does not describe that the obtained acrylic rubber is veiled.
  • Patent Document 2 Japanese Unexamined Patent Publication No. 1-135811 describes a monomer component composed of ethyl acrylate, caprolactone-added acrylic acid ester, cyanoethyl acrylate and vinyl chloroacetate, and n-dodecyl mercaptan as a chain transfer agent. 1/4 amount of the monomer mixture is emulsified with sodium lauryl sulfate, polyethylene glycol nonylphenyl ether and distilled water, and sodium sulfite and ammonium persulfate as an inorganic radical generator are added to initiate polymerization, and the temperature is 60.
  • the remaining monomer mixture and the 2% ammonium persulfate aqueous solution were added dropwise at ° C for 2 hours, and the latex having a polymerization conversion rate of 96 to 99%, in which polymerization was continued for another 2 hours after the addition, was added to the sodium chloride aqueous solution at 80 ° C.
  • a method of producing acrylic rubber by solidifying, washing thoroughly with water, and then drying to produce acrylic rubber and cross-linking with sulfur is disclosed.
  • the acrylic rubber obtained by this method has problems that the roll processability and the Banbury processability are not sufficient, and the storage stability, the strength characteristics of the crosslinked product, and the water resistance are inferior.
  • Patent Document 3 Japanese Unexamined Patent Publication No. 2018-168343
  • a monomer component composed of ethyl acrylate, butyl acrylate and monobutyl fumarate, pure water, sodium lauryl sulfate, polyethylene glycol monostearate and a chain transfer agent.
  • a monomeric emulsion consisting of n-dodecyl mercaptan was prepared, and then a part of the monomeric emulsion and pure water were added to the polymerization reaction tank and cooled to 12 ° C., and then the rest of the monomeric emulsion was cooled.
  • Patent Document 4 Japanese Unexamined Patent Publication No. 9-143229
  • a monomer mixture composed of ethyl acrylate, special acrylate and monochloroacetate, sodium lauryl sulfate as an emulsifier, n-octyl mercaptan as a chain transfer agent and water are reacted.
  • ammonium hydrogen sulfite and sodium persulfate as an inorganic radical generator were added to initiate the polymerization reaction, and the reaction was copolymerized at 55 ° C. for 3 hours at a reaction conversion rate of 93 to 96% to obtain acrylic rubber.
  • a method of manufacturing and cross-linking with sulfur is disclosed.
  • the Akuri rubber obtained by this method has a problem that the Banbury workability is not sufficient, and the strength characteristics and water resistance of the crosslinked product are inferior.
  • Patent Document 5 Japanese Unexamined Patent Publication No. 62-64809
  • at least one compound of acrylic acid alkyl ester and acrylic acid alkoxyalkyl ester is 50 to 99.9% by weight, and an unsaturated carboxylic having a radically reactive group.
  • Coweight of a monomer composition consisting of 0.1 to 20% by weight of a dihydrodicyclopentenyl group-containing ester of acid and 0 to 20% by weight of at least one of other monovinyl-based, monovinylidene-based and monovinylene-based unsaturated compounds.
  • the compound has a polystyrene-equivalent number average molecular weight (Mn) of 200,000 to 1.2 million using the tetrahydrofuran as a developing solvent, and the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn). ) Is 10 or less, and an acrylic rubber having excellent processability, compression set, tensile strength and capable of sulfur sulfurization is disclosed.
  • the number average molecular weight (Mn) is 200,000 to 1,000,000, preferably 200,000 to 1,000,000. If Mn is less than 200,000, the physical properties and processability of the vulcanized product are inferior, and if it exceeds 1.2 million, it is processed.
  • the properties are inferior and that the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) becomes large when it exceeds 10, which is not preferable.
  • Specific examples thereof include monomer components including ethyl acrylate and radical crosslinkable dihydrodicyclopentenyl acrylate, sodium lauryl sulfate as an emulsifier, potassium persulfate as an inorganic radical generator, and a molecular weight modifier.
  • Octyl thioglycolate and t-dodecyl mercaptan are added in varying amounts, with a number average molecular weight (Mn) of 53-1.15 million, a weight average molecular weight (Mw) of 354 to 6.26 million, and a weight average molecular weight (Mw) and a number average molecular weight.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mw weight average molecular weight
  • Mw weight average molecular weight
  • a production method is disclosed in which an acrylic rubber having a ratio (Mw / Mn) of 4.7 to 8 to (Mn) is polymerized, coagulated in an aqueous calcium chloride solution, washed thoroughly with water, and directly dried.
  • the obtained acrylic rubber has a large number average molecular weight (Mw) of 5 million, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.
  • the number average molecular weight (Mn) is as small as 200,000, and the ratio (Mw / Mn) of the quantity average molecular weight (Mw) to the number average molecular weight (Mn) is 17 and extremely. It is shown in the comparative examples of Examples that it becomes wider.
  • the acrylic rubber obtained by this method is inferior in compression-resistant permanent strain resistance and storage stability, and contains a radical-reactive group, so that an appropriate molecular weight distribution (appropriate molecular weight distribution in a polymerization reaction using a radical generator) ( Even if Mw / Mn) is obtained, there is also a problem that the molecular weight (Mw, Mn) is too large and complicated, and the Banbury processability and the roll processability are not sufficient.
  • the acrylic rubber obtained by this method is subjected to sulfur as a cross-linking agent and a vulcanization accelerator, kneaded with a roll, and then subjected to a 100 kg / cm 2 vulcanization press at 170 ° C.
  • cross-linking is required for a long time of 4 hours at 175 ° C, and the obtained cross-linked product is also inferior in compression-resistant permanent strain resistance, water resistance and strength characteristics, and also inferior in physical property change after thermal deterioration. There was a problem.
  • Patent Document 6 Japanese Unexamined Patent Publication No. 2006-3282319
  • a crumb slurry containing a crumb-like rubber polymer is obtained by contacting the polymer latex with a coagulating liquid.
  • a method for producing a rubber polymer which comprises a dehydration step of removing water from the material to obtain a crumb-shaped rubber polymer and a step of heating and drying the crumb-shaped rubber polymer from which the water has been removed. , It is described that it is introduced into a baler in the form of flakes, compressed and veiled.
  • an unsaturated nitrile-conjugated diene copolymer latex obtained by emulsification polymerization is specifically shown, and an ethyl acrylate / n-butyl acrylate copolymer and an ethyl acrylate / It has been shown that it can be applied to a copolymer composed only of an acrylate such as an n-butyl acrylate / 2-methoxyethyl acrylate copolymer.
  • acrylic rubber composed only of acrylate has a problem that it is inferior in crosslinked rubber properties such as heat resistance and compression set resistance.
  • Patent Document 7 International Publication No. 2018/116828 describes ethyl acrylate and acrylic acid.
  • a monomer component consisting of n-butyl and mono-butyl fumarate is emulsified with sodium lauryl sulfate as an emulsifier, polyethylene glycol monostearate, and water, and cumenehydroperoxide, which is an organic radical generator, is added.
  • Acrylic rubber latex emulsion-polymerized until the polymerization conversion rate reaches 95% is added to an aqueous solution of magnesium sulfate and a polymer flocculant dimethylamine-ammonia-epichlorohydrin polycondensate, and then stirred at 85 ° C.
  • a method is disclosed in which a crumb slurry is generated, and then the crumb slurry is washed once with water and then passed through a 100-mesh wire net in its entirety to capture only the solid content and recover the crumb-shaped acrylic rubber. According to this method, it is described that the obtained hydrous crumb is dehydrated by centrifugation or the like, dried at 50 to 120 ° C.
  • Patent Document 8 Japanese Patent No. 3599962 contains radically reactive unsaturated groups having different reactivity from 95 to 99.9% by weight of alkyl acrylate or alkoxyalkyl acrylate.
  • acrylic rubber compositions which are composed of a reinforcing filler and an organic peroxide-based sulfide and have excellent extrusion processability such as extrusion speed, die well, and surface skin.
  • the acrylic rubber having a very small gel content used here is an acrylic rubber having a high gel content (60%) obtained in a normal acidic region (prepolymerization pH 4, post-polymerization pH 3.4). On the other hand, it is obtained by adjusting the pH of the polymerization solution to 6 to 8 with sodium hydrogen carbonate or the like. Specifically, after adding water, sodium lauryl sulfate and polyoxyethylene nonylphenyl ether, sodium carbonate and boric acid as emulsifiers and adjusting the temperature to 75 ° C., t-butyl hydroperoxide and longalit, which are organic radical generators, are used.
  • Ethylenediamine disodium tetraacetate and ferrous sulfate were added (pH at this time was 7.1), and then the monomer components of ethyl acrylate and allyl methacrylate were added dropwise to carry out emulsion polymerization, and the obtained emulsion ( pH7) is salted using an aqueous sodium sulfate solution, washed with water and dried to obtain an acrylic rubber.
  • acrylic rubber containing (meth) acrylic acid ester as a main component decomposes in the neutral to alkaline region, and even if the processability is improved, there is a problem that the storage stability and strength characteristics are inferior, and the roll processability is also good. There is also a problem that the Banbury workability, the crosslinkability and the compression resistance permanent strain property are inferior.
  • Patent Document 9 International Publication No. 2018/143101 pamphlet
  • a (meth) acrylic acid ester and an ion-crosslinkable monomer are emulsion-polymerized and have a complex viscosity at 100 ° C. ([ ⁇ ] 100 ° C.). Is 3,500 Pa ⁇ s or less, and the ratio of the complex viscosity at 60 ° C. ([ ⁇ ] 60 ° C.) to the complex viscosity at 100 ° C.
  • the amount of gel which is a THF (tetrahydrofuran) insoluble component of acrylic rubber used in the same technique, is 80% by weight or less, preferably 5 to 80% by weight, and preferably exists as much as possible in the range of 70% or less. It is stated that when the amount of gel is less than 5%, the extrudability deteriorates.
  • the weight average molecular weight (Mw) of the acrylic rubber used is 200,000 to 1,000,000, and when the weight average molecular weight (Mw) exceeds 1,000,000, the viscoelasticity of the acrylic rubber is high. It is stated that it is too much to be preferable. However, there is no description of a method for improving workability such as roll workability and Banbury.
  • the present invention has been made in view of the actual conditions of the prior art, is excellent in both roll workability and rubbery workability, and has short-time crosslinkability, water resistance, strength characteristics, and compression set resistance. It is an object of the present invention to provide an acrylic rubber veil having excellent properties, a method for producing the same, a rubber mixture containing the acrylic rubber veil, and a rubber crosslinked product obtained by cross-linking the acrylic rubber veil.
  • the present inventors have a molecular weight distribution (Mw / Mn) in which the acrylic rubber veil has at least one reactive group selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom. ) Is made of the specified acrylic rubber, the amount of ash and the amount of gel are within the specified range, and the variation in the amount of gel in the acrylic rubber veil is controlled, so that the roll workability and the bumperry workability are excellent, and It has been found that it is highly excellent in short-time cross-linking property, water resistance, strength property and compression set resistance property.
  • the present inventors particularly correlate with BIT (Black Corporation Time) at the time of Banbury processing, and the gel of the specific solvent insoluble content in the acrylic rubber veil. It was found that if the amount varies, the solventy workability deteriorates, and by controlling the gel amount variation in those acrylic rubber veils, the solventy workability can be significantly improved.
  • BIT Black Corporation Time
  • the present inventors have found that the smaller the amount of gel in the specific solvent-insoluble portion of the acrylic rubber veil, the better the Banbury processability.
  • the amount of the insoluble content of the specific solvent in the acrylic rubber veil is generated during the polymerization reaction, and in particular, when the polymerization conversion rate is increased in order to improve the strength characteristics, it rapidly increases and is difficult to control, but in the latter half of the polymerization reaction. It can be suppressed to some extent by emulsion polymerization in the presence of a chain transfer agent, and acrylic rubber is melt-mixed in a screw-type twin-screw extruder in a screw-type twin-screw extruder in a state where the gel amount of the specific solvent-insoluble component that has increased rapidly increases. It was found that by smelting and drying, the gel amount of the specific solvent insoluble matter that increased rapidly disappeared, and the Banbury workability could be significantly improved without impairing the strength characteristics of the acrylic rubber veil.
  • the present inventors have a great relationship with the roll processability in terms of the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the acrylic rubber constituting the acrylic rubber veil, and the weight average molecular weight. It has been found that the larger the ratio (Mw / Mn) of (Mw) to the number average molecular weight (Mn), the better the roll processability. Although it was difficult to produce acrylic rubber having a large ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), the present inventors initially added a chain transfer agent. It was found that this can be achieved by adding it in batches during the polymerization without using it.
  • the present inventors also dried the hydrous crumb produced by the solidification reaction with a high share using a screw type twin-screw extruder to obtain the weight average molecular weight (Mw) without impairing the number average molecular weight (Mn). It was found that the ratio (Mw / Mn) to the number average molecular weight (Mn) was greatly widened and the roll processability was further improved.
  • the present inventors have found that the amount of ash in the acrylic rubber veil has a great influence on the water resistance. It is difficult to reduce the ash content of acrylic rubber, which uses a large amount of emulsifier and coagulant in emulsion polymerization, but the hydrous crumb produced by coagulation by a specific method has cleaning efficiency in warm water and ash removal by dehydration. It has been found that the efficiency is significantly improved, and as a result, the water resistance of the acrylic rubber veil can be significantly improved.
  • the present inventors also have excellent water resistance of the acrylic rubber veil and a mold when a specific emulsifier is used in the emulsion polymerization of acrylic rubber, or when a specific coagulant is used when the emulsion polymerization solution is coagulated. It was found that the releasability to the like is significantly enhanced.
  • the present inventors also have a specific reactive group in which the acrylic rubber veil can react with a cross-linking agent such as a carboxyl group, an epoxy group, and a chlorine atom, whereby the cross-linking property and compression-resistant permanent strain of the acrylic rubber bale cross-linked product are obtained.
  • a cross-linking agent such as a carboxyl group, an epoxy group, and a chlorine atom
  • the acrylic rubber constituting the acrylic rubber veil has such a specific reactive group and has a weight average molecular weight (Mw) or a ratio of z average molecular weight (Mz) to weight average molecular weight (Mw) (Mz / Mw). It has been found that when is within a specific range, the normal physical properties including the crosslinkability, the compression resistance permanent strain property and the strength property of the crosslinked product of the acrylic rubber veil are highly balanced.
  • the present inventors are sufficient to use the crosslink used for the GPC measurement of the radically reactive acrylic rubber copolymerized with the above-mentioned prior art ethyl acrylate, dihydrodicyclopentenyl acrylate and the like. It was not possible to measure each molecular weight and molecular weight distribution neatly and reproducibly because it could not be dissolved in It has been found that by specifying the value, it is possible to highly balance the roll processability and cross-linking property of acrylic rubber, the strength property of the cross-linked product, and the compression resistance permanent strain property.
  • the present inventors further improve the roll processability, Banbury processability, cross-linking property, water resistance, strength property, compression set resistance property, and the like of the acrylic rubber veil. It was found that the storage stability can be significantly improved while maintaining the storage stability.
  • Acrylic rubber having a specific reactive group such as a carboxyl group is sticky and difficult to remove once air is entrained, and a crumb-shaped acrylic rubber obtained by directly drying a hydrous crumb entrains a large amount of air (specific gravity). It became smaller) and the storage stability was deteriorated.
  • the present inventors can remove some air by compressing the crumb-shaped acrylic rubber with a high-pressure veil or the like to form a veil, and can improve the storage stability of the acrylic rubber veil.
  • Acrylic rubber veil with almost no air (high specific density) and significantly improved storage stability can be manufactured by extruding and drying under reduced pressure with a twin-screw extruder and extruding in the form of an air-free sheet and laminating. I found.
  • the present inventors have also found that the specific gravity including the content of such air can be measured according to the method A of JIS K6268 crosslinked rubber-density measurement using the difference in buoyancy.
  • the present inventors also increase the cooling rate after drying to stabilize the Mooney scorch without impairing the roll processability, bumper processability, water resistance, strength characteristics, compression permanent strain resistance, and other characteristics of the acrylic rubber veil. We found that we could significantly improve our sexuality.
  • the present inventors also started emulsion polymerization in the presence of a redox catalyst composed of an inorganic radical generator such as potassium persulfate and a reducing agent after emulsifying a specific monomer component with water and an emulsifying agent.
  • a redox catalyst composed of an inorganic radical generator such as potassium persulfate and a reducing agent after emulsifying a specific monomer component with water and an emulsifying agent.
  • the present inventors can also reduce the ash content and improve the water resistance of the acrylic rubber veil by squeezing (dehydrating) the water-containing crumb after washing to a specific water content, and emulsion polymerization to the coagulating liquid in the coagulation step. It was found that the cleaning efficiency of the hydrous crumb generated by adding a liquid to generate the hydrous crumb with warm water and the ash removal efficiency at the time of dehydration can be remarkably improved, and the water resistance of the obtained acrylic rubber veil can be remarkably improved. rice field.
  • the present inventors rapidly increase the amount of gel insoluble in a specific solvent (methyl ethyl ketone) and deteriorate the Banbury processability of the acrylic rubber veil produced, but it is produced in the coagulation step.
  • a specific solvent methyl ethyl ketone
  • After washing the water-containing crumb it is melt-kneaded and dried in a specific extruder and dryer in a state where it is substantially free of water (moisture content is less than 1% by weight), so that the specific solvent insoluble rapidly increases during emulsion polymerization. It was found that the amount of gel in the amount disappeared, the amount of gel in the acrylic rubber was small, and the amount of gel was almost eliminated, and the solventy processability of the acrylic rubber veil could be significantly improved.
  • the present inventors further melt and knead acrylic rubber under a high share condition using a specific extruder dryer and dry it to roll processability, Banbury processability, short-time cross-linking property, strength characteristics and resistance. It has been found that acrylic rubber having further improved compression set characteristics can be produced.
  • the present inventors further, in the rubber mixture containing the acrylic rubber veil, the filler and the cross-linking agent of the present invention, by blending carbon black or silica as the filler, the roll processability, the Banbury processability and the short time can be achieved. It has been found that the crosslinked product is excellent in crosslinkability, and the crosslinked product is highly excellent in water resistance, strength characteristics and compression set resistance.
  • the present inventors also preferably use an organic compound, a polyvalent compound or an ionic cross-linking compound as the cross-linking agent, for example, an ionic reaction of an acrylic rubber veil such as an amine group, an epoxy group, a carboxyl group or a thiol group.
  • the present inventors have completed the present invention based on these findings.
  • the present invention has at least one reactive group selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom, and has a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) (Mn).
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • it is made of acrylic rubber having Mw / Mn) of 3.7 or more, the ash content is 0.2% by weight or less, the gel amount is 30% by weight or less, and the gel amount is arbitrarily sampled at multiple points to measure the variation.
  • An acrylic rubber veil is provided in which all of the above samplings measured in the range of (average value ⁇ 5)% by weight are contained.
  • the multi-point sampling is preferably 20-point sampling.
  • the gel amount is preferably the insoluble amount of methyl ethyl ketone.
  • the number average molecular weight (Mn) is preferably in the range of 100,000 to 500,000.
  • the weight average molecular weight (Mw) is preferably in the range of 1 million to 3.5 million.
  • the total amount of sodium, magnesium, calcium, phosphorus and sulfur in the ash is preferably 60% by weight or more.
  • the acrylic rubber veil of the present invention preferably has a specific gravity of 0.9 or more.
  • the acrylic rubber veil of the present invention it is preferably emulsion-polymerized using a phosphoric acid ester salt or a sulfate ester salt as an emulsifier.
  • the emulsion polymerized solution is coagulated by using an alkali metal salt or a metal salt of Group 2 of the periodic table as a coagulant and dried.
  • the acrylic rubber veil of the present invention it is preferable that the acrylic rubber veil is melt-kneaded and dried after solidification, and the melt-kneading and drying are carried out in a state of substantially no moisture. It is preferable that the melt kneading and drying are carried out under reduced pressure. Further, in the acrylic rubber veil of the present invention, it is preferable that the acrylic rubber veil is cooled at a cooling rate of 40 ° C./hr or more by the above-mentioned melt kneading and drying.
  • an acrylic rubber monomer component containing a monomer containing at least one reactive group selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom is emulsion with water and an emulsifier.
  • the process of converting The polymerization reaction was started in the presence of a redox catalyst containing an inorganic radical generator and a reducing agent, and a chain transfer agent was added in batches during the polymerization to continue the polymerization until the polymerization conversion rate was 90% by weight or more.
  • Emulsion polymerization process and A coagulation step in which the obtained emulsion polymerization solution and the coagulation solution are brought into contact with each other to form a hydrous crumb, A cleaning process to clean the generated hydrous crumbs, A step of dehydrating the washed water-containing crumb 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 twin-screw extruder having a die at the tip.
  • a drying process that dries to less than 1% by weight in a drying barrel The molding process of extruding sheet-shaped dry rubber from the die, Laminating process of laminating extruded sheet-shaped dry rubber, A method for manufacturing an acrylic rubber veil including the above is provided.
  • the method for producing an acrylic rubber veil of the present invention is preferably the method for producing an acrylic rubber veil for producing the above acrylic rubber veil.
  • the contact between the emulsion polymerization solution and the coagulation solution in the coagulation step is performed by adding the emulsion polymerization solution to the coagulation solution.
  • the maximum torque of the screw type twin-screw extruder is 25 N ⁇ m or more.
  • the method for producing an acrylic rubber veil of the present invention it is preferable to carry out emulsion polymerization using a phosphate ester salt or a sulfate ester salt as an emulsifier in the emulsion polymerization step.
  • the polymerization solution produced in the emulsion polymerization step is coagulated by using an alkali metal salt or a metal salt of Group 2 of the periodic table as a coagulant and dried.
  • the polymerization solution produced in the emulsion polymerization step is added to an aqueous solution containing a coagulant containing an alkali metal salt or a metal salt of Group 2 of the periodic table and coagulated by stirring. Is preferable.
  • the polymerization solution produced in the emulsion polymerization step is brought into contact with a coagulant to coagulate, and then melt-kneaded and dried.
  • the melt kneading and drying are carried out in a state of substantially no moisture.
  • the above-mentioned melt kneading and drying are performed under reduced pressure.
  • the acrylic rubber veil of the present invention it is preferable to cool the acrylic rubber after melt kneading and drying at a cooling rate of 40 ° C./hr or more.
  • a rubber mixture containing the acrylic rubber veil, a filler and a cross-linking agent.
  • the filler is a reinforcing filler. Further, in the rubber mixture of the present invention, it is preferable that the filler is carbon blacks. Further, in the rubber mixture of the present invention, it is preferable that the filler is silica.
  • the cross-linking agent is an organic cross-linking agent. Further, in the rubber mixture of the present invention, it is preferable that the cross-linking agent is a polyvalent compound. Further, in the rubber mixture of the present invention, it is preferable that the cross-linking agent is an ionic cross-linking compound. Further, in the rubber mixture of the present invention, it is preferable that the cross-linking agent is an ionic cross-linking organic compound. Further, in the rubber mixture of the present invention, it is preferable that the cross-linking agent is a polyvalent ion organic compound.
  • At least the ion of the ion-crosslinkable compound, the ion-crosslinkable organic compound or the polyvalent ion organic compound as the cross-linking agent is selected from the group consisting of an amino group, an epoxy group, a carboxyl group and a thiol group. It is preferably one type of ionic reactive group.
  • the cross-linking agent is at least one polyvalent ion compound selected from the group consisting of a polyvalent amine compound, a polyvalent epoxy compound, a polyvalent carboxylic acid compound and a polyvalent thiol compound. preferable.
  • the content of the cross-linking agent is preferably in the range of 0.001 to 20 parts by weight with respect to 100 parts by weight of the rubber component.
  • the rubber mixture of the present invention preferably further contains an anti-aging agent. Further, in the rubber mixture of the present invention, it is preferable that the anti-aging agent is an amine-based anti-aging agent.
  • a method for producing a rubber mixture in which a rubber component containing the acrylic rubber veil, a filler and, if necessary, an antiaging agent are mixed, and then a cross-linking agent is mixed.
  • a rubber crosslinked product obtained by cross-linking the above rubber mixture is further provided.
  • the crosslinking of the rubber mixture is performed after molding.
  • the cross-linking of the rubber mixture is a primary cross-linking and a secondary cross-linking.
  • an acrylic rubber veil having highly excellent roll workability, Banbury workability, short-time crosslinking property, water resistance, strength property and compression set resistance property, an efficient manufacturing method thereof, and the acrylic rubber.
  • a high quality rubber mixture containing a veil and a rubber crosslinked product obtained by cross-linking the same are provided.
  • the acrylic rubber veil of the present invention has at least one reactive group selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom, and has a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) (Mn).
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • the ash content is 0.2% by weight or less
  • the gel amount is 30% by weight or less
  • the gel amount is arbitrarily sampled at multiple points to measure the variation.
  • the value of is characterized in that all of the above-mentioned samples measured within the range of the average value of ⁇ 5% by weight are included.
  • the acrylic rubber veil of the present invention is characterized by having at least one reactive group selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom.
  • the at least one reactive group selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom is not particularly limited, but is preferably an ionic reactive group involved in an ionic reaction, and more preferably an epoxy group.
  • it is a carboxyl group, particularly preferably a carboxyl group, it is suitable because it can highly improve the crosslinkability in a short time and the compression set resistance and water resistance of the crosslinked product.
  • the content of at least one reactive group selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom of the acrylic rubber veil of the present invention is not particularly limited and may be appropriately selected according to the purpose of use.
  • the reactive group itself is usually 0.001 to 5% by weight, preferably 0.01 to 3% by weight, more preferably 0.05 to 1% by weight, and particularly preferably 0.1 to 0% by weight. When it is in the range of 5% by weight, the workability and crosslinkability, and the strength characteristics, compression permanent strain resistance, oil resistance, cold resistance, and water resistance of the crosslinked product are highly balanced. Therefore, it is suitable.
  • the acrylic rubber veil having at least one reactive group selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom of the present invention is selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom in a post-reaction to acrylic rubber.
  • at least one reactive group may be introduced, an acrylic rubber obtained by copolymerizing a monomer containing the reactive group is preferable.
  • the monomer component of the acrylic rubber constituting the acrylic rubber veil of the present invention has at least one reactive group selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom, and simply constitutes an ordinary acrylic rubber.
  • (meth) acrylic acid ester selected from the group consisting of (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester, a carboxyl group, an epoxy group and a chlorine atom. It consists of a monomer containing at least one reactive group and, if necessary, other monomers copolymerizable.
  • (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 a (meth) acrylic having an alkyl having 1 to 8 carbon atoms.
  • An acid alkyl ester, more preferably a (meth) acrylic acid alkyl ester having an alkyl group having 2 to 6 carbon atoms is used.
  • the (meth) acrylic acid alkyl ester examples include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n- (meth) acrylic acid.
  • examples thereof include butyl, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and among these, ethyl (meth) acrylate, (meth). ) N-butyl acrylate is preferable, and ethyl acrylate and n-butyl acrylate are more preferable.
  • the (meth) acrylic acid alkoxyalkyl ester is not particularly limited, but usually has a (meth) acrylic acid alkoxyalkyl ester having 2 to 12 alkoxyalkyl groups, preferably a (meth) acrylic having 2 to 8 alkoxyalkyl groups.
  • An acid alkoxyalkyl ester, more preferably a (meth) acrylic acid alkoxy ester having an alkoxyalkyl group having 2 to 6 carbon atoms is used.
  • (meth) acrylate alkoxyalkyl ester examples include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, methoxybutyl (meth) acrylate, and (meth) acrylic.
  • examples thereof include ethoxymethyl acid, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate and the like.
  • methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and the like are preferable, and methoxyethyl acrylate and ethoxyethyl acrylate are more preferable.
  • At least one (meth) acrylic acid ester selected from the group consisting of these (meth) acrylic acid alkyl esters and (meth) acrylic acid alkoxyalkyl esters may be used alone or in combination of two or more. These proportions in the total components of the weight are usually 50-99.99% by weight, preferably 62-99.95% by weight, more preferably 74-99.9% by weight, particularly preferably 80-99.5% by weight. %, Most preferably in the range of 87 to 99% by weight, the acrylic rubber veil has highly excellent weather resistance, heat resistance and oil resistance.
  • the monomer containing at least one reactive group selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom is appropriately selected according to the purpose of use without any particular limitation, but is preferably an ionic reaction.
  • Short-term crosslinkability and compression-resistant permanent strain resistance of the crosslinked product when it is a reactive group of sex more preferably a monomer having a carboxyl group and / or an epoxy group, and more preferably a monomer having a carboxyl group. It is suitable because its properties and water resistance can be highly improved.
  • the monomer having a carboxyl group is not particularly limited, but an ethylenically unsaturated carboxylic acid can be preferably used.
  • the ethylenically unsaturated carboxylic acid include ethylenically unsaturated monocarboxylic acid, ethylenically unsaturated dicarboxylic acid, and ethylenically unsaturated dicarboxylic acid monoester, and among these, ethylenically unsaturated dicarboxylic acid monoester.
  • the ester can further enhance the compression resistance permanent strain property when the acrylic rubber veil is used as a rubber crosslinked product.
  • the ethylenically unsaturated monocarboxylic acid is not particularly limited, but an ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms is preferable, for example, acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, crotonic acid, and the like. Examples include cinnamic acid.
  • the ethylenically unsaturated dicarboxylic acid is not particularly limited, but is preferably an ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms, and examples thereof include butendionic acids such as fumaric acid and maleic acid, itaconic acid, and citraconic acid. Can be mentioned.
  • the ethylenically unsaturated dicarboxylic acid includes those existing as an anhydride.
  • the ethylenically unsaturated dicarboxylic acid monoester is not particularly limited, but is usually an ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms and an alkyl monoester having 1 to 12 carbon atoms, preferably 4 to 12 carbon atoms.
  • Examples thereof include ethylenically unsaturated dicarboxylic acid of 6 and an alkyl monoester having 2 to 8 carbon atoms, more preferably an alkyl monoester having 2 to 6 carbon atoms of butendionic acid having 4 carbon atoms.
  • ethylenically unsaturated dicarboxylic acid monoester examples include monomethyl fumarate, monoethyl fumarate, monon-butyl fumarate, monomethyl maleate, monoethyl maleate, monon-butyl maleate, monocyclopentyl fumarate, and fumaric acid.
  • Butendionic acid monoalkyl esters such as monocyclohexyl acid, monocyclohexenyl fumarate, monocyclopentyl maleate, monocyclohexyl maleate; monomethyl itaconate, monoethyl itaconate, monon-butyl itaconate, monocyclohexyl itaconate, etc. Examples thereof include monoalkyl esters; among these, mono n-butyl fumarate and mono n-butyl maleate are preferable, and mono n-butyl fumarate is particularly preferable.
  • Examples of the monomer having an epoxy group include an epoxy group-containing (meth) acrylic acid ester such as glycidyl (meth) acrylate; and an epoxy group-containing vinyl ether such as allyl glycidyl ether and vinyl glycidyl ether.
  • the monomer having a chlorine atom is not particularly limited, but for example, an unsaturated alcohol ester of a saturated carboxylic acid containing a chlorine atom, a (meth) acrylic acid chloroalkyl ester, and a (meth) acrylic acid chloroacyloxy.
  • Examples thereof include unsaturated monomers contained.
  • the unsaturated alcohol ester of the chlorine atom-containing saturated carboxylic acid include vinyl chloroacetate, vinyl 2-chloropropionate, and allyl chloroacetic acid.
  • Specific examples of (meth) acrylic acid chloroalkyl ester include (meth) acrylic acid chloromethyl, (meth) acrylic acid 1-chloroethyl, (meth) acrylic acid 2-chloroethyl, and (meth) acrylic acid 1,2-dichloroethyl. , (Meta) acrylic acid 2-chloropropyl, (meth) acrylic acid 3-chloropropyl, (meth) acrylic acid 2,3-dichloropropyl and the like.
  • (meth) acrylic acid chloroacyloxyalkyl 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 (chloroacetylcarbamoyloxy) alkyl ester include (meth) acrylic acid 2- (chloroacetylcarbamoyloxy) ethyl and (meth) acrylic acid 3- (chloroacetylcarbamoyloxy) propyl. Be done.
  • Specific examples of the chlorine atom-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.
  • chlorine atom-containing unsaturated ketone examples include 2-chloroethyl vinyl ketone, 3-chloropropyl vinyl ketone, 2-chloroethyl allyl ketone and the like.
  • chloromethyl group-containing aromatic vinyl compound examples include p-chloromethylstyrene, m-chloromethylstyrene, o-chloromethylstyrene, p-chloromethyl- ⁇ -methylstyrene and the like.
  • Specific examples of the chlorine atom-containing unsaturated amide include N-chloromethyl (meth) acrylamide.
  • Specific examples of the chloroacetyl group-containing unsaturated monomer include 3- (hydroxychloroacetoxy) propyl allyl ether and p-vinylbenzylchloroacetic acid ester.
  • the monomer containing at least one reactive group selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom is used alone or in combination of two or more, and is used in all the components of the monomer.
  • the proportion is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 6% by weight, particularly preferably 0.5 to 5% by weight, and most preferably 1 to 3%. It is in the range of% by weight.
  • any monomer copolymerizable with the above monomer can be used.
  • aromatic vinyl such as styrene, ⁇ -methylstyrene, divinylbenzene; ethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile; acrylamide-based monomers such as acrylamide and methacrylicamide; ethylene.
  • Olefin monomers such as propylene, vinyl acetate, ethyl vinyl ether, butyl vinyl ether and the like.
  • the ratio in the total components of the monomer is usually 0 to 40% by weight, preferably 0 to 30% by weight, and more preferably 0. It is suppressed to the range of about 20% by weight, particularly preferably 0 to 15% by weight, and most preferably 0 to 10% by weight.
  • the acrylic rubber constituting the acrylic rubber veil of the present invention has at least one reactive group selected from the group consisting of the above-mentioned carboxyl group, epoxy group and chlorine atom, and preferably the above-mentioned (meth) acrylic acid alkyl ester and the above-mentioned (meth) acrylic acid alkyl ester.
  • the bonding unit derived from at least one (meth) acrylic acid ester selected is usually 50 to 99.99% by weight, preferably 62 to 99.95% by weight, more preferably 74 to 99.9% by weight, and particularly preferably. Is in the range of 80 to 99.5% by weight, most preferably 87 to 99% by weight, and is derived from a monomer containing at least one reactive group selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom.
  • the bonding unit is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 6% by weight, particularly preferably 0.5 to 5% by weight, and most preferably 1.
  • the bond unit derived from other monomers is usually 0 to 40% by weight, preferably 0 to 30% by weight, more preferably 0 to 20% by weight, and particularly preferably 0 to 15% by weight. It is in the range of% by weight, most preferably 0 to 10% by weight.
  • the properties such as short-time cross-linking property, compression permanent strain resistance, weather resistance, heat resistance, and oil resistance of the acrylic rubber veil are highly balanced and suitable. ..
  • the number average molecular weight (Mn) of the acrylic rubber constituting the acrylic rubber veil of the present invention is not particularly limited, but is usually 100,000 to 500,000 (100,000 to 500,000), preferably 200,000.
  • Strength characteristics and compression resistance permanent strain characteristics are highly balanced and suitable.
  • the weight average molecular weight (Mw) of the acrylic rubber constituting the acrylic rubber veil of the present invention is not particularly limited and may be appropriately selected according to the purpose of use, but is usually 1,000,000 to 3,500,000. (1 million to 3.5 million), preferably 1200,000 to 3,000,000, more preferably 1,300,000 to 3,000,000, particularly preferably 1,500,000 to 2,500, 000, most preferably in the range of 1,900,000 to 2,100,000, the roll processability, strength characteristics, and compression resistance permanent strain characteristics of the acrylic rubber veil are highly balanced and suitable.
  • the z average molecular weight (Mz) of the acrylic rubber constituting the acrylic rubber veil of the present invention is not particularly limited and may be appropriately selected according to the purpose of use, but is usually 1,500,000 to 6,000,000. (1.5 million to 6 million), preferably 2,000,000 to 5,000,000, more preferably 2,500,000 to 4,500,000, particularly preferably 3,000,000 to 4,000, When the range is in the range of 000, the roll workability, the Banbury workability, the strength property, and the compression resistance permanent strain property of the acrylic rubber veil are highly balanced and suitable.
  • the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the acrylic rubber constituting the acrylic rubber veil of the present invention is 3.7 or more, preferably 3.8 or more, more preferably 3.8 or more. It is 4 or more, particularly preferably 4.5 or more, and most preferably 4.7 or more. If the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the acrylic rubber constituting the acrylic rubber veil of the present invention is excessively small, the roll processability of the acrylic rubber veil is inferior, which is not preferable.
  • the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the acrylic rubber constituting the acrylic rubber of the present invention is also usually 3.7 to 6.5, preferably 3.8.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the acrylic rubber constituting the acrylic rubber of the present invention is also usually 3.7 to 6.5, preferably 3.8.
  • the ratio (Mz / Mw) of the z average molecular weight (Mz) and the weight average molecular weight (Mw) of the acrylic rubber constituting the acrylic rubber veil of the present invention is 1.8 or more, preferably 1.8 to 2.4. More preferably, when it is in the range of 1.8 to 2, the roll workability and the molecular weight workability can be highly improved without impairing the strength characteristics of the acrylic rubber veil, which is preferable.
  • the molecular weight (Mn, Mw, Mz) and molecular weight distribution (Mw / Mn, Mz / Mw) of the acrylic rubber constituting the acrylic rubber veil of the present invention are the absolute molecular weight and the absolute molecular weight distribution measured by the GPC-MALS method.
  • the "GPC-MALS method” has the following contents.
  • the GPC (gel permeation chromatography) method is a kind of liquid chromatography in which separation is performed based on the difference in molecular size.
  • a multi-angle laser light scattering photometric meter (MALS) and a differential refractometer (RI) are incorporated into this device, and the light scattering intensity and refractive index difference of the molecular chain solution size-separated by the GPC device are measured with the melting time.
  • MALS multi-angle laser light scattering photometric meter
  • RI differential refractometer
  • the measuring solvent of the GPC-MALS method for measuring the molecular weight and the molecular weight distribution is not particularly limited as long as the acrylic rubber veil of the present invention can be dissolved and measured, but a dimethylformamide-based solvent is preferable.
  • the dimethylformamide-based solvent used is not particularly limited as long as it contains dimethylformamide as a main component, but 100% of dimethylformamide or the ratio of dimethylformamide in the dimethylformamide-based solvent is 90% by weight, preferably 90% by weight. It is 95% by weight, more preferably 97% by weight or more.
  • the compound to be added to dimethylformamide is not particularly limited, but in the present invention, lithium chloride is added to dimethylformamide at a concentration of 0.05 mol / L and 37% concentrated hydrochloric acid is added at a concentration of 0.01%, respectively.
  • Dimethylformamide is suitable.
  • the glass transition temperature (Tg) of the acrylic rubber constituting the acrylic rubber veil of the present invention may be appropriately selected depending on the intended use of the acrylic rubber, but is usually 20 ° C. or lower, preferably 10 ° C. or lower, more preferably. It is suitable because it has excellent workability and cold resistance when the temperature is 0 ° C. or lower.
  • the lower limit of the glass transition temperature (Tg) of acrylic rubber is not particularly limited, but is usually ⁇ 80 ° C. or higher, preferably ⁇ 60 ° C. or higher, and more preferably ⁇ 40 ° C. or higher.
  • the acrylic rubber veil of the present invention has at least one reactive group selected from the group consisting of the carboxyl group, the epoxy group and the chlorine atom, preferably made of the acrylic rubber, and has an ash content, a gel amount and a gel amount. It is characterized by specific variations.
  • the ash content of the acrylic rubber veil of the present invention is 0.2% by weight or less, preferably 0.15% by weight or less, more preferably 0.13% by weight or less, and when it is in this range, water resistance and strength characteristics. And workability is highly balanced and suitable.
  • the lower limit of the ash content of the acrylic rubber veil of the present invention is not particularly limited and may be appropriately selected depending on the intended use, but is usually 0.0001% by weight or more, preferably 0.0005% by weight or more. When it is preferably 0.001% by weight or more, particularly preferably 0.005% by weight or more, and most preferably 0.01% by weight or more, the metal adhesion of the rubber is reduced and the workability is excellent. be.
  • the ash content is usually 0.0001 to 0.5% by weight, preferably 0.0005 to 0.3. It is in the range of% by weight, more preferably 0.001 to 0.2% by weight, particularly preferably 0.005 to 0.15% by weight, and most preferably 0.01 to 0.13% by weight.
  • the total amount of sodium, magnesium, calcium, phosphorus and sulfur in the ash content of the acrylic rubber veil of the present invention may be appropriately selected according to the purpose of use without any particular limitation, but is usually 50% by weight or more, preferably 50% by weight or more. When it is 60% by weight or more, more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more, the water resistance of the acrylic rubber veil is highly improved and suitable. Further, when the total amount of sodium, magnesium, calcium, phosphorus and sulfur in the ash content of the acrylic rubber veil of the present invention is in this range, the metal adhesion is reduced and the workability is excellent and suitable.
  • the total amount of magnesium and phosphorus in the ash content of the acrylic rubber veil of the present invention is not particularly limited and may be appropriately selected depending on the intended use, but is usually 30% by weight or more, preferably 50% by weight or more. When it is more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more, the water resistance, strength characteristics and processability of the acrylic rubber veil are highly balanced and preferable. Further, when the total amount of magnesium and phosphorus in the ash content of the acrylic rubber veil of the present invention is in this range, the metal adhesion is reduced and the workability is excellent and suitable.
  • the amount of magnesium in the ash content of the acrylic rubber veil of the present invention is not particularly limited and may be appropriately selected depending on the intended use, but is usually 10% by weight or more, preferably 15 to 60% by weight, and more preferably 20 to 50% by weight. It is in the range of% by weight, particularly preferably 25 to 45% by weight, and most preferably 30 to 40% by weight.
  • the amount of phosphorus in the ash content of the acrylic rubber veil of the present invention is not particularly limited and may be appropriately selected depending on the intended use, but is usually 10% by weight or more, preferably 20 to 90% by weight, and more preferably 30 to 80% by weight. It is in the range of% by weight, particularly preferably 40 to 70% by weight, and most preferably 50 to 60% by weight.
  • the ratio of magnesium to phosphorus ([Mg] / [P]) in the ash content of the acrylic rubber veil of the present invention is not particularly limited and may be appropriately selected according to the purpose of use, but is usually a weight ratio.
  • the range is 0.4 to 2.5, preferably 0.45 to 1.2, more preferably 0.45 to 1, particularly preferably 0.5 to 0.8, and most preferably 0.55 to 0.7.
  • the water resistance, strength characteristics and workability of the acrylic rubber veil are highly balanced and suitable.
  • the ash content in the acrylic rubber veil is mainly derived from the emulsifier used when emulsifying the monomer component and emulsion polymerization and the coagulant used when coagulating the emulsion polymerization solution, but the total ash content.
  • the content of each component in the ash and the content of each component varies depending not only on the conditions of the emulsion polymerization step and the solidification step but also on the conditions of each subsequent step.
  • the acrylic rubber veil of the present invention uses an anionic emulsifier, a cationic emulsifier, or a nonionic emulsifier, preferably an anionic emulsifier, more preferably a phosphoric acid ester salt or a sulfate ester salt, as an emulsifier during emulsion polymerization described later.
  • an anionic emulsifier more preferably a phosphoric acid ester salt or a sulfate ester salt
  • mold releasability and workability can be highly improved, which is suitable.
  • the water resistance of the acrylic rubber veil is uniquely correlated with the amount of ash in the acrylic rubber and the total amount of sodium, magnesium, calcium, phosphorus and sulfur in the ash.
  • the water resistance, strength characteristics, mold releasability and processability of the above can be further balanced, which is suitable.
  • the acrylic rubber veil of the present invention has not only water resistance and strength characteristics but also mold releasability and mold releasability when a metal salt, preferably an alkali metal salt or a group 2 metal salt of the periodic table is used as a coagulant described later. It is suitable because it can greatly improve workability.
  • the water resistance of the acrylic rubber veil is uniquely correlated with the amount of ash in the acrylic rubber and the total amount of sodium, magnesium, calcium, phosphorus and sulfur in the ash.
  • the water resistance, strength characteristics, mold releasability and processability of the bale are more highly balanced and suitable.
  • the amount of gel of the acrylic rubber veil of the present invention is not particularly limited and may be appropriately selected depending on the intended use, but the amount of methyl ethyl ketone insoluble is 30% by weight or less, preferably 20% by weight or less, more preferably. When it is 15% by weight or less, particularly preferably 10% by weight or less, and most preferably 5% by weight or less, the processability at the time of kneading such as Banbury is highly improved and is preferable.
  • the values when the amount of gel in the acrylic rubber veil is arbitrarily sampled at a plurality of points and the variation is measured are all the values when measured within the range of the average value ⁇ 5% by weight. It is characterized by being something that can be entered.
  • the "method of arbitrarily sampling and measuring the gel amount at a plurality of points” refers to a method of measuring the variation in the gel amount by arbitrarily sampling 20 points from the inside of a large veil. In the method according to the present application (melt-kneaded in a screw type twin-screw extruder with substantially no water content (water content less than 1% by weight)), it is a specific effect and melt-kneaded.
  • the amount of gel in the veil varies.
  • all 20 points are within the range of the average value ⁇ 5% by weight, preferably all 20 points are within the range of the average value ⁇ 3% by weight, there is no workability variation and the rubber is rubber. It is suitable because the physical characteristics of the mixture and the crosslinked rubber are stabilized.
  • the value when the gel amount of the acrylic rubber veil is arbitrarily measured at 20 points is within the range of the average value ⁇ 5, and it is (average value -5) to (average value + 5) weight%. It means that all the measured gel amounts of 20 points are included in the range of, for example, when the average value of the measured gel amounts is 20% by weight, all 20 points are within the range of 15 to 25% by weight. It means that the measured value of is entered.
  • the acrylic rubber veil of the present invention is obtained by melt-kneading and drying a water-containing crumb produced by a solidification reaction in a state where almost all water is removed by a screw-type twin-screw extruder (water content less than 1% by weight). Sometimes Banbury workability and strength characteristics are highly balanced and suitable.
  • the complex viscosity ([ ⁇ ] 60 ° C.) of the acrylic rubber veil of the present invention at 60 ° C. is not particularly limited and may be appropriately selected according to the purpose of use, but is usually 15,000 [Pa ⁇ s] or less. , Preferably 1,000 to 10,000 [Pa ⁇ s], more preferably 2,000 to 5,000 [Pa ⁇ s], particularly preferably 2,500 to 4,000 [Pa ⁇ s], most preferably. Is excellent in workability, oil resistance and shape retention when it is in the range of 2,500 to 3,000 [Pa ⁇ s] and is suitable.
  • the complex viscosity ([ ⁇ ] 100 ° C.) of the acrylic rubber veil of the present invention at 100 ° C. is not particularly limited and may be appropriately selected according to the purpose of use, but is usually 1,500 to 6,000 [Pa. S], preferably 2,000 to 5,000 [Pa ⁇ s], more preferably 2,300 to 4,000 [Pa ⁇ s], and particularly preferably 2,500 to 3,500 [Pa ⁇ s]. Most preferably, it is excellent in processability, oil resistance and shape retention when it is in the range of 2,500 to 3,000 [Pa ⁇ s].
  • the ratio of the complex viscosity ([ ⁇ ] 100 ° C.) of the acrylic rubber veil of the present invention at 100 ° C. to the complex viscosity ([ ⁇ ] 60 ° C.) at 60 ° C. Is not particularly limited and may be appropriately selected according to the purpose of use, but is usually 0.5 or more, preferably 0.6 or more, more preferably 0.7 or more, particularly preferably 0.8 or more, and most. It is preferably 0.83 or more.
  • the water content of the acrylic rubber veil of the present invention is not particularly limited and is appropriately selected depending on the intended use, but is usually less than 1% by weight, preferably 0.8% by weight or less, more preferably 0.6% by weight.
  • the vulcanization characteristics of the acrylic rubber veil are optimized and the characteristics such as heat resistance and water resistance are highly improved, which is suitable.
  • the pH of the acrylic rubber veil of the present invention is not particularly limited and may be appropriately selected depending on the intended use, but is usually 6 or less, preferably 3 to 6, and more preferably 3 to 5.
  • the storage stability of the acrylic rubber veil is highly improved and is suitable.
  • the Mooney viscosity (ML1 + 4,100 ° C.) of the acrylic rubber veil of the present invention is not particularly limited and may be appropriately selected depending on the intended use, but is usually 10 to 150, preferably 20 to 100, and more preferably 25. When the range is in the range of ⁇ 70, the processability and strength characteristics of the acrylic rubber veil are highly balanced and suitable.
  • the specific gravity of the acrylic rubber veil 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, particularly preferably 0.95 or more, most preferably. When it is 1 or more, almost no air is contained therein, and it is excellent in storage stability and suitable.
  • the specific gravity of the acrylic rubber veil of the present invention is also usually 0.7 to 1.6, preferably 0.8 to 1.5, more preferably 0.9 to 1.4, and particularly preferably 0.95 to 1. 3.3, most preferably in the range of 1.0 to 1.2, productivity, storage stability, cross-linking property stability of crosslinked products, etc. are highly balanced and suitable.
  • the specific gravity of the acrylic rubber veil of the present invention is obtained by dividing the mass by the capacity including voids, that is, the mass measured in the air divided by the buoyancy, and is usually JIS K6268 crosslinked rubber-A of density measurement. It is measured according to the law.
  • the hydrous crumb produced by the solidification reaction is dried under reduced pressure by a screw type twin-screw extruder, or melt-kneaded and dried under reduced pressure to obtain storage stability. It is suitable because the roll workability and strength characteristics are particularly excellent and highly balanced. It was
  • the size of the acrylic rubber veil of the present invention is not particularly limited and may be appropriately selected depending on 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. It is suitable to be in the range of 150 to 250 mm.
  • the shape of the acrylic rubber veil of the present invention is not limited and is appropriately selected depending on the intended use of the acrylic rubber veil, but in many cases, a rectangular parallelepiped is suitable.
  • the method for producing the acrylic rubber veil is not particularly limited, but for example, acrylic containing a monomer containing at least one reactive group selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom.
  • Emulsion polymerization process and A coagulation step in which the obtained emulsion polymerization solution and the coagulation solution are brought into contact with each other to form a hydrous crumb, A cleaning process to clean the generated hydrous crumbs, A step of dehydrating the washed water-containing crumb 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 twin-screw extruder having a die at the tip.
  • a drying process that dries to less than 1% by weight in a drying barrel The molding process of extruding sheet-shaped dry rubber from the die, Laminating process of laminating extruded sheet-shaped dry rubber, It can be efficiently manufactured by the manufacturing method of the acrylic rubber veil containing.
  • the monomer component containing a monomer containing at least one reactive group selected from the group consisting of a carboxyl group, an epoxy group and a chlorine atom used in the present invention is not particularly limited, but is preferable. At least one selected from the group consisting of (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester, at least one selected from the group consisting of (meth) acrylic acid ester, carboxyl group, epoxy group and chlorine atom. It is composed of a monomer containing the reactive group of the above and other monomers copolymerizable as necessary, and is the same as the above-mentioned examples of the monomer components and the preferable range. The amount of the monomer component used is also as described above, and in the emulsion polymerization, each monomer may be appropriately selected so as to have the above composition of the acrylic rubber constituting the acrylic rubber veil of the present invention. ..
  • the emulsifier used in the present invention is not particularly limited, and examples thereof include an anionic emulsifier, a cationic emulsifier, and a nonionic emulsifier, and an anionic emulsifier is preferable.
  • the anionic emulsifier is not particularly limited, for example, salts of fatty acids such as myristic acid, palmitic acid, oleic acid, linolenic acid; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; sulfate esters such as sodium laurylsulfate.
  • Phosphate ester salts such as salts and polyoxyalkylene alkyl ether phosphate ester salts; alkyl sulfosuccinates and the like can be mentioned.
  • phosphoric acid ester salts and sulfate ester salts are preferable, phosphoric acid ester salts are particularly preferable, and divalent phosphoric acid ester salts are most preferable, and the water resistance, strength characteristics, and gold of the obtained acrylic rubber veil are preferable. It is suitable because it can highly balance mold releasability and workability.
  • the acrylic rubber veil obtained when these phosphate ester salts and sulfate ester salts are preferably alkali metal salts of phosphate esters and sulfate esters, and more preferably sodium salts of phosphate esters and sulfate esters. It is suitable because it can highly balance water resistance, strength characteristics, mold releasability and workability.
  • the divalent phosphoric acid ester salt is not particularly limited as long as it can be used as an emulsifier in the emulsification polymerization reaction, but is not particularly limited.
  • Examples thereof include ester salts, among which these metal salts are preferable, these alkali metal salts are more preferable, and these sodium salts are most preferable.
  • alkyloxypolyoxyalkylene phosphate ester salt examples include alkyloxypolyoxyethylene phosphoric acid ester salts and alkyloxypolyoxypropylene phosphate ester salts. Among these, alkyloxypolyoxyethylene phosphoric acid is used. Ester salts are preferred.
  • alkyloxypolyoxyethylene phosphoric acid ester examples include octyloxydioxyethylene phosphoric acid ester, octyloxytrioxyethylene phosphoric acid ester, octyloxytetraoxyethylene phosphoric acid ester, and decyloxytetraoxyethylene phosphoric acid ester.
  • alkyloxypolyoxypropylene phosphate ester examples include octyloxydioxypropylene phosphate, octyloxytrioxypropylene phosphate, octyloxytetraoxypropylene phosphate, and decyloxytetraoxypropylene phosphate.
  • alkylphenyloxypolyoxyalkylene phosphate ester examples include alkylphenyloxypolyoxyethylene phosphate and alkylphenyloxypolyoxypropylene phosphate, among which alkylphenyloxypoly is used.
  • Oxyethylene phosphate ester salts are preferred.
  • alkylphenyloxypolyoxyethylene phosphate ester examples include methyloxyoxytetraoxyethylene phosphate, ethylphenyloxytetraoxyethylene phosphate, butylphenyloxytetraoxyethylene phosphate, and hexylphenyloxytetra.
  • Oxyethylene Phosphate Nonylphenyloxytetraoxyethylene Phosphorate, Dodecylphenyloxytetraoxyethylene Phosphate, Octadecyloxytetraoxyethylene Phosphate, Methylphenyloxypentaoxyethylene Phosphate, Ethylphenyloxypentaoxy Ethylene Phosphate, Butylphenyloxypentaoxyethylene Phosphate, Hexylphenyloxypentaoxyethylene Phosphate, Nonylphenyloxypentaoxyethylene Phosphate, Dodecylphenyloxypentaoxyethylene Phosphate, Methylphenyloxyhexaoxy Ethylene Phosphate, Ethylphenyloxyhexaoxyethylene Phosphate, Butylphenyloxyhexaoxyethylene Phosphate, Hexylphenyloxyhexaoxyethylene Phosp
  • alkylphenyloxypolyoxypropylene phosphate ester examples include methylphenyloxytetraoxypropylene phosphate, ethylphenyloxytetraoxypropylene phosphate, butylphenyloxytetraoxypropylene phosphate, and hexylphenyloxytetra.
  • a monovalent phosphoric acid ester salt such as a di (alkyloxypolyoxyalkylene) phosphoric acid ester sodium salt can be used alone or in combination with a divalent phosphoric acid ester salt.
  • sulfate ester salt examples include sodium lauryl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate, sodium mystic sulfate, sodium polyoxyethylene alkyl sulfate, sodium polyoxyethylene alkylaryl sulfate, and the like, and sodium lauryl sulfate is preferable.
  • cationic emulsifier examples include alkyltrimethylammonium chloride, dialkylammonium chloride, benzylammonium chloride and the like.
  • nonionic emulsifier examples include polyoxyalkylene fatty acid esters such as polyoxyethylene stearate 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.
  • Each of these emulsifiers can be used alone or in combination of two or more, and the amount used is usually 0.01 to 10 parts by weight, preferably 0, with respect to 100 parts by weight of the monomer component. It is in the range of 1 to 5 parts by weight, more preferably 1 to 3 parts by weight.
  • the method of mixing the monomer component, water and emulsifier may follow a conventional method.
  • the amount of water used is usually 1 to 1000 parts by weight, preferably 5 to 500 parts by weight, more preferably 4 to 300 parts by weight, and particularly preferably 3 to 150 parts by weight, based on 100 parts by weight of the monomer component. Most preferably, it is in the range of 20 to 80 parts by weight.
  • the polymerization catalyst used in the present invention is characterized by using a redox catalyst composed of an inorganic radical generator and a reducing agent.
  • a redox catalyst composed of an inorganic radical generator and a reducing agent.
  • the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of acrylic rubber can be widened, and a roll of acrylic rubber veil to be produced or the like can be widened. It is suitable because it can highly improve the workability in the above.
  • the inorganic radical generator is not particularly limited as long as it is usually used in emulsion polymerization, and examples thereof include persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate, hydrogen peroxide, and the like. Among them, persulfate is preferable, potassium persulfate and ammonium persulfate are more preferable, and potassium persulfate is particularly preferable.
  • inorganic radical generators can be used individually 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 0.25 part by weight, particularly preferably 0.01 to 0.21 part by weight, and most preferably 0.1 to 0.2 part by weight.
  • the reducing agent used in the present invention is not particularly limited as long as it is usually used in emulsion polymerization, but preferably at least two kinds of reducing agents are used, and it is a metal ion compound in a reduced state. It is preferable to be able to further balance the vanbury workability, roll workability and strength characteristics of the acrylic rubber veil that can be obtained by combining with other reducing agents.
  • the metal ion compound in the reduced state is not particularly limited, and examples thereof include ferrous sulfate, sodium hexamethylenediamine tetraacetate, and ferrous naphthenate, and among these, ferrous sulfate is preferable.
  • These metal ion compounds in the reduced state can be used alone or in combination of two or more, and the amount used is usually 0.000001 to 0. With respect to 100 parts by weight of the monomer component. It is in the range of 01 parts by weight, preferably 0.00001 to 0.001 parts by weight, and more preferably 0.00005 to 0.0005 parts by weight.
  • the reducing agent other than the metal ion compound in the reduced state used in the present invention is not particularly limited, and is, for example, ascorbic acid such as ascorbic acid, sodium ascorbate, potassium ascorbate or a salt thereof; erythorbic acid, sodium erythorbate.
  • Elysorbic acid such as potassium erythorbinate or a salt thereof; sulphinate such as sodium hydroxymethane sulfine; sodium sulfite, potassium sulfite, sodium hydrogen sulfite, sodium aldehyde hydrogen sulfite, sulfite of potassium hydrogen sulfite; sodium pyrosulfate, pyro Pyro sulfites such as potassium sulfite, sodium pyrosulfate, potassium pyrosulfate; thiosulfates such as sodium thiosulfate, potassium thiosulfate; Pyroarophosphate or a salt thereof; Pyroarophosphate or a salt thereof such as Pyrophosic acid, Sodium Pyrophosphite, Potassium Pyrophosphite, Sodium Pyrophosphite, Potassium hydrogen Pyrophosphite; Sodium formaldehyde sulfoxylate and the like. Be done. Among these, al
  • reducing agents other than the metal ion compound in the reduced state can be used alone or in combination of two or more, and the amount used is usually 0.001 with respect to 100 parts by weight of the monomer component.
  • the range is from 1 part by weight, preferably 0.005 to 0.5 part by weight, and more preferably 0.01 to 0.1 part by weight.
  • a preferred 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. It is a combination with alcorbic acid or a salt thereof.
  • the amount of ferrous sulfate used at this time is usually 0.000001 to 0.01 parts by weight, preferably 0.00001 to 0.001 parts by weight, and more preferably 0, based on 100 parts by weight of the monomer component.
  • the amount of ascorbic acid or a salt thereof and / or sodium formaldehyde sulfoxylate is usually 0.001 to 1 part by weight, preferably 0.001 to 1 part by weight, based on 100 parts by weight of both components. It is in the range of 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.1 parts by weight.
  • the amount of water used in the emulsion polymerization reaction may be only the amount used at the time of emulsification of the monomer component, but is usually 10 to 1000 parts by weight, preferably 50 to 50 parts by weight with respect to 100 parts by weight of the monomer component used for polymerization. It is adjusted to be in the range of 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 method, a semi-batch method, or a continuous method.
  • the polymerization temperature and the polymerization time are not particularly limited and can be appropriately selected from the type of the polymerization initiator to be used and the like.
  • the polymerization time is usually 0.5 to 100 hours, preferably 1 to 10 hours.
  • the emulsion polymerization reaction is an exothermic reaction, and if not controlled, the temperature may rise and the polymerization reaction can be shortened.
  • the emulsion polymerization reaction temperature is usually 35 ° C. or lower, preferably 0 to 35 ° C., more preferably. It is preferable to control the temperature at 5 to 30 ° C, particularly preferably 10 to 25 ° C, because the strength characteristics of the produced acrylic rubber veil and the processability at the time of kneading such as Banbury are highly balanced.
  • the present invention is characterized in that the chain transfer agent is not added at the initial stage but is added in batches during the polymerization, whereby an acrylic rubber having a high molecular weight component and a low molecular weight component separated can be produced. ,
  • the strength characteristics of the acrylic rubber veil to be manufactured and the processability at the time of kneading such as rolls are highly balanced and suitable.
  • the chain transfer agent used is not particularly limited as long as it is usually used in emulsion polymerization, and for example, a mercaptan compound can be preferably used.
  • a mercaptan compound can be preferably used as the mercaptan compound.
  • an alkyl mercaptan compound having 2 to 20 carbon atoms preferably an alkyl mercaptan compound having 5 to 15 carbon atoms, and more preferably an alkyl mercaptan compound having 6 to 14 carbon atoms can be used.
  • the alkyl mercaptan compound may be any of n-alkyl mercaptan compound, sec-alkyl mercaptan compound and t-alkyl mercaptan compound, but is preferably n-alkyl mercaptan compound and t-alkyl mercaptan compound, and more preferably n-alkyl.
  • it is a mercaptan compound, the effect of the chain transfer agent can be stably exhibited, and the processability of the produced acrylic rubber roll or the like can be highly improved, which is suitable.
  • alkyl mercaptan compound examples include n-pentyl mercaptan, n-hexyl mercaptan, n-heptyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, n-tridecane mercaptan, and n-tetradecyl mercaptan.
  • chain transfer agents can be used alone or in combination of two or more.
  • the amount of the chain transfer agent used is not particularly limited, but is usually 0.0001 to 1 part by weight, preferably 0.0005 to 0.5 part by weight, based on 100 parts by weight of the monomer component.
  • the acrylic rubber veil produced preferably in the range of 0.001 to 0.5 parts by weight, particularly preferably 0.005 to 0.1 parts by weight, most preferably 0.01 to 0.06 parts by weight. It is suitable because it has a high balance between strength characteristics and roll workability.
  • the present invention is characterized in that the chain transfer agent is not added at the initial stage of polymerization but is added in batches during the polymerization, and the produced acrylic rubber becomes a high molecular weight component and a low molecular weight component, and the molecular weight distribution is specified.
  • the strength characteristics of the acrylic rubber veil and the processability of rolls and the like can be highly balanced, which is suitable.
  • the number of batch post-additions of the chain transfer agent is not particularly limited and is appropriately selected depending on the purpose of use, but is usually 1 to 5 times, preferably 2 to 4 times, more preferably 2 to 3 times. Particularly preferably, the strength characteristics of the acrylic rubber veil produced when the number of times is twice and the processability of the roll or the like can be highly balanced, which is preferable.
  • the time to start the batch post-addition of the chain transfer agent is not particularly limited and is appropriately selected according to the purpose of use, but is usually 20 minutes or later after the start of the polymerization, preferably 30 minutes or later after the start of the polymerization.
  • the strength characteristics of the acrylic rubber veil and the processability of rolls and the like are more preferably 30 to 200 minutes after the start of polymerization, particularly preferably 35 to 150 minutes after the start of polymerization, and most preferably 40 to 120 minutes. Can be highly balanced and is suitable.
  • the amount to be added per batch in the batch post-addition of the chain transfer agent is not particularly limited and is appropriately selected according to the purpose of use, but is usually 0.00005 to 100 parts by weight of the monomer component. 0.5 parts by weight, preferably 0.0001 to 0.1 parts by weight, more preferably 0.0005 to 0.05 parts by weight, particularly preferably 0.001 to 0.03 parts by weight, most preferably 0.002. It is suitable because the strength characteristics and roll workability of the acrylic rubber veil manufactured when the content is in the range of about 0.02 parts by weight can be highly balanced.
  • the polymerization reaction can be continued for usually 30 minutes or longer, preferably 45 minutes or longer, more preferably 1 hour or longer, and then terminated.
  • the reducing agent of the redox catalyst can be post-added during the polymerization, and the strength characteristics of the acrylic rubber veil produced by doing so and the processability of the roll and the like can be highly balanced. Suitable.
  • the reducing agent to be added after the polymerization As the reducing agent to be added after the polymerization, the above-mentioned examples of the reducing agent and the preferable range are the same. In the present invention, ascorbic acid or a salt thereof is suitable as the reducing agent to be added later.
  • the amount of the reducing agent to be added after the polymerization is not particularly limited and may be appropriately selected according to the purpose of use, but is usually 0.0001 to 1 with respect to 100 parts by weight of the monomer component.
  • weight preferably 0.0005 to 0.5 parts by weight, more preferably 0.001 to 0.5 parts by weight, particularly preferably 0.005 to 0.1 parts by weight, most preferably 0.01 to 0.
  • productivity of acrylic rubber production is excellent, and the strength characteristics and processability of the acrylic rubber veil to be produced can be highly balanced, which is suitable.
  • the reducing agent added after the polymerization may be continuous or batch, but is preferably batch.
  • the number of times the reducing agent is added in batches during the polymerization is not particularly limited, but is usually 1 to 5 times, preferably 1 to 3 times, and more preferably 1 to 2 times.
  • the ratio of the amount of ascorbic acid or a salt thereof added at the initial stage to the amount of ascorbic acid or a salt thereof added afterwards is exceptional.
  • the weight ratio of "initially added ascorbic acid or a salt thereof" / "a batch post-added ascorbic acid or a salt thereof” is usually 1/9 to 8/2, preferably 2/8 to 2. When it is in the range of 6/4, more preferably 3/7 to 5/5, the productivity of acrylic rubber production is excellent, and the strength characteristics and workability of the produced acrylic rubber veil can be highly balanced, which is suitable.
  • the timing of the post-addition of the reducing agent is not particularly limited and is appropriately selected according to the purpose of use. However, it is usually 1 hour or later after the start of polymerization, preferably 1 to 3 hours after the start of polymerization, and more preferably 1. When it is in the range of 5 to 2.5 hours, the productivity of acrylic rubber production is excellent, and the strength characteristics of the produced acrylic rubber veil and the processability of rolls and the like can be highly balanced, which is suitable.
  • the amount of the reducing agent added per batch in the batch post-addition is not particularly limited and is appropriately selected according to the purpose of use, but is usually 0.00005 to 0 with respect to 100 parts by weight of the monomer component.
  • the operation after the addition of the reducing agent is not particularly limited, but the polymerization reaction can be terminated after the polymerization reaction is continued for usually 30 minutes or longer, preferably 45 minutes or longer, more preferably 1 hour or longer.
  • the polymerization conversion rate of the emulsion polymerization reaction is 90% by weight or more, preferably 95% by weight or more, and the acrylic rubber veil produced at this time is suitable because it has excellent strength characteristics and no monomeric odor.
  • a polymerization inhibitor may be used to terminate the polymerization.
  • the coagulation step in the method for producing an acrylic rubber veil of the present invention is a step of coagulating the emulsion polymerization solution after emulsion polymerization with a coagulation solution (contacting the emulsion polymerization solution and the coagulation solution) to form a water-containing crumb.
  • the solid content concentration of the emulsion polymer used in this coagulation reaction 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. Will be done.
  • the coagulant used in the coagulant is not particularly limited, but usually a metal salt is used.
  • the metal salt include alkali metals, Group 2 metal salts of the Periodic Table, and other metal salts, preferably alkali metal salts, Group 2 metal salts of the Periodic Table, and more preferably Group 2 metals of the Periodic Table. It is suitable because it can highly balance the water resistance, strength characteristics, mold releasability and processability of the acrylic rubber obtained when it is a salt, particularly preferably a magnesium salt.
  • alkali metal salt examples include sodium salts such as sodium chloride, sodium nitrate and sodium sulfate; potassium salts such as potassium chloride, potassium nitrate and potassium sulfate; and lithium salts such as lithium chloride, lithium nitrate and lithium sulfate.
  • sodium salts are preferable, and sodium chloride and sodium sulfate are particularly preferable.
  • Examples of the Group 2 metal salt in the periodic table include magnesium chloride, calcium chloride, magnesium nitrate, calcium nitrate, magnesium sulfate, calcium sulfate and the like, and calcium chloride and magnesium sulfate are preferable.
  • metal salts include, for example, zinc chloride, titanium chloride, manganese chloride, iron chloride, cobalt chloride, nickel chloride, aluminum chloride, tin chloride, zinc nitrate, titanium nitrate, manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate. , Aluminum nitrate, tin nitrate, zinc sulfate, titanium sulfate, manganese sulfate, iron sulfate, cobalt sulfate, nickel sulfate, aluminum sulfate, tin sulfate and the like.
  • Each of these coagulants can be used alone or in combination of two or more, and the amount thereof is usually 0.01 to 100 parts by weight, preferably 0, with respect to 100 parts by weight of the monomer component. It is in the range of 1 to 50 parts by weight, more preferably 1 to 30 parts by weight. When the coagulant is in this range, it is suitable because it can sufficiently improve the coagulation of the acrylic rubber and highly improve the compression resistance permanent strain resistance and the water resistance when the acrylic rubber veil is crosslinked.
  • the coagulant used is usually used as an aqueous solution, and the coagulant concentration of the aqueous solution is usually 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight.
  • the particle size of the hydrous crumb generated when it is in the range of 1.5 to 5% by weight can be uniformly focused in a specific region, which is preferable.
  • the temperature of the coagulant is not particularly limited, but is preferably 40 ° C. or higher, preferably 40 to 90 ° C., more preferably 50 to 80 ° C., to generate a uniform water-containing crumb.
  • the method for coagulating the emulsified heavy liquid with the coagulating liquid is not particularly limited, but for example, a method of adding the coagulating liquid to the emulsion polymerization liquid, a method of adding the coagulation liquid to the stirred emulsion polymerization liquid, and the like. Any method may be used, such as a method of adding the emulsion polymerization solution to the coagulation liquid or a method of adding the emulsion polymerization solution to the agitated coagulation liquid, but a method of adding the emulsion polymerization solution to the agitated coagulation liquid. It is suitable because it is excellent in cleaning efficiency and dehydration efficiency of the water-containing crumb produced by the emulsion and can significantly improve the water resistance and storage stability of the obtained acrylic rubber veil.
  • the stirring speed (rotation speed) of the coagulated liquid being stirred is, that is, the rotation speed of the stirring blade of the stirring device, and is not particularly limited, but is usually 100 rpm or more, preferably 200 rpm or more, more preferably 200 to 1000 rpm. It is particularly preferably in the range of 300 to 900 rpm, and most preferably in the range of 400 to 800 rpm.
  • the rotation speed is a rotation speed that is agitated violently to some extent because the water-containing crumb particle size to be generated can be made small and uniform. It is possible to suppress the formation of and, and by setting it to the upper limit or less, it is possible to more easily control the coagulation reaction.
  • the peripheral speed of the coagulated liquid being stirred that is, the speed of the outer periphery of the stirring blade of the stirring device is not particularly limited, but the water-containing crumb particle size generated by being vigorously stirred to a certain degree is smaller and It can be made uniform and is preferable, usually 0.5 m / s or more, preferably 1 m / s or more, more preferably 1.5 m / s or more, particularly preferably 2 m / s or more, and most preferably 2.5 m / s or more. ..
  • the upper limit of the peripheral speed is not particularly limited, but is usually solidified 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.
  • a water-containing crumb produced by setting the above conditions of the coagulation reaction (contact method, solid content concentration of emulsion polymerization solution, concentration and temperature of coagulation liquid, rotation speed and peripheral speed of coagulation liquid at the time of stirring, etc.) in a specific range.
  • the shape and crumb diameter of the product are uniform and focused, the removal of emulsifiers and coagulants during cleaning and dehydration is significantly improved, and the water resistance and storage stability of the resulting acrylic rubber veil can be greatly improved. Therefore, it is suitable.
  • the cleaning step in the method for producing an acrylic rubber veil of the present invention is a step of cleaning the water-containing crumb produced by the solidification reaction.
  • the cleaning method is not particularly limited, and for example, the generated hydrous crumb can be mixed with a large amount of water.
  • the amount of water added for washing is not particularly limited, but the amount per washing with water is usually 50 parts by weight or more, preferably 50 to 15,000 parts by weight, based on 100 parts by weight of the monomer component. It is preferable that the amount of ash in the acrylic rubber veil can be effectively reduced when the amount is preferably in the range of 100 to 10,000 parts by weight, more preferably 500 to 5,000 parts by weight.
  • the temperature of the water used is not particularly limited, but it is preferable to use hot water, usually 40 ° C. or higher, preferably 40 to 100 ° C., more preferably 50 to 90 ° C., and particularly when 60 to 80 ° C. It is optimal because it can significantly improve the cleaning efficiency.
  • the temperature of the water used is equal to or higher than the above-mentioned lower limit, the emulsifier and coagulant are liberated from the water-containing crumb to further improve the cleaning efficiency.
  • the cleaning time is not particularly limited, but is usually in the range of 1 to 120 minutes, preferably 2 to 60 minutes, and more preferably 3 to 30 minutes.
  • the number of washings is also not particularly limited, and is usually 1 to 10 times, preferably 1 to 5 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 veil, it is desirable that the number of washings with water is large, but as described above, the shape of the water-containing crumb and the diameter of the water-containing crumb are set within a specific range. By doing so and / or setting the washing temperature within the above range, the number of washings with water can be significantly reduced.
  • draining process it is preferable to provide a draining step for separating free water from the water-containing crumb after washing with a draining machine in order to improve the dehydration efficiency.
  • a known one can be used without any particular limitation, and examples thereof include a wire mesh, a screen, an electric sieve, and the like, preferably a wire mesh and a screen.
  • the opening of the drainer is not particularly limited, but when it is usually in the range of 0.01 to 5 mm, preferably 0.1 to 1 mm, and more preferably 0.2 to 0.6 mm, the water content crumb loss is small. Moreover, draining can be done efficiently, which is suitable.
  • the water content of the water-containing crumb after draining is not particularly limited, but is usually 50 to 80% by weight, preferably 50 to 70% by weight, and more. It is preferably in the range of 50 to 60% by weight.
  • the temperature of the water-containing crumb after draining that is, the temperature of the water-containing crumb charged in the dehydration / drying / molding step is not particularly limited, but is usually 40 ° C. or higher, preferably 40 to 100 ° C., more preferably 50 ° C.
  • the specific heat is 1.5 to 2.5 KJ / like the acrylic rubber constituting the acrylic rubber veil of the present invention. It is suitable because the hydrous crumb, which has a high temperature of kg ⁇ K and is difficult to raise the temperature, can be efficiently dehydrated and dried using a screw type twin-screw extruder.
  • the water-containing crumb that has been washed and preferably drained is dewatered in a dehydration barrel having a dehydration slit, a drying barrel under reduced pressure, and a screw having a die at the tip.
  • This is a step of dehydrating to a water content of 1 to 40% by weight in a dehydration barrel using a mold twin-screw extrusion dryer, then drying to less than 1% by weight in a drying barrel, and extruding the sheet-shaped dried rubber from the die.
  • Dehydration of the water-containing crumb is performed in a dehydration barrel in a screw-type twin-screw extruder with a dehydration slit.
  • the opening of the dehydration slit may be appropriately selected according to the usage conditions, 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 water-containing crumb loss is small and the water-containing crumb can be efficiently dehydrated, which is suitable.
  • the number of dehydration barrels in the screw type twin-screw extruder is not particularly limited, but is usually a plurality, preferably 2 to 10, more preferably 3 to 6, and sticky acrylic rubber. It is suitable for efficient dehydration.
  • Exhaust steam is defined as pre-drying to distinguish it.
  • the water discharged from the dehydration slit in the dehydration of the water-containing crumb may be in a liquid (drainage) state or a steam state (exhaust steam), but it is carried out using a screw type twin-screw extruder equipped with a plurality of dehydration barrels. In this case, it is preferable to combine drainage and exhaust steam because the adhesive acrylic rubber can be efficiently dehydrated.
  • the selection between the drainage type dehydration barrel and the exhaust steam type dehydration barrel of the screw type twin-screw extruder equipped with three or more dehydration barrels may be appropriately performed according to the purpose of use, but in the acrylic rubber veil usually manufactured. If the ash content is to be reduced, the number of drainage barrels is increased, and if the water content is to be reduced, the number of drainage type barrels is increased.
  • the set temperature of the dehydration barrel is appropriately selected depending on the monomer composition of the acrylic rubber, the ash content, the water content, the operating conditions, etc., 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 for dehydrating 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 for dehydration 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 not particularly limited, but is 1 to 40% by weight, preferably 5 to 40% by weight, more preferably 5 to 35% by weight, and particularly preferably. When is 10 to 35% by weight, productivity and ash removal efficiency are highly balanced and suitable.
  • the acrylic rubber adheres to the dehydration slit portion and can hardly be dehydrated (water content is up to about 45 to 55% by weight). ),
  • the water content can be reduced to this extent by using a screw type twin-screw extruder having a dehydration slit and forcibly squeezed with a screw.
  • the water content after drainage in the drainage type dehydration barrel portion is usually 5 to 40% by weight, preferably 10 to 40% by weight, more preferably. Is 15 to 35% by weight, and the water content after pre-drying in the exhaust steam type dehydration barrel portion is usually 1 to 30% by weight, preferably 3 to 20% by weight, and more preferably 5 to 15% by weight.
  • the dehydration time can be shortened and deterioration of acrylic rubber can be suppressed, and by setting it to be lower than the upper limit, the amount of ash can be sufficiently reduced.
  • the storage stability of the acrylic rubber veil can be largely correlated with the specific gravity of the acrylic rubber veil and can be controlled, but when the specific gravity is large and a high degree of storage stability is controlled, it can be controlled by the degree of decompression of extrusion drying or the like.
  • the degree of decompression of the drying barrel may be appropriately selected, but when it is usually 1 to 50 kPa, preferably 2 to 30 kPa, more preferably 3 to 20 kPa, the water-containing crumb can be efficiently dried and the air in the acrylic rubber can be removed. It is suitable because it can be removed and the storage stability of the acrylic rubber veil can be significantly improved.
  • the set temperature of the drying barrel may be appropriately selected, but when it is usually in the range of 100 to 250 ° C., preferably 110 to 200 ° C., more preferably 120 to 180 ° C., there is no discoloration or deterioration of the acrylic rubber. It is suitable because it can be dried efficiently and the amount of gel of the insoluble matter of methyl ethyl ketone in the acrylic rubber veil can be reduced.
  • the number of drying barrels in the screw type twin-screw 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.
  • the set temperature may be an approximate temperature for all the dry barrels or may be changed, but it is closer to the discharge part (closer to the die) than the temperature of the introduction part (closer to the dehydration barrel). It is preferable that the temperature of (1) is higher because the drying efficiency can be increased.
  • the water content of the dried rubber after drying is usually less than 1% by weight, preferably 0.8% by weight or less, and more preferably 0.6% by weight or less.
  • the methyl ethyl ketone insoluble content of the acrylic rubber veil is extruded by melting and kneading with the water content of the dried rubber set to this value (with almost all water removed), especially in a screw type twin-screw extruder. It is suitable because the amount of gel can be reduced.
  • an acrylic rubber bale that has been melt-kneaded or melt-kneaded and dried with a screw-type twin-screw extruder is suitable because both strength characteristics and Banbury processability characteristics are highly balanced.
  • melt kneading or “melt kneading and drying” as used in the present invention means that acrylic rubber is kneaded (mixed) or extruded in a molten state in a screw type twin-screw extruder, and the stage thereof. It means that acrylic rubber is kneaded in a molten (plasticized) state by a screw-type twin-screw extruder and then extruded and dried.
  • the shear rate applied to the drying barrel of the screw type twin-screw extruder in a state where the acrylic rubber does not contain water is not particularly limited, but is usually 10 [1 / s].
  • the storage stability, roll workability, Banbury workability, and strength characteristics of the acrylic rubber veil obtained preferably in the range of 10 to 400 [1 / s], more preferably 50 to 250 [1 / s].
  • the compression resistance permanent strain characteristics are highly balanced and suitable.
  • the shear viscosity of acrylic rubber in the screw type twin-screw extruder used in the present invention, particularly in a drying barrel, is not particularly limited, but is usually 12000 [Pa ⁇ s] or less, preferably 1000 to 12000 [Pa ⁇ s]. ], More preferably 2000 to 10000 [Pa ⁇ s], particularly preferably 3000 to 7000 [Pa ⁇ s], and most preferably 4000 to 6000 [Pa ⁇ s]. Stability, roll workability, Banbury workability and strength characteristics are highly balanced and suitable.
  • the dried rubber dehydrated and dried by the screw portion of the dehydration barrel and the dry barrel is sent to a rectifying die portion without a screw, and is extruded from the die portion into a desired shape.
  • a breaker plate or wire mesh may or may not be provided between the screw portion and the die portion.
  • the extruded dry rubber is suitable because the die shape is made into a substantially rectangular shape and the die is formed into a sheet, so that air entrainment is small, the specific gravity is large, and the dry rubber is excellent in storage stability.
  • the acrylic rubber melt-kneaded without containing air is extruded into a sheet without containing air as it is.
  • the resin pressure in the die portion is not particularly limited, but when it is usually in the range of 0.1 to 10 MPa, preferably 0.5 to 5 MPa, and more preferably 1 to 3 MPa, the amount of air entrained in the acrylic rubber sheet is small ( It has a high specific gravity) and is excellent in productivity and suitable. Screw type twin-screw extruder and operating conditions
  • the screw length (L) of the screw type twin-screw extruder to be used may be appropriately selected according to the purpose of use, but is usually in the range of 3000 to 15000 mm, preferably 4000 to 10000 mm, and more preferably 4500 to 8000 mm. Is.
  • the screw diameter (D) of the screw type twin-screw extruder to be 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. Is.
  • the ratio (L / D) of the screw length (L) to the screw diameter (D) of the screw type twin-screw extruder used is not particularly limited, but is usually 10 to 100, preferably 20 to 20. When it is in the range of 80, more preferably 30 to 60, the water content can be 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 twin-screw extruder used may be appropriately selected according to various conditions, but is usually 10 to 1000 rpm, preferably 50 to 750 rpm, more preferably 100 to 500 rpm, and most preferably. It is preferable that the water content and the gel amount of the acrylic rubber veil can be efficiently reduced at 120 to 300 rpm.
  • the extrusion amount (Q) of the screw type twin-screw extruder used is not particularly limited, but is usually 100 to 1,500 kg / hr, preferably 300 to 1200 kg / hr, more preferably 400 to 1000 kg / hr, and most. It is preferably in the range of 500 to 800 kg / hr.
  • the ratio (Q / N) of the extrusion amount (Q) to the rotation speed (N) of the screw type twin-screw extruder used is not particularly limited, but is usually 2 to 10, preferably 3 to 8. , More preferably in the range of 4-6.
  • the roll workability, Banbury workability and strength characteristics of the acrylic rubber veil obtained by drying the water-containing crumb under the condition of high share using a screw type twin-screw extruder having two screws. Can be highly balanced and is suitable.
  • the maximum torque of the screw type twin-screw extruder used is not particularly limited, but is usually 25 N ⁇ m or more, preferably 30 N ⁇ m or more, more preferably 35 N ⁇ m or more, and particularly preferably 40 N ⁇ m or more. It is m or more.
  • the maximum torque of the screw type twin-screw extruder used in the present invention is also usually 25 to 125 Nm, preferably 30 to 100 Nm, more preferably 35 to 75 Nm, and particularly preferably 40 to 60 N. -When it is in the range of m, the roll processability, the bumper processability and the strength characteristics of the produced acrylic rubber veil can be highly balanced, which is suitable.
  • the specific power of the screw type twin-screw extruder used is not particularly limited, but is usually 0.1 to 0.25 [kW ⁇ h / kg] or more, preferably 0.13 to 0.23 [kW].
  • ⁇ H / kg] more preferably in the range of 0.15 to 0.2 [kW ⁇ h / kg]
  • the roll workability, Banbury workability and strength characteristics of the acrylic rubber bale obtained are highly balanced. Suitable.
  • the specific power of the screw type twin-screw extruder used is not particularly limited, but is usually 0.2 to 0.6 [A ⁇ h / kg] or more, preferably 0.25 to 0.55 [A].
  • ⁇ H / kg] more preferably in the range of 0.35 to 0.5 [A ⁇ h / kg]
  • the roll workability, Banbury workability and strength characteristics of the acrylic rubber veil obtained are highly balanced. Suitable.
  • the shear rate of the screw type twin-screw extruder used is not particularly limited, but is usually 40 to 150 [1 / s] or more, preferably 45 to 125 [1 / s], and more preferably 50 to 100.
  • the storage stability, roll workability, Banbury workability and strength characteristics of the acrylic rubber veil obtained in the range of [1 / s] are highly balanced and suitable.
  • the shear viscosity of the acrylic rubber in the screw type twin-screw extruder used is not particularly limited, but is usually 4000 to 8000 [Pa ⁇ s] or less, preferably 4500 to 7500 [Pa ⁇ s], more preferably.
  • the storage stability, roll workability, Banbury workability and strength characteristics of the acrylic rubber veil obtained in the range of 5000 to 7000 [Pa ⁇ s] are highly balanced and suitable.
  • the shape of the dried rubber extruded from the screw-type twin-screw extruder is sheet-like, and at this time, the specific gravity can be increased without entraining air, and the storage stability is highly improved, which is suitable.
  • the sheet-shaped dry rubber extruded from the screw-type twin-screw extruder is usually cooled and cut to be used as an acrylic rubber sheet.
  • the thickness of the sheet-shaped dry rubber extruded from the screw-type twin-screw extruder is not particularly limited, but is usually 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 when it is within the range of. In particular, since the thermal conductivity of the sheet-shaped dried rubber is as low as 0.15 to 0.35 W / mK, the thickness of the sheet-shaped dried rubber is usually 1 to 30 mm when the cooling efficiency is increased and the productivity is significantly 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 twin-screw extruder is appropriately selected according to the purpose of use, but is usually in the range of 300 to 1200 mm, preferably 400 to 1000 mm, and more preferably 500 to 800 mm. ..
  • the temperature of the sheet drying rubber extruded from the screw type twin-screw 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 sheet drying rubber extruded from the screw type twin-screw 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. be.
  • the complex viscosity ([ ⁇ ] 100 ° C.) of the sheet-shaped dried rubber extruded from the screw-type twin-screw extruder at 100 ° C. is not particularly limited, but is usually 1500 to 6000 [Pa ⁇ s], preferably 1500 to 6000 [Pa ⁇ s]. Is in the range of 2000 to 5000 [Pa ⁇ s], more preferably 2500 to 4000 [Pa ⁇ s], and most preferably 2500 to 3500 [Pa ⁇ s]. Is highly balanced and suitable. That is, when it is set to the lower limit or more, the extrudability can be improved, and when it is set to the upper limit or less, the shape of the sheet-shaped dried rubber can be suppressed from collapsing or breaking.
  • the sheet-shaped dry rubber extruded from the screw-type twin-screw 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 it.
  • the cutting temperature of the sheet-shaped dry rubber is not particularly limited, but is preferably 60 ° C. or lower, preferably 55 ° C. or lower, more preferably 50 ° C. or lower, in which the cutability and productivity are highly balanced. Is.
  • the complex viscosity ([ ⁇ ] 60 ° C.) of the sheet-shaped dried rubber at 60 ° C. is not particularly limited, but is usually 15,000 or less, preferably 2000 to 10.000 [Pa ⁇ s], more preferably. Is suitable because it can cut continuously without entraining air when it is in the range of 2500 to 7000 [Pa ⁇ s], most preferably 2700 to 5500 [Pa ⁇ s].
  • 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 little air entrainment and has a high balance between cutting and productivity.
  • the cooling method of the sheet-shaped dried rubber is not particularly limited and may be left at room temperature. However, since the heat conductivity of the sheet-shaped dried 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 watering method of spraying water, or a dipping method of immersing in water is preferable for increasing productivity, and an air cooling method of blowing air or cooling 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 is usually 40 ° C./hr or more, preferably 50 ° C./hr or more, more preferably 100 ° C./hr or more, and particularly preferably 150 ° C./hr or more. In this case, cutting becomes easy and storage stability can be improved without entraining air in the molded body, which is suitable.
  • the cooling rate of the sheet-shaped dry rubber is usually 40 ° C./hr or more, preferably 50 ° C./hr or more, more preferably 100 ° C./hr or more, and particularly preferably 150 ° C./hr or more. Sometimes the scorch stability when the acrylic rubber veil is made into a rubber composition is remarkably excellent and suitable.
  • the cutting length of the sheet-shaped dried 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 to crumb-shaped acrylic rubber, and is also excellent in roll workability, strength characteristics and compression set resistance, storage stability, Banbury workability, crosslinkability and water resistance. It has excellent properties and can be used as it is or laminated and veiled.
  • the acrylic rubber veil of the present invention can be obtained by laminating the above acrylic rubber sheets, and by laminating the sheet-shaped acrylic rubber, an acrylic rubber veil with less air entrainment and excellent storage stability can be obtained.
  • the laminating temperature of the sheet-shaped acrylic rubber is not particularly limited, but is suitable because air entrained during laminating can be released when it is usually 30 ° C. or higher, preferably 35 ° C. or higher, and more preferably 40 ° C. or higher.
  • the number of laminated layers may be appropriately selected according to the size or weight of the acrylic rubber veil.
  • the acrylic rubber veil of the present invention is integrated by the weight of the laminated sheet-shaped acrylic rubber.
  • the acrylic rubber veil of the present invention thus obtained is superior in operability as compared with crumb-shaped acrylic rubber, and is also excellent in roll workability, strength characteristics and compression set resistance permanent strain resistance, as well as storage stability, Banbury workability and crosslinkability. It also has excellent water resistance, and the acrylic rubber veil can be used as it is or by cutting a required amount and putting it into a mixer such as a Banbury or a roll.
  • the rubber mixture of the present invention is characterized by containing the acrylic rubber veil, a filler and a cross-linking agent.
  • the filler contained in the rubber mixture is not particularly limited, and examples thereof include a reinforcing filler and a non-reinforcing filler, and when the filler is preferably a reinforcing filler, the roll processability of the rubber mixture is preferable. It is suitable because it is excellent in rubbery workability and short-time cross-linking property, and is highly excellent in water resistance, strength property and compression set resistance property of the cross-linked product.
  • Examples of the reinforcing filler include carbon blacks such as furnace black, acetylene black, thermal black, channel black and graphite; silicas such as wet silica, dry silica and colloidal silica; and the like.
  • Examples of the non-reinforcing filler include quartz powder, silica soil, zinc flower, basic magnesium carbonate, active calcium carbonate, magnesium silicate, aluminum silicate, titanium dioxide, talc, aluminum sulfate, calcium sulfate, barium sulfate and the like. be able to.
  • fillers can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected within a range that does not impair the effect of the present invention, and is used in 100 parts by weight of the acrylic rubber veil of the present invention. On the other hand, it is usually in the range of 1 to 200 parts by weight, preferably 10 to 150 parts by weight, and more preferably 20 to 100 parts by weight.
  • the cross-linking agent used in the rubber mixture is not particularly limited, and conventionally known cross-linking agents are selected according to the purpose of use. Examples thereof include inorganic cross-linking agents such as sulfur compounds and organic cross-linking agents, which are preferable. It is an organic cross-linking agent.
  • the cross-linking agent may be either a polyvalent compound or a monovalent compound, but a polyvalent compound having two or more reactivity is preferable.
  • the cross-linking agent may be either an ionic cross-linking compound or a radical cross-linking compound, but is preferably an ionic cross-linking compound.
  • the organic cross-linking agent is not particularly limited, but an ion-crosslinkable organic compound is preferable, and a polyvalent ion-organic compound is particularly preferable.
  • the cross-linking agent is a polyvalent ion organic compound (polyvalent ion cross-linking compound)
  • the rubber mixture has excellent roll processability, Banbury processability and short-time cross-linking property, and water resistance and strength characteristics of the cross-linked product. It also has excellent compression-resistant permanent strain characteristics and is particularly suitable.
  • the "ion" of the ion-crosslinkable or polyvalent ion is an ion-reactive ion, and is, for example, an ion-reactive group that reacts ionically with the ion-reactive group of the ion-reactive group-containing monomer of the acrylic rubber.
  • preferred examples thereof include an ion-crosslinkable organic compound having an ionic reactive group such as an amine group, an epoxy group, a carboxyl group and a thiol group.
  • polyvalent ion organic compound examples include a polyvalent amine compound, a polyvalent epoxy compound, a polyvalent carboxylic acid compound, a polyvalent thiol compound, and the like, preferably a polyvalent amine compound and a polyvalent thiol compound, more preferably. Is a polyvalent amine compound.
  • polyvalent amine compound examples include aliphatic polyvalent amine compounds such as hexamethylenediamine, hexamethylenediamine carbamate, 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 carbonates can also be preferably used.
  • These polyvalent amine compounds are particularly preferably used in combination with a carboxyl group-containing acrylic rubber veil or an epoxy group-containing acrylic rubber veil.
  • a triazine thiol compound is preferably used, for example, 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, Examples thereof include 1-hexylamino-3,5-dimercaptotriazine.
  • These triazine thiol compounds are particularly preferably used in combination with an acrylic rubber veil containing a chlorine atom.
  • polyvalent organic compounds examples include polyvalent carboxylic acid compounds such as tetradecanedioic acid and dithiocarbamate metal salts such as zinc dimethyldithiocarbamate. These other polyvalent organic compounds are particularly preferably used in combination with an epoxy group-containing acrylic rubber veil.
  • cross-linking agents can be used individually or in combination of two or more, and the blending amount thereof is usually 0.001 to 20 parts by weight, preferably 0, with respect to 100 parts by weight of the acrylic rubber veil of the present invention. It is 1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.
  • the rubber mixture of the present invention can be blended with an antiaging agent as needed.
  • the type of antiaging agent is not particularly limited, but is, for example, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butylphenol, butylhydroxyanisole, 2,6-di-t.
  • anti-aging agents can be used alone or in combination of two or more, and the blending amount thereof is preferably 0.01 to 15 parts by weight, preferably 0.01 to 15 parts by weight, based on 100 parts by weight of the acrylic rubber veil of the present invention. It is in the range of 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight.
  • the acrylic rubber veil of the present invention may be used alone, or, if necessary, the acrylic rubber veil of the present invention and other rubber components may be combined in combination. You may use it.
  • the other rubber components to be combined with the acrylic rubber veil of the present invention are not particularly limited, and are, for example, natural rubber, polybutadiene rubber, polyisoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, silicon rubber, fluororubber, and olefin.
  • examples thereof include 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 rubber components may be any of a crumb shape, a strand shape, a veil shape, a sheet shape, a powder shape and the like.
  • the amount of the other rubber component used is appropriately selected within a range that does not impair the effect of the present invention. It is preferably 30 parts by weight or less, particularly preferably 20 parts by weight or less, and most preferably 10 parts by weight or less.
  • the rubber mixture of the present invention contains the acrylic rubber veil, filler and cross-linking agent of the present invention as essential components, and if necessary, an antiaging agent and other rubber components, and further, if necessary, the technical field.
  • These other compounding agents can be used alone or in combination of two or more, and the compounding amount thereof is appropriately selected as long as the effect of the present invention is not impaired.
  • Examples of the method for producing a rubber mixture of the present invention include a method of mixing the acrylic rubber veil of the present invention, a filler, a cross-linking agent, an antiaging agent which can be contained as needed, other rubber components, and other compounding agents.
  • any means used in the conventional rubber processing field for example, an open roll, a Banbury mixer, various kneaders and the like can be used.
  • the mixing procedure of each component may be carried out by a normal procedure performed in the field of rubber processing. For example, a component that is difficult to react or decompose by heat is sufficiently mixed, and then a component that easily reacts or decomposes by heat is used. It is preferable to mix a certain cross-linking agent or the like at a temperature at which reaction or decomposition does not occur in a short time.
  • the rubber crosslinked product of the present invention is obtained by cross-linking the above rubber mixture.
  • the rubber crosslinked product of the present invention is formed by using the rubber mixture of the present invention with a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor or a roll, and then heated to carry out a cross-linking reaction. It can be manufactured by fixing the shape as a rubber crosslinked product. In this case, cross-linking may be performed after molding in advance, or cross-linking may be performed at the same time as molding.
  • the molding temperature is usually 10 to 200 ° C, preferably 25 to 150 ° C.
  • the crosslinking temperature is usually 100 to 250 ° C., preferably 130 to 220 ° C., more preferably 150 to 200 ° C.
  • the crosslinking time is usually 0.1 minutes to 10 hours, preferably 1 minute to 5 hours.
  • a method used for cross-linking rubber such as press heating, steam heating, oven heating, and hot air heating may be appropriately selected.
  • the rubber crosslinked product of the present invention may be further heated for secondary cross-linking depending on the shape, 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 rubber crosslinked product of the present invention has excellent compression-resistant permanent strain resistance and water resistance while maintaining basic rubber properties such as tensile strength, elongation, and hardness.
  • the rubber crosslinked product of the present invention makes use of the above characteristics, for example, O-ring, packing, diaphragm, oil seal, shaft seal, bearing seal, mechanical seal, well head seal, seal for electric / electronic equipment, air compression equipment.
  • Sealing materials such as 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 negative electrode.
  • 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; cushioning material, anti-vibration material; wire coating material; industrial belts; tubes -Preferably used as hoses; sheets; etc.
  • the rubber cross-linked product of the present invention is also used as an extruded mold product and a mold cross-linked product for automobile applications, for example, fuel oil for fuel tanks such as fuel hoses, filler neck hoses, bent hoses, paper hoses, and oil hoses. It is suitably used for various hoses such as air hoses such as system hoses, turbo air hoses and mission control hoses, radiator hoses, heater hoses, brake hoses and air conditioner hoses.
  • FIG. 1 is a diagram schematically showing an example of an acrylic rubber manufacturing system having an apparatus configuration used for manufacturing an acrylic rubber veil according to an embodiment of the present invention.
  • the acrylic rubber production system 1 shown in FIG. 1 can be used.
  • the acrylic rubber manufacturing system 1 shown in FIG. 1 is composed of an emulsion polymerization reactor (not shown), a coagulation device 3, a cleaning device 4, a drainer 43, and a screw type twin-screw extruder.
  • the emulsion polymerization reactor is configured to perform the treatment related to the emulsion polymerization step described above.
  • this emulsion polymerization reactor has, for example, a polymerization reaction tank, a temperature control unit for controlling the reaction temperature, a motor, and a stirring device including a stirring blade.
  • water and an emulsifier are mixed with a monomer component for forming acrylic rubber and emulsified while being appropriately stirred with a stirrer, and a redox catalyst consisting of an inorganic radical generator and a reducing agent is present.
  • 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 processing related to the above-mentioned coagulation step.
  • 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 generated by bringing the emulsion polymerization solution obtained by the emulsion polymerization reactor into contact with the coagulation solution and coagulating it.
  • a method of adding the emulsion polymerization solution to the stirring coagulation liquid is adopted for the contact between the emulsion polymerization solution and the coagulation liquid. That is, a water-containing crumb is generated by filling the stirring tank 30 of the coagulation device 3 with a coagulation liquid and adding and contacting the emulsion polymerization liquid with the coagulation liquid to coagulate the emulsion polymerization liquid.
  • the heating unit 31 of the coagulation device 3 is configured to heat the coagulation liquid filled in the stirring tank 30. Further, the temperature control unit of the coagulation device 3 controls the temperature inside the stirring tank 30 by controlling the heating operation by the heating unit 31 while monitoring the temperature inside the stirring tank 30 measured by the thermometer. It is configured. The temperature of the coagulating liquid in the stirring tank 30 is controlled by the temperature control unit to be usually in the range of 40 ° C. or higher, preferably 40 to 90 ° C., and more preferably 50 to 80 ° C.
  • the stirring device 34 of the coagulating device 3 is configured to stir the coagulating liquid filled in the stirring tank 30.
  • the stirring device 34 includes a motor 32 that generates rotational power, and a stirring blade 33 that extends in a direction perpendicular to the rotation axis of the motor 32.
  • the stirring blade 33 can flow the coagulating liquid by rotating around the rotation axis by the rotational power of the motor 32 in the coagulating liquid filled in the stirring tank 30.
  • the shape and size of the stirring blade 33, the number of installations, and the like are not particularly limited.
  • the drive control unit of the coagulation device 3 is configured to control the rotational drive of the motor 32 of the stirring device 34 to set the rotation speed and the rotation speed of the stirring blade 33 of the stirring device 34 to predetermined values.
  • the rotation of the stirring blade 33 is controlled by the drive control unit so that the stirring number of the coagulating liquid is usually in the range of 100 rpm or more, preferably 200 to 1000 rpm, more preferably 300 to 900 rpm, and particularly preferably 400 to 800 rpm. Will be done.
  • the peripheral speed of the coagulant is usually 0.5 m / s or more, preferably 1 m / s or more, more preferably 1.5 m / s or more, particularly preferably 2 m / s or more, and most preferably 2.5 m / s or more.
  • the rotation of the stirring blade 33 is controlled by the drive control unit. Further, the drive control unit agitates the coagulant so that the upper limit of the peripheral speed is usually 50 m / s or less, preferably 30 m / s or less, more preferably 25 m / s or less, and most preferably 20 m / s or less.
  • the rotation of the wing 33 is controlled.
  • the cleaning device 4 shown in FIG. 1 is configured to perform the processing related to the above-mentioned cleaning step.
  • the cleaning device 4 includes, for example, a cleaning tank 40, a heating unit 41 for heating the inside of the cleaning tank 40, and a temperature control unit (not shown) for controlling the temperature inside the cleaning tank 40.
  • a temperature control unit not shown for controlling the temperature inside the cleaning tank 40.
  • the water-containing crumb generated by the coagulation device 3 is mixed with a large amount of water for cleaning, so that the amount of ash in the finally obtained acrylic rubber veil can be effectively reduced.
  • 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. Ru.
  • the water-containing crumb washed by the washing device 4 is supplied to the screw type twin-screw extruder 5 that performs the dehydration step and the drying step. At this time, it is preferable that the water-containing crumb after washing is supplied to the screw type twin-screw 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 twin-screw extruder 5 is set to 60 ° C. or higher. It may be possible to maintain it, and even if it is heated so that the temperature of the water-containing crumb is 40 ° C. or higher, preferably 60 ° C.
  • the screw type twin-screw 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 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 for performing the above treatment.
  • the screw type twin-screw 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 twin-screw 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 function as a dryer for drying the hydrous crumb.
  • the drying 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 twin-screw extruder 5.
  • FIG. 2 shows the configuration of a specific example suitable for the screw type twin-screw extruder 5 shown in FIG.
  • the screw type twin-screw extruder 5 can suitably perform the above-mentioned dehydration / drying step.
  • the screw-type twin-screw 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 twin-screw extruder 5 has a drive unit 50 that rotationally drives a pair of screws in the barrel unit 51. With this configuration, acrylic rubber can be dried with a high share, which is suitable.
  • the drive unit 50 is attached to the upstream end (left end in FIG. 2) of the barrel unit 51. Further, the screw type twin-screw 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 dry barrel portion 54 has eight dry barrels, that is, a first dry barrel 54a, a second dry barrel 54b, a third dry barrel 54c, a fourth dry barrel 54d, and a fifth dry 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 the 13 divided barrels 52a to 52b, 53a to 53c, 54a to 54h from the upstream side to the downstream side.
  • the water-containing crumbs in the barrels 52a to 52b, 53a to 53c, 54a to 54h are individually heated by heating the barrels 52a to 52b, 53a to 53c, 54a to 54h individually.
  • Each has a heating means (not shown) for heating to a predetermined 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 jacket formed in each barrel 52a to 52b, 53a to 53c, 54a to 54h. It is not limited to this.
  • the screw type twin-screw 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 dry barrels constituting 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 not limited to the mode shown in FIG.
  • 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 the water-containing crumbs of the adhesive acrylic rubber can be efficiently dehydrated.
  • 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 drive means such as a motor housed in the drive 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, and may be any shape required for the barrel portions 52, 53, 54, and is not particularly limited.
  • the supply barrel portion 52 is a region for supplying the water-containing 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 water-containing crumb.
  • the first to third dehydration barrels 53a to 53c constituting the dehydration barrel portion 53 each have dehydration slits 56a, 56b, 56c for discharging the water content of the water-containing crumb to the outside.
  • a plurality of each dehydration slit 56a, 56b, 56c is formed in each dehydration barrel 53a to 53c, respectively.
  • the slit widths that is, the openings of the dehydration slits 56a, 56b, 56c may be appropriately selected according to the usage conditions, and are usually 0.01 to 5 mm, the loss of the water-containing crumb is small, and the water-containing crumb is dehydrated. It is preferably 0.1 to 1 mm, and more preferably 0.2 to 0.6 mm from the viewpoint that the above can be efficiently performed.
  • the dehydration barrel portion 53 is suitable because the water content of the adhesive acrylic rubber can be efficiently reduced 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 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 for drying the hydrous crumb after dehydration 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, 58d for degassing, respectively. Vent pipes (not shown) are connected to the vent openings 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 temperature in all the dry barrels 54a to 54h may be an approximate value or may be different, but the upstream side (dehydration 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 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 by 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 passing through the die 59 can be molded into various shapes such as granular, columnar, round bar, and sheet depending on the nozzle shape of the die 59, but in the present invention, it is molded into a sheet.
  • 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 to the supply barrel portion 52 from the feed port 55.
  • 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 water 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 plastically 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 the vent pipes (not shown) connected to the vent ports 58a, 58b, 58c, 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 1000 rpm, and the water content of acrylic rubber and the insoluble content of methyl ethyl ketone 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 1500 kg / hr, preferably 300 to 1200 kg / hr, more preferably 400 to 1000 kg / hr, and 500 to 800 kg / hr. 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 3 to. It is 8, and 4 to 6 are particularly preferable.
  • the maximum torque in the barrel unit 51 is not particularly limited, but is usually in the range of 30 to 100 Nm, preferably 35 to 75 Nm, and more preferably 40 to 60 Nm.
  • the specific power in the barrel unit 51 is not particularly limited, but is usually 0.1 to 0.25 [kW ⁇ h / kg] or more, preferably 0.13 to 0.23 [kW ⁇ h / kg]. More preferably, it is in the range of 0.15 to 0.2 [kW ⁇ h / kg].
  • the specific power in the barrel unit 51 is not particularly limited, but is usually 0.2 to 0.6 [A ⁇ h / kg] or more, preferably 0.25 to 0.55 [A ⁇ h / kg]. More preferably, it is in the range of 0.35 to 0.5 [A.h / kg].
  • the shear rate in the barrel unit 51 is not particularly limited, but is usually 40 to 150 [1 / s] or more, preferably 45 to 125 [1 / s], and more preferably 50 to 100 [1 / s]. The range.
  • the shear viscosity of the acrylic rubber in the barrel unit 51 is not particularly limited, but is usually 4000 to 8000 [Pa ⁇ s] or less, preferably 4500 to 7500 [Pa ⁇ s], and more preferably 5000 to 7000 [Pa ⁇ s]. s].
  • the cooling device 6 shown in FIG. 1 is configured to cool the dried rubber obtained through the dehydration step by the dehydrator and the drying step by the dryer.
  • the cooling method by the cooling device 6 various methods including an air cooling method by blowing air or cooling, a water spraying method of spraying water, a dipping method of immersing in water, and the like can be adopted. Further, the dried rubber may be cooled by leaving it at room temperature.
  • the dried rubber discharged from the screw type extruder 5 is extruded into various shapes such as granular, columnar, round bar, and sheet depending on the nozzle shape of the die 59. Is molded into a sheet shape.
  • the transport type cooling device 60 for cooling the sheet-shaped dry rubber 10 formed into a sheet shape will be described with reference to FIG.
  • FIG. 3 shows the configuration of a transport type cooling device 60 suitable as the cooling device 6 shown in FIG.
  • the transport type cooling device 60 shown in FIG. 3 is configured to cool by an air cooling method while transporting the sheet-shaped dry rubber 10 discharged from the discharge port of the die 59 of the screw type extruder 5.
  • this transport type cooling device 60 the sheet-shaped dry rubber discharged from the screw type extruder 5 can be suitably cooled.
  • the transport type cooling device 60 shown in FIG. 3 is used, for example, directly connected to the die 59 of the screw type extruder 5 shown in FIG. 2 or installed in the vicinity of the die 59.
  • the transport type cooling device 60 blows cold air to the conveyor 61 that conveys the sheet-shaped dry rubber 10 discharged from the die 59 of the screw type extruder 5 in the direction of arrow A in FIG. 3 and the sheet-shaped dry rubber 10 on the conveyor 61. It has a cooling means 65 for spraying.
  • the conveyor 61 has rollers 62 and 63, and a conveyor belt 64 that is wound around the rollers 62 and 63 and on which the sheet-shaped dry rubber 10 is placed.
  • the conveyor 61 is configured to continuously convey the sheet-shaped dry rubber 10 discharged from the die 59 of the screw type extruder 5 to the downstream side (right side in FIG. 3) on the conveyor belt 64.
  • the cooling means 65 is not particularly limited, but has, for example, a structure capable of blowing cooling air sent from a cooling air generating means (not shown) onto the surface of the sheet-shaped dry rubber 10 on the conveyor belt 64. And so on.
  • the length (length of the portion where the cooling air can be blown) L1 of the conveyor 61 and the cooling means 65 of the transport type cooling device 60 is not particularly limited, but is, for example, 10 to 100 m, preferably 20 to 50 m. ..
  • the transport speed of the sheet-shaped dry rubber 10 in the transport-type cooling device 60 is the length L1 of the conveyor 61 and the cooling means 65, the discharge speed of the sheet-shaped dry rubber 10 discharged from the die 59 of the screw type extruder 5. It may be appropriately adjusted according to the target cooling rate, cooling time, etc., but is, for example, 10 to 100 m / hr, more preferably 15 to 70 m / hr.
  • the sheet-shaped dry rubber 10 discharged from the die 59 of the screw type extruder 5 is conveyed by the conveyor 61, and the sheet-shaped dry rubber 10 is transported from the cooling means 65 to the sheet-shaped dry rubber 10.
  • the sheet-shaped dry rubber 10 is cooled by blowing cooling air.
  • the transport type cooling device 60 is not particularly limited to a configuration including one conveyor 61 and one cooling means 65 as shown in FIG. 3, and two or more conveyors 61 and two or more corresponding conveyors 61. It may be configured to include the cooling means 65 of the above. In that case, the total length of each of the two or more conveyors 61 and the cooling means 65 may be within the above range.
  • the bale device 7 shown in FIG. 1 is configured to extrude from a screw type extruder 5 and further process a dry rubber cooled by the cooling device 6 to produce a bale which is a block.
  • the screw type extruder 5 can extrude the dried rubber into various shapes such as granular, columnar, round bar, and sheet, and the bale device 7 has various shapes as described above. It is configured to veil dry rubber molded into a shape.
  • the weight and shape of the acrylic rubber bale produced by the bale device 7 are not particularly limited, but for example, an acrylic rubber bale having a substantially rectangular parallelepiped shape of about 20 kg is produced.
  • the bale device 7 may include, for example, a baler, and may manufacture an acrylic rubber veil by compressing the cooled dry rubber with the baler.
  • the bale-forming device 7 arranged on the downstream side of the transport-type cooling device 60 shown in FIG. 3 may be provided with a cutting mechanism for cutting the sheet-shaped dry rubber 10.
  • the cutting mechanism of the bale device 7 continuously cuts the cooled sheet-shaped dry rubber 10 at predetermined intervals and processes the cooled sheet-shaped dry rubber 16 into a cut sheet-shaped dry rubber 16 having a predetermined size. It is configured as follows. By laminating a plurality of cut sheet-shaped dry rubbers 16 cut to a predetermined size by a cutting mechanism, a veil-shaped acrylic rubber in which the cut-sheet-shaped dry rubbers 16 are laminated can be manufactured.
  • the cut-sheet-shaped dried rubber 16 When producing a veil-shaped acrylic rubber in which the cut-sheet-shaped dried rubber 16 is laminated, it is preferable to laminate the cut-sheet-shaped dried rubber 16 at 40 ° C. or higher, for example. By laminating the cut sheet-shaped dry rubber 16 at 40 ° C. or higher, good air release is realized by further cooling and compression by its own weight.
  • [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 of them.
  • the reactive group content was confirmed by the following 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 in the rubber was The amount used for each monomer was the same.
  • the content of the reactive group in the acrylic rubber veil was measured by the following method. (1) The amount of carboxyl group was calculated by dissolving a rubber sample in acetone and performing potentiometric titration with a potassium hydroxide solution. (2) The amount of epoxy group was calculated by dissolving a rubber sample 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 the rubber sample in a combustion flask, absorbing the generated chlorine in water, and titrating with silver nitrate.
  • the amount (ppm) of each component in the acrylic rubber veil ash content was measured by XRF using ZSX Primus (manufactured by Rigaku) by pressing the ash content collected at the time of the above ash content measurement onto a ⁇ 20 mm titration filter paper.
  • the molecular weight (Mw, Mn, Mz) and molecular weight distribution (Mw / Mn and Mz / Mw) of the acrylic rubber are such that lithium chloride is 0.05 mol / L and 37% concentrated hydrochloric acid is 0.01% in dimethylformamide as a solvent. It is an absolute molecular weight and an absolute molecular weight distribution measured by the GPC-MALS method using the solutions added in 1.
  • the configuration of the gel permeation chromatography multi-angle light scattering photometer which is this device, consists of a pump (manufactured by LC-20ADOpt Shimadzu Corporation), a differential refractometer (manufactured by OptilabrEX Wyatt Technology), which is a detector, and a multi-angle. It comprises a light scattering detector (manufactured by DAWN HELEOS Wyatt Technology).
  • 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 sorted by size 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 by measuring the dissolution time.
  • the measurement conditions and measurement methods using the GPC layer are as follows.
  • 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 specific gravity of the acrylic rubber veil was measured according to the method A of JIS K6268 crosslinked rubber-density measurement.
  • the measured value obtained by the following measuring method is the density, but the density of water is 1 Mg / m 3 and the specific gravity is used.
  • the specific gravity of the rubber sample obtained according to the method A of JIS K6268 cross-linked rubber-density measurement is the mass divided by the capacity including the voids of the rubber sample, and is the JIS K6268 cross-linked rubber-density measurement. It is obtained by dividing the density of the rubber sample measured according to the method A by the density of water (when the density of the rubber sample is divided by the density of water, the numerical values are the same and the unit is lost).
  • the specific gravity of the rubber sample is determined based on the following procedure.
  • a 2.5 g test piece is cut out from a rubber sample that has been allowed to stand at a standard temperature (23 ° C ⁇ 2 ° C) for at least 3 hours, and a thin piece having a mass of less than 0.010 g is cut out from a hook on a chemical balance having an accuracy of 1 mg.
  • Using nylon thread suspend the test piece so that the bottom of the test piece is 25 mm above the distribution tray for the chemical balance, and measure the mass (m1) of the test piece twice up to mg in the air.
  • the water content was measured according to JIS K6230-1: Oven A (volatile content measurement) method.
  • the complex viscosity ⁇ is measured by measuring the temperature dispersion (40 to 120 ° C.) at a strain of 473% and 1 Hz using a dynamic viscous elasticity measuring device “Rubber Process Analyzer RPA-2000” (manufactured by Alpha Technology). The complex viscosity ⁇ at temperature was determined.
  • the dynamic viscoelasticity at 60 ° C. is defined as the complex viscoelasticity ⁇ (60 ° C.)
  • the dynamic viscoelasticity at 100 ° C. is defined as the complex viscoelasticity ⁇ (100 ° C.).
  • the value of (100 ° C.) / ⁇ (60 ° C.) was calculated.
  • Mooney viscosity (ML1 + 4,100 ° C) Mooney viscosity (ML1 + 4,100 ° C.) was measured according to the uncrosslinked rubber physical test method of JIS K6300.
  • the crosslinkability of the rubber sample is the rate of change between the breaking strength of the rubber crosslinked product subjected to secondary cross-linking for 2 hours and the breaking strength of the rubber cross-linked product subjected to 4 hours ((4 hour cross-linked rubber cross-linked product breaking strength / 2 hour cross-linking).
  • the breaking strength of the crosslinked rubber product) ⁇ 100) was calculated and judged according to the following criteria. ⁇ : Breaking strength change rate is less than 10% ⁇ : Breaking strength change rate is 10% or more
  • compression-resistant permanent strain characteristics The compression permanent strain resistance of the rubber sample was evaluated according to the following criteria by measuring the compression permanent strain rate after leaving the rubber crosslinked product of the rubber sample at 175 ° C. for 90 hours in a state of being compressed by 25% according to JIS K6262. .. ⁇ : The compression set is less than 15% ⁇ : The compression set is 15% or more.
  • the normal physical properties of the rubber sample were evaluated according to the following criteria by measuring the breaking strength, 100% tensile stress and breaking elongation of the crosslinked rubber sample of the rubber sample according to JIS K6251. (1) The breaking strength was evaluated as ⁇ when it was 10 MPa or more and ⁇ when it was less than 10 MPa. (2) The 100% tensile stress was evaluated as ⁇ for 5 MPa or more and ⁇ for less than 5 MPa. (3) The elongation at break was evaluated as ⁇ for 150% or more and ⁇ for less than 150%.
  • Example 1 As shown in Table 2-1 in a mixing container equipped with a homomixer, 46 parts of pure water, 74.5 parts of ethyl acrylate as a monomer component, 17 parts of n-butyl acrylate, and 7 parts of methoxyethyl acrylate. And 1.5 parts of mono-n-butyl fumarate and 1.8 parts of tridecyloxyhexaoxyethylene phosphate sodium salt as an emulsifier were charged and stirred to obtain a monomeric emulsion.
  • the mixture was heated to 80 ° C. and vigorously stirred at a stirring blade rotation speed of 600 rpm (peripheral speed 3.1 m / s) of the stirrer.
  • the emulsion polymer solution obtained above is heated to 80 ° C. and continuously added to coagulate the polymer in 350 parts of a coagulation solution using magnesium sulfate as an agent to coagulate the polymer, and the crumb of acrylic rubber which is a coagulated product.
  • a solidified slurry containing water was obtained. Moisture was discharged from the solidified layer while filtering the crumbs from the obtained slurry to obtain a hydrous crumb.
  • the screw type twin-screw dryer 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 consists of a barrel).
  • the first dehydration barrel drains water, and the second and third dehydration barrels drain steam.
  • Table 2-1 shows the water content, maximum torque, specific power, specific power, shear rate and shear viscosity of the screw type twin-screw extruder after dehydration (drainage).
  • Moisture content Moisture content of the hydrous crumb after drainage in the first dehydration barrel: 20% Moisture content of the hydrous crumb after steam exhaust in the third dehydration barrel: 10% Moisture content of the hydrous crumb after drying in the 5th drying barrel: 0.4% Rubber temperature: -The temperature of the hydrous crumb supplied to the supply barrel: 65 ° C -The temperature of the rubber discharged from the screw type twin-screw extruder: 140 ° C Set temperature of each barrel: -First dehydration barrel: 100 ° C -Second dehydration barrel: 120 ° C -Third dehydration barrel: 120 ° C -First drying barrel: 120 ° C -Second drying barrel: 130 ° C -Third dry barrel: 140 ° C -Fourth drying barrel: 160 ° C -Fifth drying barrel: 180 ° C Operating conditions: -Screw diameter (D): 132 mm -Overall length (L) of the screw: 4620
  • the extruded sheet-shaped dry rubber was cooled to 50 ° C., cut with a cutter, and laminated to 20 parts (20 kg) before the temperature fell below 40 ° C. to obtain an acrylic rubber veil (A). .. Reactive group content, ash content, ash component content, gel amount, pH, specific gravity, glass transition temperature (Tg), water content, molecular weight, molecular weight distribution, and 100 ° C. and 60 of the obtained acrylic rubber veil (A).
  • the complex viscosity at ° C was measured and the results are shown in Table 2-2.
  • the gel amount variation of the acrylic rubber veil (A) and the storage stability test were performed to determine the water content change rate.
  • the obtained rubber mixture was placed in a mold having a length of 15 cm, a width of 15 cm, and a depth of 0.2 cm, and was primarily crosslinked by pressing at 180 ° C. for 10 minutes while pressurizing at a press pressure of 10 MPa, and the obtained primary crosslinked product was obtained.
  • a test piece having a size of 3 cm ⁇ 2 cm ⁇ 0.2 cm was cut out from the obtained sheet-shaped rubber crosslinked product, and water resistance, compression resistance permanent strain resistance and normal physical properties were evaluated.
  • the normal physical properties of the sheet-shaped rubber crosslinked product obtained by performing the secondary cross-linking for another 2 hours were measured to evaluate the cross-linking property.
  • Table 2-2 The results are shown in Table 2-2.
  • Example 2 As a monomer component, 4.5 parts of ethyl acrylate, 64.5 parts of n-butyl acrylate, 29.5 parts of methoxyethyl acrylate and 1.5 parts of mono n-butyl fumarate, and nonylphenyloxyhexaoxy as an emulsifier. The same procedure as in Example 1 was carried out except for changing to 1.8 parts of ethylene phosphate sodium salt, acrylic rubber veil (B) was obtained, each characteristic was evaluated, and the results are shown in Table 2-2.
  • Example 3 The same procedure as in Example 1 was carried out except that the amount of potassium persulfate was changed to 0.2 part and the post-addition of n-dodecyl mercaptan was changed to 0.0072 part after 50 minutes and 0.0036 part after 100 minutes. Acrylic rubber veil (C) was obtained, each characteristic was evaluated, and the results are shown in Table 2-2.
  • Example 4 As a monomer component, 4.5 parts of ethyl acrylate, 64.5 parts of n-butyl acrylate, 29.5 parts of methoxyethyl acrylate and 1.5 parts of mono-n-butyl fumarate, and octyloxyhexoxyethylene as an emulsifier. The procedure was the same as in Example 3 except that the amount was changed to 1.8 parts of the sodium phosphate salt, acrylic rubber veil (D) was obtained, each characteristic was evaluated, and the results are shown in Table 2-2.
  • Example 5 Ethyl acrylate 28 parts, n-butyl acrylate 38 parts, methoxyethyl acrylate 27 parts, acrylonitrile 5 parts and allyl glycidyl ether 2 parts, maximum torque of screw type twin-screw extruder is 45 Nm Acrylic rubber veil (E) was obtained, each characteristic (the compounding agent was changed to "formulation 2") was evaluated, and the results are shown in Table 2-2. rice field.
  • Example 6 The same procedure as in Example 5 was carried out except that the monomer component was changed to 48.5 parts of ethyl acrylate, 50 parts of n-butyl acrylate and 1.5 parts of mono-n-butyl fumarate, and the acrylic rubber veil (F) was used. Each characteristic (the compounding agent was changed to "formulation 1") was evaluated, and the results are shown in Table 2-2.
  • Example 7 The same procedure as in Example 5 was carried out except that the monomer component was changed to 48.25 parts of ethyl acrylate, 50 parts of n-butyl acrylate and 1.75 parts of mono-n-butyl fumarate, and the acrylic rubber veil (G) was used. Each characteristic (the compounding agent was changed to "formulation 3") was evaluated, and the results are shown in Table 2-2.
  • Example 8 Ethyl acrylate 28 parts, n-butyl acrylate 38 parts, methoxyethyl acrylate 27 parts, acrylonitrile 5 parts and allyl glycidyl ether 2 parts, maximum torque of screw type twin-screw extruder is 45 Nm Acrylic rubber veil (H) was obtained, each characteristic (the compounding agent was changed to "formulation 2") was evaluated, and the results are shown in Table 2-2. rice field.
  • Example 9 Acrylic rubber veil (I) was carried out in the same manner as in Example 8 except that the monomer component was changed to 48.5 parts of ethyl acrylate, 50 parts of n-butyl acrylate and 1.5 parts of mono-n-butyl fumarate. Each characteristic (the compounding agent was changed to "formulation 1") was evaluated, and the results are shown in Table 2-2.
  • Example 10 The same procedure as in Example 8 was carried out except that the monomer component was changed to 48.25 parts of ethyl acrylate, 50 parts of n-butyl acrylate and 1.75 parts of mono-n-butyl fumarate, and the acrylic rubber veil (J) was used. Each characteristic (the compounding agent was changed to "formulation 3") was evaluated, and the results are shown in Table 2-2.
  • the emulsion polymerization solution was heated to 80 ° C., and while stirring at a stirring blade rotation speed of 100 rpm (peripheral speed 0.5 m / s) of the stirrer, a 0.7% magnesium sulfate aqueous solution (sulfate as a coagulant) was used.
  • a coagulation liquid using magnesium was added to coagulate the polymer to obtain a coagulation slurry containing a solidified acrylic rubber crumb and water. Moisture was discharged from the solidified layer while filtering the crumbs from the obtained slurry to obtain a hydrous crumb.
  • the acrylic rubber veil (A) to (J) and the crumb-shaped acrylic rubber (K) to (L) produced under the conditions of the Examples and Comparative Examples of the present application have a carboxyl group, an epoxy group and chlorine. Since it has an ionic reactive group such as an atom and the absolute molecular weight (Mn, Mw, Mz) measured by the GPC-MALS method has a certain size, it has short-time crosslinkability and compression resistance. It can be seen that it is excellent in both the permanent strain characteristics and the normal physical properties including the strength characteristics (Examples 1 to 10 and Comparative Examples 1 to 2). However, it can be seen that the crumb-shaped acrylic rubbers (K) to (L) are inferior in both gel amount variation, roll processability and Banbury processability, and are also inferior in water resistance and storage stability (comparison). Examples 1-2).
  • the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn), which is the molecular weight distribution in the low molecular weight region, is important. It can be seen that the roll workability can be significantly improved by expanding the roll (comparison between Examples 1 to 10 and Comparative Examples 1 and 2).
  • the acrylic rubber veil having excellent roll processability and highly balanced with the strength characteristics is added with a small amount of the inorganic radical generator and the chain transfer agent (n-). It can be seen that it can be produced by adding dodecyl mercaptan) in batches (Examples 1 to 10). This is because the amount of the inorganic radical generator is reduced to extend one polymerized chain, and the chain transfer agent (n-dodecyl mercaptan) is post-added in batches to combine the high molecular weight component and the low molecular weight component to achieve a high molecular weight. It is presumed that the roll workability could be improved without impairing the strength characteristics by increasing Mw / Mn with an emphasis on the region.
  • the reducing agent sodium ascorbate was added 120 minutes after the start of polymerization, whereby the high molecular weight component of acrylic rubber could be easily generated.
  • the strength characteristics and roll workability characteristics are highly balanced.
  • the acrylic rubber veils (A) to (J) of the present invention having an overwhelmingly small amount of gel are excellent (Examples 1 to 10 and Comparative Examples 1 to 2). Comparison with).
  • the polymerization conversion rate is emulsified to about 100% in order to improve the strength characteristics, but the gel amount of the methyl ethyl ketone insoluble content increases sharply as the polymerization conversion rate is increased, and the Banbury processability is improved.
  • the gel amount of BIT Black Corporation Time
  • the amount of methyl ethyl ketone insoluble matter is on the line of a very high correlation coefficient.
  • the gel amount of the methyl ethyl ketone insoluble portion of the crumb-shaped acrylic rubber obtained by directly drying the hydrous crumb that had been washed as in Example 1 was 23% by weight, and the Banbury processability index was about 36. I have confirmed that it was there.
  • the method that can reduce the gel amount of the methyl ethyl ketone insoluble matter in the acrylic rubber veil or the crumb-shaped acrylic rubber is the method of post-adding a chain transfer agent in the latter half of the emulsion polymerization of the acrylic rubber or washing the water-containing crumb generated in the coagulation step.
  • a method of melt-kneading and extrusion-drying with a screw-type twin-screw extruder in a state of substantially no water content (water content of less than 1% by weight) but the latter method was overwhelmingly superior. ..
  • the acrylic rubber veil of the present invention is remarkably excellent and that the amount of ash in the acrylic rubber veil is greatly involved (Examples 1 to 10).
  • the amount of ash in the acrylic rubber veil is determined by the type of emulsifier or coagulant, coagulant method, property method, dehydration method, etc., but the amount of ash in the acrylic rubber veil (A) to (J) of the present invention is determined.
  • the amount can be significantly reduced (comparison between Examples 1 to 10 and Comparative Examples 1 and 2).
  • the emulsion polymerization solution is added to the coagulating liquid that is agitated very violently at a peripheral speed of 1 m / s or more, and the coagulation reaction is carried out.
  • most of the hydrous crumbs produced by the coagulation method performed in this example are focused on a small particle size of 710 ⁇ m to 4.75 mm, and therefore, the washing efficiency and dehydration with warm water are achieved. It is presumed that the ash removal efficiency was significantly improved and the water resistance of the acrylic rubber veil of the present invention could be improved.
  • the acrylic rubber veil obtained by performing the operation after the solidification step in the same manner as in Example 1 after the polymerization reaction of Comparative Example 2 the ash content is about 0.08% by weight. It has been confirmed that the water resistance can be improved.
  • the acrylic rubber veils (A) to (J) of the present invention have a variation in gel amount, both processability of roll processability and Banbury processability, and crosslinkability. It can be seen that it is excellent in compression resistance permanent strain resistance and strength characteristics, and is also remarkably excellent in storage stability (Examples 1 to 10).
  • the acrylic rubber veils (A) to (J) of the present invention have a large specific gravity, that is, they do not entrain air and are excellent in storage stability. In the present invention, since the acrylic rubber veil does not entrain air, the air inside the acrylic rubber is removed under reduced pressure at the drying barrel portion in the screw type twin-screw extruder, and the moisture is substantially not contained.
  • the resin pressure of the die part is limitedly extruded, the sheet-shaped dry rubber is cut and laminated at a specific temperature, and the sheet-shaped dry rubber after cutting is set to a specific temperature.
  • the specific gravity is increased (the contained air is eliminated) and the storage stability is remarkably improved (comparison between Examples 1 to 10 and Comparative Examples 1 and 2).
  • the pH of the acrylic rubber veil of the present invention is in a specific region of 3 to 6, which also contributes to storage stability (comparison between Examples 1 to 10 and Comparative Example 2).
  • the evaluation of each characteristic of the acrylic rubber veils (A) to (J) of the present invention was the same as the evaluation of each characteristic of the corresponding acrylic rubber sheets (A) to (J) of the present invention.
  • the Mooney scorch time t5 (minutes) at a temperature of 125 ° C. was set by the above-mentioned method for evaluating the processing stability by suppressing Mooney scorch. Measurements were made according to JIS K 6300, and Mooney Scorch storage stability was evaluated according to the following criteria. As a result, all of them were good results of " ⁇ ".
  • Mooney scorch time t5 exceeds 2.0 minutes ⁇ : Mooney scorch time t5 is 1.5 to 2.0 minutes ⁇ : Mooney scorch time t5 is less than 1.5 minutes
  • the cooling rate of the sheet-shaped dry rubber extruded from the screw type twin-screw extruder is approximately 200 ° C./hr, which is as fast as 40 ° C./hr or more, as in Example 1. Is.

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