JPH09137000A - Elastomer composition containing metal salt of ethylenically unsaturated carboxylic acid, and vulcanized elastomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an elastomer compsn. contg. a metal salt of ethylenically unsatd. carboxylic acid which compsn. has a good mold releasability without lowering of the properties of a vulcanization product of an elastomer by blending the elastomer with a specific surfactant. SOLUTION: An elastomer is blended with a metal salt of ethylenically unsatd. carboxylic acid and a sulfur element- or phosphorus element-contg. anionic surfactant to prepare an elastomer compsn. contg. the metal salt of ethylenically unsatd. carboxylic acid. The nonionic surfactant is a sulfuric acid salt, sulfuric ester salt or phosphoric ester salt surfactant. 100 pts.wt. elastomer is usually blended with 3-120 pts.wt. metal salt of ethylenically unsatd. carboxylic acid and 0.5-10 pts.wt. nonionic surfactant. This compsn. can be converted into a vulcanized elastomer by using an org. peroxide. Vulcanization molding can be efficiently done in a mold coated with an org. fluorine compd. base releasing agent.

Description

Detailed Description of the Invention TECHNICAL FIELD OF THE INVENTION

The present invention relates to an elastomer composition having excellent mold releasability and a molding method for efficiently vulcanizing the elastomer composition, and more specifically, an ethylenically unsaturated carboxylic acid having excellent mold releasability. The present invention relates to a method for molding a vulcanized elastomer, which comprises using an organic fluorine compound-based release agent when vulcanizing and molding using a metal salt-containing elastomer composition and an organic peroxide.

[0002]

2. Description of the Related Art Ethylenically unsaturated nitrile-conjugated diene copolymer rubber and other diene rubber and ethylene-
A vulcanizable elastomer composition prepared by blending a propylene copolymer rubber or the like with a methacrylic acid or other α, β-ethylenically unsaturated carboxylic acid, a divalent metal compound such as zinc and an organic peroxide, It is known to provide a vulcanized elastomer product having high mechanical strength (JP-A-54-57553, JP-A-60-215085, JP-A-1-306443). These vulcanizable elastomer compositions react with not only the elastomer component but also methacrylic acid and other α, β-ethylenically unsaturated carboxylic acids, zinc and other divalent metal compounds and organic peroxides during vulcanization. Is believed to form a crosslinked polymer. However, in the case of an elastomer composition containing an α, β-ethylenically unsaturated carboxylic acid and a divalent metal compound, the mold releasability is extremely poor in spite of excellent strength properties, Only a large amount of release agent can be used at the expense of the properties of the elastomer product, or the nickel plating / Teflon coating of the mold can be repeated at the expense of economy, resulting in excellent strength properties. There has been a need for an ethylenically unsaturated carboxylic acid metal salt-containing elastomer composition which has the above-mentioned properties and which can inexpensively obtain an elastomer product having a clean surface.

The applicant has already reported a method of blending a higher fatty acid metal salt such as sodium stearate in order to meet such requirements (Japanese Patent Laid-Open No. 4-298546).
JP-A-6-107740). However, although the mold releasability is improved by this method, the tensile stress of the elastomer product tends to be slightly decreased because a relatively large amount of higher fatty acid salt is required. found.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an ethylenically unsaturated carboxylic acid metal salt-containing elastomer composition having good mold releasability without deteriorating the properties of the elastomer vulcanizate. It is in. A further object of the present invention is to provide a molding method for efficiently vulcanizing the ethylenically unsaturated carboxylic acid metal salt-containing elastomer composition having good mold releasability. Therefore, as a result of intensive studies by the present inventor, by mixing sodium alkylbenzene sulfonate with an ethylenically unsaturated carboxylic acid metal salt-containing elastomer composition, the mold releasability is improved while maintaining the properties of the elastomer product. It was found that it is possible to further vulcanize and mold the elastomer composition efficiently by using an organic fluorine compound-based mold release agent as an external mold release agent together,
The present invention has been completed based on this finding.

[0005]

According to the present invention, the following [1] and [2] are provided. [1] Elastomer composition containing ethylenically unsaturated carboxylic acid metal salt obtained by blending (A) elastomer, (B) ethylenically unsaturated carboxylic acid metal salt and (C) elemental sulfur-containing or phosphorus element-containing anionic surfactant Stuff. [2] A vulcanizable composition obtained by blending the ethylenically unsaturated carboxylic acid metal salt-containing elastomer composition described in [1] with an organic peroxide is coated with an organic fluorine compound-based release agent. A method for molding a vulcanized elastomer, which comprises vulcanizing and molding in a mold.

The specific modes of the present invention are as follows. (1) The ethylenically unsaturated carboxylic acid metal salt-containing elastomer composition is (B) ethylenically unsaturated carboxylic acid metal salt 3 to 12 with respect to 100 parts by weight of the elastomer (A).
0 parts by weight and 0.5 to 10 parts by weight of (C) elemental sulfur or phosphorus-containing anionic surfactant. (2) The elastomer (A) has an iodine value of 1 to 50, a bound unsaturated nitrile amount of 10 to 60% by weight, and a Mooney viscosity of 20.
~ 150 hydrogenated acrylonitrile-butadiene copolymer rubber. (3) The (B) ethylenically unsaturated carboxylic acid metal salt is zinc dimethacrylate. (4) The (C) elemental sulfur-containing or phosphorus-containing anionic surfactant is a sulfonate-based surfactant. (5) The sulfonate-based surfactant has 10 to 18 carbon atoms.
It is an alkylbenzene sulfonate having an alkyl group of. (6) The sulfonate surfactant is sodium dodecylbenzene sulfonate. (7) In the method for molding a vulcanized elastomer, the amount of the organic peroxide used is 1 with respect to 100 parts by weight of the elastomer.
To 10 parts by weight. (8) The organic fluorine compound-based release agent used in the method for molding a vulcanized elastomer contains a perfluorosulfonic acid salt-based organic fluorine compound.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The elastomer used in the present invention is not particularly limited as long as it is generally used for producing various elastomer products, and examples thereof include natural rubber (NR) and polyisoprene rubber (IR). , Polybutadiene rubber (BR), chloroprene rubber (CR), isobutylene-isoprene copolymer rubber (IIR), styrene-butadiene copolymer rubber (SBR), acrylonitrile-isoprene copolymer rubber (NIR), acrylonitrile-butadiene copolymer Polymer rubber (NBR), hydrogenated acrylonitrile-butadiene copolymer rubber (HNB
R), ethylene-propylene-diene copolymer rubber (E
PDM) and the like. The Mooney viscosity of these various elastomers is usually 20 to 150. BR is high ci
s-1,4-bonded BR and high vinyl bonded BR.
SBR usually has a styrene content of 5 to 35% by weight. NB
R is usually 10 to 60% by weight of bound acrylonitrile.
It is. The elastomers may be used alone or in combination of two or more.

Among these elastomers, when hydrogenated acrylonitrile-butadiene copolymer rubber is used, an elastomer composition having a high hardness and a low viscosity can be obtained, and a high strength excellent in heat resistance, oil resistance and the like can be obtained. An elastomer product can be obtained. Hydrogenated acrylonitrile-
The butadiene-based copolymer is a hydrogenated butadiene unit portion of an acrylonitrile-butadiene copolymer and an acrylonitrile-butadiene-ethylenically unsaturated monomer copolymer.

These are obtained by subjecting a copolymer produced by emulsion polymerization or solution polymerization to a conventional method (for example, Japanese Examined Patent Publication No.
The conjugated diene unit portion in the copolymer is hydrogenated by the method described in JP-A No. 0-58242, JP-B No. 62-61045, etc.). The iodine value is 1 to 120, preferably 1 to 50 in view of heat resistance.

The copolymerizable ethylenically unsaturated monomers used in the production of these copolymers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid; methyl acrylate, butyl acrylate,
Dimethyl maleate, diethyl fumarate, di-fumarate
alkyl esters of said carboxylic acids such as n-butyl, di-n-butyl itaconic acid; methoxy acrylate,
Alkoxyalkyl monoesters or diesters of said unsaturated carboxylic acids such as ethoxyethyl acrylate, methoxyethoxyethyl acrylate; α- and β-cyanoethyl acrylate, α-, β- and γ-
Acrylates having a cyanoalkyl group such as cyanopropyl acrylate, cyanobutyl acrylate and cyanooctyl acrylate; acrylates having a hydroxyalkyl group such as 2-hydroxyethyl acrylate and hydroxypropyl acrylate; acrylamide, methacrylamide; N-methylol (meth) It includes N-substituted (meth) acrylamides such as acrylamide, N, N-dimethylol (meth) acrylamide, N-ethoxymethyl (meth) acrylamide and the like. In addition to these monomers, a part of the unsaturated monomer is usually 0 to 10% by weight within a range not impairing the gist of the present invention.
It may be substituted with a vinyl-based monomer such as styrene or vinyl pyridine, or a non-conjugated diene such as vinyl norbornene, dicyclopentadiene or 1,4-hexadiene.

Specific examples of hydrogenated acrylonitrile-butadiene type copolymers include hydrogenated butadiene-acrylonitrile copolymer rubbers; butadiene-methyl acrylate-acrylonitrile copolymer rubbers, butadiene-acrylic acid-acrylonitrile copolymer rubbers, Examples include hydrogenated butadiene-di-n-butyl itaconic acid-acrylonitrile copolymer rubber and the like.

The amount of bound unsaturated nitrile in the copolymer rubber is usually 5 to 60% by weight, preferably 10 because of the requirement of oil resistance.
５０50% by weight. Further, the amount of the copolymerizable ethylenically unsaturated monomer in the copolymer is usually 0 to 40% by weight.

The ethylenically unsaturated carboxylic acid metal salt used in the present invention has a structure in which an ionic bond is formed between an ethylenically unsaturated carboxylic acid having 1 or 2 or more carboxyl groups and having 5 or less carbon atoms and a metal. Anything will do.

Examples of the ethylenically unsaturated carboxylic acid include monocarboxylic acids such as acrylic acid and methacrylic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; unsaturated carboxylic acids such as monomethyl maleate and monoethyl itaconate. Examples thereof include monoester compounds having an alkyl group having 1 to 8 carbon atoms. The metal is not particularly limited as long as it forms a salt with the ethylenically unsaturated carboxylic acid, but usually zinc, magnesium, calcium, barium, titanium, chromium, iron, cobalt, nickel, aluminum, tin, lead. Among these, zinc, magnesium, calcium, and aluminum are suitable from the viewpoint of strength characteristics, and zinc is particularly preferable.

The molar ratio of the above ethylenically unsaturated carboxylic acid to the metal is preferably within the range of 1 / 0.5 to 1/3.

These ethylenically unsaturated carboxylic acid metal salts may be added to the elastomer in the form of metal salts when the elastomer composition is produced by blending and kneading with other components. The unsaturated carboxylic acid and the oxide, hydroxide, or carbonate of the above-mentioned metal may be added to react with each other during an operation such as kneading to generate the carboxylic acid.

The amount of the ethylenically unsaturated carboxylic acid metal salt used is not particularly limited, but is usually 3 to 120 parts by weight, preferably 5 to 100 parts by weight, particularly preferably 10 to 60 parts by weight, per 100 parts by weight of the elastomer. Used in the range. If the amount used is too small or too large, the strength properties of the elastomer product will be poor, which is not preferable.

The elemental sulfur-containing or phosphorus-containing anionic surfactant used in the present invention is (1) sulfonic acid IA, I
Sulfonate type surfactant which is a salt of IA or IIB metal, (2) IA and II of ester of sulfuric acid and alcohol
Sulfate ester salt-based surfactant which is a salt of A or IIB metal, and (3) phosphate ester IA, IIA or I
It is a phosphate ester salt type surfactant which is a salt of IB metal.

Examples of the IA, IIA or IIB metal include lithium, sodium, potassium, magnesium, calcium, barium and zinc. Among them, sodium is awarded.

As the sulfonic acid of the sulfonate surfactant (1), alkylsulfonic acid having 11 to 18 carbon atoms; lower alkylnaphthalenesulfonic acid having lower alkyl group having 1 to 4 carbon atoms, lower dialkylnaphthalene sulfone Acid, benzylnaphthalenesulfonic acid, dinaphthylmethanesulfonic acid, α-naphthalenesulfonic acid, 1,
3,6-naphthalene trisulfonic acid, tetralin sulfonic acid, octahydroanthracene sulfonic acid, benzyl sulfanilic acid, dimethylmethanilic acid, alkylphenol sulfonic acid, alkylnaphthol sulfonic acid, cyclohexylnaphthalene sulfonic acid, naphthalene condensate sulfonic acid, rosin sulfone Acids, lower alkylaryl sulfonic acids such as terpineol sulfonic acid, lignin sulfonic acid; alkylbenzene sulfonic acids having alkyl groups having 10 to 18 carbon atoms, alkylnaphthalene sulfonic acids, alkylphenol sulfonic acids, oleic acid-bonded aryl sulfonic acids, alkenylphenol sulfones acid,
Higher alkylaryl sulfonic acids such as terpene phenol sulfonic acid, dilauryl naphthalene sulfonic acid, alkyldesoxybenzoin sulfonic acid, acylbenzene (naphthalene) sulfonic acid, alkyl rosin sulfonic acid; sulfophthalic acid ester, substituted sulfophthalic acid ester, sulfobenzoic acid Ester-linked alkylaryl sulfonic acids such as esters, sulfosalicylic acid esters, sulfophenoxyacetic acid esters, phenolic ester sulfonic acids; arylamidosulfonic acid, acylmethanilic acid, o-toluididsulfonic acid, naphthenic acid anilidesulfonic acid, acylaminoarylsulfonic acid , Acylanidine (toluidine) sulfonic acid, phenoxyacetic acid octylcyclohexylamide sulfonic acid, hexadecylamine-4-sulfof Ruamido, 4-sulfophthalic acid acyl amino anilide, acylaminomethyl phenolsulfonic acid, acyl aminoethyl ether sulfonate, amide-bonded alkyl aryl sulfonic acids such as fatty acid-phenyl hydrazide acid; carbons 8-2
Alkane sulfonic acids having 0 alkyl group, petroleum sulfonic acid, hydroxyalkyl sulfonic acid, α-sulfo fatty acid, keto sulfonic acid, ethylene telomerized sulfonic acid and the like; taurine-derived amide bond sulfonic acid, aminomethane sulfonic acid Type amide-bonded sulfonic acid, formaldehyde condensate of amide and taurine, amide-bonded sulfonic acid obtained from aliphatic amine, mercaptoethanesulfonic acid derivative, urethane-bonded sulfonic acid, urea-bonded sulfonic acid, amide-urethane-bonded sulfonic acid, mixed amide Amide-bonded sulfonic acids such as stilsulfonic acid, sulfosuccinimide, and sulfomaronic acid dialkylamide; ether-bonded sulfonic acids such as aliphatic ether-bonded sulfonic acids and aromatic ether-bonded sulfonic acids; sulfoxide-bonded sulfonic acids Phosphoric acid, thioether-bonded sulfonic acid, amide thioether-bonded sulfonic acid, sulfonamido-bonded sulfonic acid, thioether-bonded sulfonic acid such as thioamide-bonded sulfonic acid; phenol ether sulfonic acid, cresol ether sulfonic acid, resorcin ether sulfonic acid, phenoxyethyl alkyl ether Sulfonic acid, phenoxyethyl alkylphenol ether sulfonic acid, benzyl ether sulfonic acid, phenylbenzyl ether sulfonic acid, thioether linked alkylaryl sulfonic acid, sulfone linked alkylaryl sulfonic acid, acetal linked alkylaryl sulfonic acid, sulfonic acid / ester linked alkylaryl sulfone Ether bond of acid, heterocyclic bond alkylaryl sulfonic acid, indole sulfonic acid, etc. Bonding type alkyl aryl sulfonic acid and the like.

As the sulfuric acid ester of the sulfuric acid ester salt surfactant (2), higher alcohols having an alkyl group having 8 to 18 carbon atoms such as sodium octyl sulfate, sodium laurate, sodium cetyl sulfate, and sodium stearyl sulfate can be obtained. Sulfate, higher alcohol
Sulfate amine salt, oxo alcohol sulfate, elaidyl alcohol sulfate, abiethyl alcohol sulfate, naphthene alcohol sulfate, sterine sulfate, 4-octyl-2
-Sulfate of alicyclic alcohol such as methylcyclohexanol, hydrogenated benzylcresol, hydrogenated amylphenol and hydrogenated bisphenol, sulfate of halogen alcohol such as chlorohydrin, sulfate of alcohol such as higher glycol sulfate; 1 -Hexadecene sulphate, heptadecene sulphate,
Sulfuric acid ester of petroleum olefin, paraffin wax Pyrolytic olefinic sulfuric acid ester, polymerized olefin (C8
~ 20) sulfate ester, squalene sulfate ester,
Olefin sulfate such as terpene sulfate; sulfated monoglyceride, ricinoleic acid monoglyceride sulfate, ricinol, oleic acid propyl,
Sulfate of fatty acid ester obtained from butyl, amine ester, etc., sulfate of acetylated ricinoleic acid,
Sulfate of oleyl alcohol, Sulfate of sperm whale oil, Sulfate of naphthenate, Sulfate of glycol naphthenate, Sulfate of hexanediol fatty acid ester, Sulfate of oxyester, Sulfate of polyoxycarboxylic acid Sulfate of fatty acid tetrahydrofurfuryl ester, formaldehyde condensed ester-bound sulfate, methacrylic alcohol fatty acid ester sulfate, hydrogenated rosin pentaerythritol ester sulfate, polyhydric alcohol monoester sulfate ester-linked sulfate ester Fatty acid amide sulfate, fatty acid anilide sulfate, fatty acid ethanolamide sulfate, acylaminocyclohexanol sulfate, fatty acid allylamide sulfate, Amido-sulfated esters such as gomic acid amide-sulfuric acid ester, urethane-bonded sulfuric acid ester, amide-sulfonamide-bonded sulfuric acid ester; glycol ether, polyethylene glycol ether, alkylphenol glycol ether, alkylphenol-glycerin ether, alkylphenylcarbinol glycerin ether, alkoxycyclo Hexanol, fatty acid polyoxyethylene amide, alkylphenol allyl ether, fatty alcohol glycoside, hydroxythioether, hydroxysulfone, ether-bonded sulfuric acid ester which is a sulfuric acid ester such as sulfonylaminoethanol and the like can be mentioned.

As the phosphoric acid ester salt-based surfactant (3), a phosphoric acid ester of choline, an alkyl phosphoric acid ester, an unsaturated acid phosphoric acid ester, a fatty alcohol polyoxyalkyl ether phosphoric acid ester, an alkylphenol phosphoric acid ester, Examples thereof include polyhydric alcohol / fatty acid / phosphoric acid ester, oxyacid ester phosphoric acid ester, alkyl perphosphoric acid ester, alkyl phosphorous acid ester and other phosphoric acid esters.

In addition to these compounds, alkylphosphonic acid, alkylarylphosphonic acid, phosphinic acid amine salt, acyloxyphosphonic acid, ketophosphonic acid, phosphonic acid sulfate, and other phosphonic acids; alkylsulfinic acid, alkylthiosulfate, alkylhydro Sulfite ester, alkyl persulfate ester, alkylsulfamic acid, amide bond sulfamic acid, alkylsulfonamide, alkylacylsulfonamide, alkyldisulfonimide, alkylsulfonylurea, alkyldithiocarbamic acid and the like can also be used.

These anionic surfactants can be blended alone or in combination of two or more. Among the surfactants, a sulfonate-based surfactant (1) is awarded, and an alkylbenzene sulfonate having an alkyl group having 10 to 18 carbon atoms is particularly preferable, and sodium dodecylbenzene sulfonate is particularly preferable. .

The amount of the anionic surfactant used is not particularly limited, but is usually 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight with respect to 100 parts by weight of the elastomer.
If the amount used is too small, the mold releasability is not improved. On the other hand, if the amount is excessively large, the strength characteristics of the elastomer vulcanizate deteriorate, which is not preferable.

A higher fatty acid metal salt may be further added to the elastomer composition of the present invention, if desired. Examples of higher fatty acids include caproic acid, caprylic acid, capric acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotone. Saturated fatty acids such as acids, montanic acid and melissic acid; unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, linolenic acid and arachidonic acid.

The metal used for synthesizing the metal salt of higher fatty acid is not particularly limited, but lithium,
Alkali metals such as potassium and sodium; magnesium; alkaline earth metals such as calcium and barium; zinc group metals such as zinc and cadmium; carbon group metals such as tin and lead; group VIII metals such as nickel; preferred elastomer products. From the characteristics, among others, alkali metals, alkaline earth metals, zinc group metals, carbon group metals,
Lithium, sodium, potassium, calcium, barium, zinc and tin are preferred.

The amount of the higher fatty acid metal salt used is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the elastomer.

The ethylenically unsaturated carboxylic acid metal salt-containing elastomer composition of the present invention can be made into a vulcanized elastomer by using an organic peroxide.

Although the organic peroxide is not particularly limited, it is usually dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy). Hexin-3,
2,5-dimethyl-2,5-di (benzoylperoxy) hexane and the like can be mentioned. These organic peroxides are used alone or in combination of two or more, and are usually used in an amount of 0.2 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the elastomer.

The elastomer composition of the present invention is prepared by kneading the above-mentioned elastomer and each compounding agent with a roll, Banbury, or the like. In addition to these compounding agents, various carbon blacks normally used in the elastomer industry,
Various compounding agents such as a reinforcing agent such as white carbon, a filler such as calcium carbonate, clay and talc, a plasticizer, an antiaging agent, an ultraviolet absorber, a softening agent, a foaming agent and a coloring agent can be added.

Vulcanization of the elastomer composition of the present invention may be carried out in either one step or two steps, but in the case of carrying out in two steps, the vulcanization temperature of the first step is preferably about 140 to 180 ° C. The vulcanization time depends on the temperature, but is generally 2 minutes to 20 minutes. 2
The vulcanization temperature of the first step is preferably about 10 ° C. higher than the temperature of the first step.

The elastomer composition of the present invention can be vulcanized and molded into various elastomer products by known molding methods such as die press molding, injection molding, transfer molding and the like. By performing such vulcanization molding in a mold coated with an organic fluorine compound-based release agent, the vulcanized elastomer can be molded efficiently.

The organic fluorine compound-based release agent used is one which forms a liquid or a solid at the molding temperature of the vulcanized elastomer, and includes, for example, perfluorosulfonic acid salt-based compounds, fluorinated organic compound-based compounds, and fluorine-based compounds. Examples thereof include those containing an addition polymer system of fluorinated olefin and a fluorinated ether type organic fluorine compound.

The perfluorosulfonic acid salt-based organic fluorine compounds include disodium N-perfluorooctanesulfonylglutamate and sodium 3- (fluoroalkyl (C6 to C11) oxy-1-alkyl (C3 to C4) sulfonate. , 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium salt, N- [3- (perfluorooctanesulfonamido) propyl] -1-N, N-dimethyl- N-carboxymethylene ammonium betaine, perfluorooctanesulfonic acid diethanolamide, perfluoroalkyl (C4 to C12) lithium sulfonate,
Perfluoroalkyl (C4 -C12) sulfonate potassium, sodium perfluoroalkyl (C4 -C12) sulfonate, N-propyl-N- (2-hydroxyethyl) perfluorooctane sulfonamide, perfluoroalkyl (C6 -C10) Octanesulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6 to C10) -N-ethylsulfonylglycinate potassium, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate and the like.

Fluorinated organic compound-based organic fluorine compounds include perfluoroacetic acid, perfluorobutyric acid, and perfluorocarboxylic acids such as lithium salt, sodium salt or potassium salt thereof and salts thereof; fluoroalkyl (C 2-). C10) Carboxylic acid and its salts; Perfluorocarboxylic acid alkyl esters such as methyl ester, ethyl ester, propyl ester and butyl ester of perfluorocarboxylic acid; Fluoroalkyl (C2 -C
10) Alkyl esters of carboxylic acids; polymers of perfluoroalkyl acrylates or methacrylates, or copolymers thereof with butyl acrylate, butyl methacrylate, stearyl acrylate, stearyl methacrylate, etc.

Examples of the addition polymer type organic fluorine compound of fluorinated olefins include polyhexafluoropropene, polytetrafluoroethylene, polytrifluoroethylene chloride, and polyvinylidene fluoride, which are oily or resinous polymers. Is.

Examples of the fluorinated ether type organic fluorine compound include methyl polyoxyethylene perfluorononyl ether, methyl polyoxypropylene perfluorononyl ether, methyl polyoxyethylene perfluorooctyl ether, and methyl polyoxyethylene perfluorostearyl. Ether, perfluoroalkyl ether such as ethyl polyoxyethylene perfluorononyl ether; 3-perfluoropentyl-1,2-epoxypropane ring-opening polymer, 3-perfluoropentyl-
An oily or resin-like ring-opening polymer of fluoroepoxide such as a ring-opening copolymer of 1,2-epoxypropane and ethylene oxide, epichlorohydrin or the like.

Of these, the perfluorosulfonate system is superior in performance. Each of these organic fluorine compound-based release agents can be used alone, but two or more of them may be used in combination. Further, a release agent other than the organic fluorine compound release agent, for example, a silicon release agent or a metal soap release agent may be used in combination. The use amount thereof is suitably 50% by weight or less, preferably 30% by weight or less based on the organic fluorine compound-based release agent from the viewpoint of not impairing the performance of the organic fluorine compound-based release agent.

The organic fluorine compound-based release agent used in the present invention is usually dissolved or dispersed in an organic solvent or an aqueous medium before use. As the organic solvent or aqueous medium,
For example, alcohols such as methanol, ethanol, propanol and isopropanol; ketones such as acetone, methyl ethyl ketone and ethyl isobutyl ketone; ethers such as ethyl ether, isopropyl ether, dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; Hydrocarbons such as hexane, cyclohexane, toluene, xylene; halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, trichloroethylene, perchlorethylene, trichloroethane, trichlorofluoromethane, tetrachlorodifluoroethane, trichlorotrifluoroethane; And water. These can be used alone, but two or more kinds may be used in combination.

The concentration of the organic fluorine compound-based release agent in the organic solvent solution or aqueous dispersion is usually preferably about 0.05 to 10% by weight.

A known method can be used for coating the mold with the organic fluorine compound-based release agent. For example, by immersing the mold in a solution or dispersion of the release agent, by spraying or brushing the solution or dispersion of the release agent on the mold, or by dipping and dipping the cloth. There is a method of coating and then evaporating and removing the organic solvent or water.

The temperature of the mold when applying the release agent is not particularly limited, but is usually 25 to 180 ° C. It is convenient for work to keep the temperature of the mold at the molding temperature.

[0044]

The present invention will be described more specifically with reference to the following examples. Parts and% in the examples are based on weight unless otherwise specified. In this example, the mold releasability and other evaluations were performed by the following methods.

(Mold releasability test) Using the test piece and hard chrome plated plate shown below, the press operation was repeated according to the following procedure, and the repeatable number of times and the adhesion state of the elastomer to the chrome plated plate were examined. It was judged. Approximately 25 mm long and 40 m wide from unvulcanized elastomer composition
A test piece having a thickness of m and a thickness of about 2 mm is prepared. About 5 g of this test piece is sandwiched between two hard chrome-plated plates and pressed at 170 ° C. under a pressure of 100 kg / cm ² for 20 minutes. Next, the press is stopped, the chrome-plated plate is removed, and the state of adhesion of the elastomer to the chrome-plated plate is visually determined according to the following criteria. Next, after removing the adhered elastomer, the pressing operation is repeated again using a new test piece. This pressing operation is repeated until the chrome plated plate cannot be easily removed due to the adhesion of the elastomer (up to 20 times). ⊚: No adhesion of elastomer. ○: A slight amount of adhesion. Δ: A small amount of adhesion. X: A large amount of adhesion.

(Tensile test) Conducted in accordance with JIS K6301 (Test piece: No. 3 dumbbell, tensile speed 500 mm /
Minutes).

(Hardness test) The hardness test is performed according to JIS K6301 (based on JIS hardness A).

(Tear Test) Conducted in accordance with JIS K6301 (using a JIS B type test piece, pulling speed 5
Measure at 00 mm / min. ).

Example 1 Experiment Nos. 1 to 12, Comparative Example
Experimental numbers 1 to 5) Hydrogenated acrylonitrile-butadiene copolymer rubber (HNBR: bound acrylonitrile amount 3)
6%, iodine value 28, Mooney viscosity 78) or acrylonitrile-butadiene copolymer rubber (NBR: bound acrylonitrile amount 33.5%, iodine value 28, Mooney viscosity 78) 100 parts, zinc methacrylate 85 parts, Naugard 445 ( Uniroyal, amine anti-aging agent)
1.5 parts, α, α′-bis (t-butylperoxy) m
-5.0 parts of diisopropylbenzene and a predetermined amount of various anionic surfactants shown in Table 1 were roll-kneaded at 50 ° C to obtain an unvulcanized elastomer composition shown in Table 1. Mold releasability and vulcanizate tensile tests of these unvulcanized elastomer compositions were conducted. Table 1 shows the results.

For comparison, the same experiment was conducted except that a commercially available silicone type release agent, metal soap type release agent, and higher fatty acid metal salt were used instead of the anionic surfactant. . The results are shown in Table 2.

The symbols in Tables 1 and 2 represent the following compounds and the like. HNBR: Hydrogenated acrylonitrile-butadiene copolymer rubber NBR: Acrylonitrile-butadiene copolymer rubber DBS-Na: Sodium dodecylbenzenesulfonate DBS-Li: Lithium dodecylbenzenesulfonate DBS-Ca: Calcium dodecylbenzenesulfonate DS-Na : Sodium dodecyl sulfonate ANAS-Na: Sodium alkylnaphthalene sulfonate AS-Na: Sodium alkyl sulfate APA-K: Potassium alkyl phosphate DBS-P: Tetraalkylphosphonium dodecylbenzene sulfonate

[0052]

[Table 1]

[0053]

[Table 2]

From the results shown in Tables 1 and 2, the elastomer composition of the present invention has a good mold releasability, and is more vulcanized than when a conventionally known release agent is used. It can be seen that the strength characteristics are excellent.

Example 2 Experiment Nos. 1 to 3 In the mold releasability test of Experiment Nos. 1 to 3 of Example 1, vulcanization was performed using an organic fluorine compound-based mold releasing agent as the external mold releasing agent. The releasability of the elastomer was evaluated. Before press-molding the elastomer composition, the mold is sprayed with an organic fluorine compound-based mold release agent shown in Table 3 to keep the solvent evaporated. The criteria for the adhesion of the elastomer to the chrome-plated plate are as described above. Further, the releasability of the vulcanized elastomer was evaluated in the following three stages. Table 1 shows the results. 3: Very good releasability 2: Releasable relatively easily 1: Releasing force is required

The symbols in Table 3 represent the following compounds and the like. F release 11: Fluorine-based solvent type fluorine-based release agent (manufactured by Neos Co., Ltd.) F release 23: Water-soluble fluorine-based release agent (manufactured by Neos Co., Ltd.)

[0057]

[Table 3]

From the results shown in Table 3, it can be seen that the elastomer composition of the present invention can be efficiently vulcanized and molded by using an organic fluorine compound-based mold release agent together during press molding.

[0059]

As described above, according to the present invention, an ethylenically unsaturated carboxylic acid metal salt-containing elastomer composition capable of obtaining an elastomer product having good mold releasability and excellent strength characteristics can be obtained.

Further, according to the present invention, by using the organic fluorine compound-based releasing agent in combination, the ethylenically unsaturated carboxylic acid metal salt-containing elastomer composition having good mold releasability can be efficiently added. It can be vulcanized.

Since the elastomer composition of the present invention is excellent in mold releasability, it is used for molding elastomer products by a mold molding method, for example, various seals such as packing and gaskets, cushion materials, sliding members, Industrial casters, rubber crawlers for construction machinery, industrial rubber rolls,
It can be widely applied to shoe soles, rubber plates for floors, industrial heat insulating materials and the like.

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Claims (2)

[Claims] 1. An ethylenically unsaturated carboxylic acid metal salt containing (A) an elastomer, (B) an ethylenically unsaturated carboxylic acid metal salt, and (C) an anionic surfactant containing a sulfur element or a phosphorus element. Elastomer composition. 2. A vulcanizable composition obtained by blending the ethylenically unsaturated carboxylic acid metal salt-containing elastomer composition according to claim 1 with an organic peroxide is treated with an organic fluorine compound-based release agent. A method for molding a vulcanized elastomer, which comprises vulcanizing and molding in a coated mold.