JP2020041089A - Adhesion preventive for unvulcanized rubber and water dispersion of adhesion preventive for unvulcanized rubber - Google Patents

Abstract

To provide an adhesion preventive for unvulcanized rubber that has excellent adhesion prevention ability, and avoids the problems of dust contamination and foamability.SOLUTION: An adhesion preventive for unvulcanized rubber contains the following components (A)-(C): (A) a fatty acid alkali metal salt, (B) a salt of a fatty acid and a metal other than an alkali metal, (C) a nonionic surfactant with an HLB of 9-18 by Griffin method.SELECTED DRAWING: None

Description

  The present invention relates to an unvulcanized rubber antiblocking agent and an aqueous dispersion of an unvulcanized rubber antiblocking agent.

  At the site of rubber production processing, an anti-adhesive agent (also referred to as a release agent or an anti-adhesion agent) is attached to the surface of the unvulcanized rubber for the purpose of preventing adhesion of the unvulcanized rubber. The unvulcanized rubber anti-adhesive is generally used in the form of an aqueous dispersion and then adhered to the rubber surface (Patent Documents 1 to 6 and the like).

JP-A-50-149770 JP 2013-001720 JP-A-62-032127 JP 2009-161667 JP 2017-088686 JP-A-56-47476

  As an unvulcanized rubber anti-adhesive, an anti-adhesive comprising an inorganic powder as a main component as in Patent Documents 1 to 4 is widely used. However, when such an anti-adhesive is applied to rubber and after the application, dust may deteriorate the working environment. Specifically, for example, dust derived from inorganic components may lead to contamination of the working environment and the factory.

  In order to solve the problem of dust, for example, Patent Literatures 5 and 6 propose an adhesion inhibitor for unvulcanized rubber containing fatty acid soap and fatty acid metal soap as main components. However, such an anti-adhesion agent can suppress dust, but may have a problem of low anti-adhesion property or foaming property. Therefore, there is a need for an unvulcanized rubber anti-adhesive agent that can solve all problems of anti-adhesion, dust contamination and foaming properties.

  Accordingly, the present invention provides an unvulcanized rubber anti-adhesive agent and an aqueous dispersion of the unvulcanized rubber anti-adhesive agent, which are excellent in anti-adhesion properties and in which the problems of dust contamination and foaming are suppressed. With the goal.

In order to achieve the above object, the anti-adhesive for unvulcanized rubber of the present invention is characterized by containing the following components (A) to (C).

(A) a fatty acid alkali metal salt (B) a salt of a fatty acid and a metal other than an alkali metal (C) a nonionic surfactant having an HLB of 9 to 18 by the Griffin method

  The aqueous dispersion of the unvulcanized rubber anti-adhesive agent of the present invention is characterized by containing the unvulcanized rubber anti-adhesive agent of the present invention and water.

  According to the present invention, it is possible to provide an unvulcanized rubber anti-adhesive agent and an unvulcanized rubber anti-adhesive agent aqueous dispersion which are excellent in anti-adhesion property and in which dust pollution and foaming problems are suppressed. Can be.

  Hereinafter, the present invention will be described with examples. However, the present invention is not limited by the following description.

  In the unvulcanized rubber antiwear agent of the present invention, for example, the proportion of the fatty acid alkali metal salt having 16 or more carbon atoms in the component (A) may be 70% by mass or more.

  In the anti-curing agent for unvulcanized rubber of the present invention, for example, the proportion of the unsaturated fatty acid alkali metal salt in the component (A) may be 70% by mass or less.

The unvulcanized rubber antiwear agent of the present invention may further contain, for example, the following component (D).

(D) Non-swellable inorganic powder

The adhesion promoter for unvulcanized rubber of the present invention may further contain, for example, the following component (E).

(E) Synthetic resin latex

  In the present invention, “alkyl” includes, for example, linear or branched alkyl. In the present invention, the alkyl group is not particularly limited, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group, pentyl group, Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl and the like.

  In the present invention, “alkylene” includes, for example, linear alkylene (methylene or polymethylene) or branched alkylene. In the present invention, the alkylene group is not particularly limited. Examples thereof include a methylene group, a dimethylene group (ethylene group), an ethylidene group, a trimethylene group, a 1-methylethylene group (propylene group), a tetramethylene group, and 1-methyltrimethylene. Groups, 2-methyltrimethylene group, 1,1-dimethylethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, and the like.

  Hereinafter, embodiments of the present invention will be described more specifically. However, the present invention is not limited to the following embodiments.

[1. Anti-adhesive for unvulcanized rubber]
As described above, the anti-adhesive agent for unvulcanized rubber of the present invention is characterized by containing the following components (A) to (C).

(A) a fatty acid alkali metal salt (B) a salt of a fatty acid and a metal other than an alkali metal (C) a nonionic surfactant having an HLB of 9 to 18 by the Griffin method

[1-1. Component (A)]
Component (A) is a fatty acid alkali metal salt as described above. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid, but is preferably a saturated fatty acid. Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium and francium, for example, sodium or potassium. The fatty acid alkali metal salt (A) (component (A)) is not particularly limited, and may be used alone or in combination of two or more. The fatty acid alkali metal salt (A) is not particularly limited, but is, for example, a sodium or potassium salt of a fatty acid having 6 to 30 carbon atoms. More specifically, for example, caproic acid, caprylic acid, capric acid Sodium of fatty acids such as lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, isooleic acid, linoleic acid, linolenic acid, arachidic acid, behenic acid, lignoceric acid, serotinic acid, montanic acid, melicic acid Salt, potassium salt and the like. Among these fatty acid soaps (fatty acid alkali metal salts), sodium salts and potassium salts of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid are listed. Preferred in terms of foaming and solubility, sodium and potassium salts of myristic acid, palmitic acid, stearic acid, and behenic acid are more preferred. In the fatty acid alkali metal salt (A), the average carbon chain length of the fatty acid may be, for example, 14 or more, 16 or more, or 18 or more, and may be 24 or less, 22 or less, or 20 or less.

  In the component (A), the proportion of the alkali metal salt of a fatty acid having 16 or more carbon atoms is preferably as large as possible, for example, 70% by mass or more, 75% by mass or more, 80% by mass or more, or 90% by mass or more. And, for example, 100% by mass or less. When the proportion of the fatty acid alkali metal salt having 16 or more carbon atoms in the component (A) is 70% by mass or more, the dispersibility of the hydrophobic component is improved, and the effect of suppressing foaming such as scum foam is further enhanced. Become.

  In the component (A), the proportion of the unsaturated fatty acid alkali metal salt is preferably 70% by mass or less, for example, 65% by mass or less, and 60% by mass or less from the viewpoint of the effect of suppressing foaming such as scum foam. , 55% by mass or less, or 50% by mass or less. The lower limit of the proportion of the unsaturated fatty acid alkali metal salt is not particularly limited, but may be, for example, 0% by mass or more, 10% by mass or more, or 30% by mass or more in the component (A).

  The content of the fatty acid alkali metal salt (A) in the unvulcanized adhesion-preventing agent of the present invention is not particularly limited, but is, for example, 30% by mass or more based on the total mass of the components (A) to (C). It may be 35% by mass or more, 40% by mass or more, 45% by mass or more, or 50% by mass or more, for example, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less. It may be not more than mass%. From the viewpoint of adhesion to rubber, it is preferable that the content of component (A) is not too high, and from the viewpoint of the effect of suppressing foaming such as scum foam, the content of component (A) is not too small. Is preferred.

[1-2. Component (B)]
The component (B) is a salt of a fatty acid and a metal other than an alkali metal, as described above. The fatty acid is not particularly limited, but may be, for example, the same as the fatty acid described in the component (A). The metal other than the alkali metal is not particularly limited, and may be, for example, a typical metal or a transition metal, such as an alkaline earth metal, a typical metal, a transition metal, or a rare earth metal. Specific examples of the metal other than the alkali metal include calcium, zinc, magnesium, aluminum, barium, strontium, manganese, tin, lead, copper, and iron. Component (B) may be, for example, a salt of a polyvalent metal ion. The component (B) is not particularly limited, and may be used alone or in combination of two or more. Although the component (B) is not particularly limited, for example, calcium caprylate, zinc caprylate, magnesium caprylate, aluminum caprylate, calcium caprate, zinc caprate, magnesium caprate, aluminum caprate, calcium laurate, zinc laurate , Magnesium laurate, aluminum laurate, calcium myristate, zinc myristate, magnesium myristate, aluminum myristate, calcium palmitate, zinc palmitate, magnesium palmitate, aluminum palmitate, calcium stearate, zinc stearate, stearic acid Magnesium, aluminum stearate, aluminum trioctadecanoate, aluminum dioctadecanoate, aluminum monooctadecanoate , Calcium octadecanoate, zinc octadecanoate, magnesium octadecanoate, aluminum octadecanoate, calcium oleate, zinc oleate, magnesium oleate, aluminum oleate, calcium behenate, zinc behenate, magnesium behenate, aluminum behenate, Calcium 12-hydroxystearate, zinc 12-hydroxystearate, magnesium 12-hydroxystearate, aluminum 12-hydroxystearate, calcium 14-octadecanoate, zinc 14-octadecanoate, magnesium 14-octadecanoate, aluminum 14-octadecanoate Octadecanoate, calcium 8-octadecanoate, magnesium 8-octadecanoate, magnesium 8-octadecanoate, Minium, calcium 6-octadecanoate, zinc 6-octadecanoate, magnesium 6-octadecanoate, aluminum 6-octadecanoate, coconut fatty acid, coconut fatty acid zinc, coconut fatty acid magnesium, coconut fatty acid aluminum, palm oil fatty acid calcium, palm oil fatty acid Zinc, palm oil fatty acid magnesium, palm oil fatty acid aluminum, palm kernel oil fatty acid calcium, palm kernel oil fatty acid zinc, palm kernel oil fatty acid magnesium, palm kernel oil fatty acid aluminum, tallow fatty acid calcium, tallow fatty acid zinc, tallow fatty acid magnesium, tallow fatty acid Aluminum, castor oil fatty acid calcium, castor oil fatty acid zinc, castor oil fatty acid magnesium, castor oil fatty acid aluminum and the like.

  The content of the component (B) in the unvulcanized adhesion-preventing agent of the present invention is not particularly limited, but is, for example, 10% by mass or more and 20% by mass based on the total mass of the components (A) to (C). The above may be 30% by mass or more, 40% by mass or more, or 50% by mass or more, for example, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, or 40% by mass or less It may be. From the viewpoint of the effect of suppressing foaming such as scum foam, the content of the component (B) is preferably not too large, and from the viewpoint of adhesion to rubber, the content of the component (B) is not too small. Is preferred.

[1-3. Component (C)]
The component (C) is a nonionic surfactant having an HLB of 9 to 18 by the Griffin method as described above. When the HLB of the component (C) by the Griffin method is within the above-mentioned numerical range, for example, the dispersibility of the hydrophobic component is improved, and foaming such as scum foam can be suppressed. The HLB may be, for example, 11-18, 11-17, 12-15, or 12-13.

Here, the HLB by the Griffin method is a numerical value that can be calculated by the following formula (I) based on the molecular structure. That is, the HLB by the Griffin method can take a value from 0 to 20, and the smaller the value (closer to 0), the more lipophilic (hydrophobic), and the larger the value (closer to 20), the more hydrophilic. It is an indicator of gender.

HLB = 20 × (sum of formula weight of hydrophilic part / molecular weight) (I)

In the present invention, the nonionic surfactant of the component (C) is not particularly limited. For example, a nonionic surfactant represented by the following chemical formula (1) can be used.

RO- (AO) _n- H (1)

In the chemical formula (1), R is an aliphatic hydrocarbon group, for example, an aliphatic hydrocarbon group having 8 to 18 carbon atoms. The aliphatic hydrocarbon group may be linear or branched. Further, the aliphatic hydrocarbon group may be any of a saturated aliphatic hydrocarbon group (alkyl group) and an unsaturated aliphatic hydrocarbon group. The number of carbon atoms of R may be, for example, 8 to 22, 8 to 18, 10 to 16, or 12 to 14 from the viewpoint of dispersibility of the hydrophobic component.
AO represents an oxyalkylene group having 2 to 4 carbon atoms, and n is the average number of moles of AO added.
n is, for example, 1 to 50, 1 to 40, 1 to 30, 1 to 25, or 1 to 15 from the viewpoint of dispersibility of the hydrophobic component.

The oxyalkylene group having 2 to 4 carbon atoms is, for example, a polymerized unit formed by addition of an alkylene oxide having 2 to 4 carbon atoms (formed by addition polymerization). Specific examples of the oxyalkylene group having 2 to 4 carbon atoms include an oxyethylene group (EO) to which ethylene oxide is added, an oxypropylene group (PO) to which propylene oxide is added, and butylene oxide. Is an oxybutylene group (BO). (AO) _n contains at least an oxyethylene group in its structure. (AO) When _n includes a plurality of types of oxyethylene group (EO), oxypropylene group (PO), and oxybutylene group (BO), even if these groups are arranged in a block shape, , May be arranged randomly. Desirable (AO) _n consists only of an oxyethylene group (EO) from the viewpoint of excellent balance between hydrophilicity and hydrophobicity.

Further, when the nonionic surfactant molecule of the component (C) is represented by the chemical formula (1), the hydrophilic part is the (AO) _n part. That is, the total formula weight of the hydrophilic part indicates the formula weight of the (AO) _n part. Therefore, when the nonionic surfactant molecule of the component (C) is represented by the chemical formula (1), the HLB by the Griffin method can be calculated by the following mathematical formula (II).

HLB = 20 × [(AO) Formula weight of _n portion / Molecular weight of chemical formula (1)] (II)

For example, in the chemical formula (1), when R is a decyl group (an alkyl group having 10 carbon atoms), AO is an oxyethylene group (EO), and n = 5, the molecular formula is the following chemical formula (2) ). In this case, the molecular weight is 361, and the formula weight of the hydrophilic part ((AO) _n part) is 220, so that the HLB by the Griffin method is 20 × (220/361) = 12.1.

_{C 10 H 21 O- (C 2} H 4 O) 5 -H (2)

  In the component (C), for example, in the chemical formula (1), R is a saturated or unsaturated aliphatic hydrocarbon group having 10 carbon atoms, AO is an oxyethylene group (EO), and n is 10. The HLB by the Griffin method may be 12 to 13.

  The content of the component (C) in the unvulcanized adhesion-preventing agent of the present invention is not particularly limited, but is, for example, 1% by mass or more and 5% by mass with respect to the total mass of the components (A) to (C). It may be 10% by mass or more, 15% by mass or more, or 20% by mass or more, for example, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less It may be. It is preferable that the content of the component (C) is not too large from the viewpoint of adhesion to rubber, and that the content of the component (C) is not too small from the viewpoint of the effect of suppressing foaming such as scum foam. Is preferred.

[1-4. Optional component]
The unvulcanized rubber adhesion-preventing agent of the present invention may or may not contain any component other than the components (A) to (C).

  Examples of the optional component include the component (D), that is, a non-swellable inorganic powder. Examples of the non-swellable inorganic powder (D) (component (D)) include, but are not particularly limited to, carbonates such as calcium carbonate, magnesium carbonate, and barium carbonate; bentonite, clay, kaolin, talc, mica, and sericite Silicates such as calcium sulfate, barium sulfate, etc .; metal oxides such as amorphous silica, alumina, magnesium oxide, antimony trioxide, titanium oxide, white carbon, iron oxide; aluminum hydroxide, hydroxide Metal hydroxides such as magnesium and iron hydroxide; bengalara; carbon black; graphite and the like. The inorganic powder may be used alone or in combination of two or more.

  The content of the component (D) in the unvulcanized adhesion-preventing agent of the present invention is not particularly limited, but is, for example, 0% by mass or more and 5% by mass based on the total mass of the components (A) to (C). It may be 10% by mass or more, 15% by mass or more, or 20% by mass or more, for example, 100% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, or 80% by mass or less It may be. It is preferable that the content of the component (D) is not too large from the viewpoint of scattering properties, and it is preferable that the content of the component (D) is not too small from the viewpoint of lubricity of rubber.

  Examples of the optional component include a surfactant other than the component (C) (hereinafter, also referred to as “component (E)” or “surfactant (E)”). The surfactant (E) is not particularly limited, and may be, for example, a cationic (cationic) surfactant, an anionic (anionic) surfactant, or a nonionic (nonionic) surfactant, Only one type may be used, or two or more types may be used in combination.

  The surfactant (E) (component (E)) is not particularly limited. Examples thereof include polyoxyalkylene alkyl ethers such as polyoxyethylene cetyl ether and polyoxyethylene lauryl ether; polyoxyethylene nonylphenyl ether; Polyoxyalkylene alkylphenyl ethers such as ethylene octyl phenyl ether; polyoxyalkylene fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monooleate; polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate Polyoxyalkylene sorbitan fatty acid ester; polyoxyalkylene alkylamine; fatty acid alkanolamide; polyoxyalkylene fatty acid amide; Polyoxyalkylene sorbitol fatty acid ester; polyglycerin fatty acid ester; alkyl glycerin ether; polyoxyalkylene cholesteryl ether; alkyl polyglucoside; sucrose fatty acid ester; oxyethylene-oxypropylene block polymer, sodium lauryl sulfate, ammonium lauryl sulfate, Alkyl sulfates such as sodium stearyl sulfate and sodium cetyl sulfate; polyoxyalkylene alkyl ether acetates such as sodium polyoxyethylene tridecyl ether acetate; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; polyoxyalkylene alkyl ether sulfate Salt; long-chain sulfosuccinate such as sodium 2-ethylhexylsulfosuccinate; N-acyl sarcosine salts such as irsarcosin Na and lauroyl sarcosine Na; higher fatty acid amide sulfonates such as stearoyl methyl taurine Na, lauroyl methyl taurine Na, myristoyl methyl taurine Na, palmitoyl methyl taurine Na; alkyl sulfonates, alkyl sulfones Saturated sulfonates such as sodium silicate; unsaturated sulfonates such as alpha-olefin sulfonate and sodium alpha-olefin sulfonate; alkyl phosphates such as sodium monostearyl phosphate; sodium polyoxyethylene oleyl ether phosphate; Polyoxyalkylene alkyl ether phosphates such as sodium oxyethylene stearyl ether phosphate; sodium monosodium N-lauroylglutamate; Long-chain N-acyl glutamates such as disodium stearoyl-L-glutamate, alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, cetyltrimethylammonium bromide; dialkyldimethylammonium salts; trialkylmethylammonium salts; Imidazoline amphoteric interfaces such as alkylamine salts, 2-undecyl-N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, and 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt Activator; 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauryl dimethylaminoacetate betaine, coconut oil fatty acid amidopropyl Betaine ampholytic surfactants such as in; N- lauryl glycine, N- lauryl β- alanine, amino acid type such as N- stearyl β- -alanine. The surfactant may be used alone or in combination of two or more.

  The content of the component (E) in the unvulcanized anti-adhesive of the present invention is not particularly limited, but is, for example, 0.1% by mass or more based on the total mass of the components (A) to (C). For example, it may be 50.0% by mass or less, 40.0% by mass or less, 30.0% by mass or less, 25.0% by mass or less, or 20.0% by mass or less. From the viewpoint of foaming of the aqueous dispersion, the content of the component (E) is preferably not too large, and from the viewpoint of dispersibility and wettability, the content of the component (E) is preferably not too small.

  Other examples of the optional component include an antifoaming agent, a wetting aid, a viscosity aid, and a foreign matter reduction aid.

  Examples of the antifoaming agent include, but are not limited to, oil and fat antifoaming agents such as castor oil, sesame oil, linseed oil, animal and vegetable oils; isoamyl stearate, distearyl succinate, ethylene glycol distearate, butyl stearate and the like. Fatty acid ester-based antifoaming agents; alcohol-based antifoaming agents such as polyoxyalkylene monohydric alcohol di-t-amylphenoxyethanol, 3-heptanol and 2-ethylhexanol; di-t-amylphenoxyethanol, 3-heptylcellosolve; Ether defoamers such as nonyl cellosolve and 3-heptyl carbitol; phosphate defoamers such as tributyl osphate and tris (butoxyethyl) phosphate; amine defoamers such as diamylamine; polyalkyleneamide; Acylate poly Amide-based defoaming agent such as Min; mineral oil; silicone oil; and the like. The antifoaming agent may be used alone or in combination of two or more.

  Examples of the wetting aid include, but are not particularly limited to, alcohols, and more specifically, for example, methanol, ethanol, hexanol, glycerin, 1,3-butanediol, propylene glycol, dipropylene glycol, Examples include pentylene glycol, hexylene glycol, polyethylene glycol, solutol, maltitol, sucrose, erythritol, xylitol, polyethylene glycol, polypropylene glycol, and adducts of polyhydric alcohols such as ethylene oxide and propylene oxide. The wetting aid may be used alone or in combination of two or more.

  The viscosity aid is not particularly limited, but includes, for example, water-soluble polymers, and more specifically, for example, proteins, polyacrylic acid, sodium polyacrylate, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone , Polyethylene glycol, polyethylene oxide, water-soluble urethane resin, water-soluble melamine resin, water-soluble epoxy resin, water-soluble butadiene resin, water-soluble phenol resin, and other synthetic water-soluble polymers; xanthan gum, guar gum, welan gum, locust bean gum, daiyu Tangum, tamarind gum, tamarind seed gum, tragacanth gum, gum arabic, carrageenan, ramzan gum, succinoglycan, tara gum, gellan gum, karaya gum, pectin, alginic acid derivatives, cellulose ethers, etc. Natural water-soluble polymer, and the like. The viscosity auxiliary may be used alone or in combination of two or more.

  The optional component in the unvulcanized rubber anti-adhesive agent of the present invention also includes water (hereinafter sometimes referred to as “component (F)” or “water (F)”). The water content is not particularly limited, but is, for example, about 60 to 90% by mass based on the entire mass of the unvulcanized rubber anti-adhesive agent of the present invention.

  As described above, the unvulcanized rubber anti-adhesive agent containing an inorganic powder (for example, bentonite) as a main component as in Patent Documents 1 to 4 has a problem of dust. On the other hand, the non-vulcanized rubber anti-adhesive agent of the present invention may or may not contain an inorganic powder (for example, bentonite) and may contain a small amount. Therefore, according to the unvulcanized rubber anti-adhesive agent of the present invention, the problem of dust contamination can be suppressed or prevented.

  The unvulcanized rubber antiblocking agent of the present invention may or may not contain a fluorine element, but preferably does not contain a fluorine element. By using a non-fluorine-based (non-fluorine) unvulcanized rubber anti-adhesive agent, the effect of the fluorine element on the environment can be prevented.

[2. Method for producing anti-curing agent for unvulcanized rubber]
The method for producing the unvulcanized rubber anti-adhesive agent of the present invention is not particularly limited. For example, all the components (components (A) to (C) of the unvulcanized rubber anti-adhesive agent and, if necessary, And the optional component to be blended). For example, component (A) (a fatty acid alkali metal salt), component (B) (a salt of a fatty acid and a metal other than an alkali metal), and component (C) (a nonionic having an HLB of 9 to 18 by the Griffin method). (Active surfactant) and water, and then other components may be added and mixed. In addition, for example, if necessary, mixing may be performed while heating or the like to facilitate mixing.

  The apparatus used for mixing is not particularly limited, but for example, an apparatus having a configuration in which a stirring blade is provided in a container can be used. Specific examples include a liquid mixer equipped with a general stirring device, a line homomixer, and a liquid mixer provided with a line homomixer.

[3. Method for using unvulcanized rubber anti-adhesive and aqueous dispersion of unvulcanized rubber anti-adhesive]
The method of using the unvulcanized rubber anti-adhesive of the present invention is not particularly limited, and for example, can be used in the same manner as a general unvulcanized rubber anti-adhesive. The unvulcanized rubber anti-adhesive agent of the present invention can be used, for example, as the unvulcanized rubber anti-adhesive water dispersion of the present invention. The method for producing the unvulcanized rubber anti-adhesive agent aqueous dispersion of the present invention is not particularly limited, for example, by mixing all the components of the unvulcanized rubber anti-adhesive agent of the present invention as described above, After producing the unvulcanized rubber anti-adhesive agent of the present invention, it may be dispersed in water. Further, for example, each component of the unvulcanized rubber anti-adhesive agent of the present invention is dissolved or dispersed in water, respectively, and mixed in water to obtain an unvulcanized rubber anti-adhesive agent aqueous dispersion of the present invention. Is also good. The method for dissolving or dispersing the above components is not particularly limited. For example, a powdery unvulcanized rubber anti-adhesive agent may be dispersed in a predetermined amount of water in a stirring tank. The total content of the components (A) to (C) in the aqueous dispersion of the unvulcanized rubber-based anti-adhesive agent of the present invention is not particularly limited. For example, from 0.5% by mass to 10% by mass, from 0.5% by mass to 8% by mass, from 0.5% by mass to 6% by mass, or from 0.5% by mass to 4% by mass with respect to the mass of the whole liquid. It may be not more than mass%.

  When the aqueous dispersion of the adhesion-preventing agent for unvulcanized rubber is used, the total content of the components (A) to (C) relative to the total mass of the components other than water in the aqueous dispersion of the adhesion-preventing agent for unvulcanized rubber is included. The amount may be, for example, 10.0% by mass or more, 15.0% by mass or more, 20.0% by mass or more, and for example, 80.0% by mass or less, 75.0% by mass or less, 70. It may be 0% by mass or less.

  When produced as an aqueous dispersion of an unvulcanized rubber anti-adhesive agent in this way, it can be used as it is by applying it to the surface of the unvulcanized rubber by a wet method described later or the like.

  The method for producing a non-vulcanized rubber that has been subjected to anti-deposition treatment using the unvulcanized rubber anti-adhesive agent of the present invention includes, for example, attaching the unvulcanized rubber anti-adhesive agent of the present invention to the surface of the unvulcanized rubber. And an anti-adhesion treatment step. Even if the unvulcanized rubber having been subjected to the anti-adhesion treatment manufactured in this way is stacked or folded and stored, for example, the unvulcanized rubbers do not adhere to each other.

  The anti-adhesion treatment step, for example, by adhering the unvulcanized rubber anti-adhesive agent aqueous dispersion of the present invention on the surface of the unvulcanized rubber, and further volatilize water, the unvulcanized rubber The step of adhering the unvulcanized rubber anti-adhesive agent of the present invention to the surface may be performed. More specifically, the anti-adhesion treatment step includes the step of adhering the aqueous dispersion of the anti-adhesive agent for unvulcanized rubber of the present invention (anti-adhesive agent suspension) to the surface of the unvulcanized rubber. And a drying step of drying the suspension of the anti-adhesive agent on the surface of the unvulcanized rubber to form a film made of the anti-adhesive agent on the surface of the unvulcanized rubber. Is preferred. Such an anti-adhesion treatment step is called, for example, a wet method.

  In the method for producing a non-vulcanized rubber having been subjected to the anti-adhesion treatment of the present invention, the wet method is not particularly limited. For example, the wet method may be performed in the same manner as a general wet method for a non-vulcanized rubber anti-adhesive agent. It is. The concentration of the unvulcanized rubber anti-adhesive agent of the present invention in the anti-adhesive agent suspension (aqueous dispersion) is, for example, as described above, and more specifically, for example, 2 to 3% by mass. However, the present invention is not limited to this, and can be arbitrarily adjusted.

  In the suspension adhering step, for example, an anti-adhesive agent suspension is adhered to unvulcanized rubber in a high temperature state (for example, about 80 to 150 ° C.) by heat generated when the suspension is formed into a sheet or the like. Is preferred.

  As a specific method of the suspension adhering step, for example, a method of spraying the anti-adhesive agent suspension to the unvulcanized rubber with a shower device, the method of applying the unvulcanized rubber to a tank containing the anti-adhesive agent suspension A dipping method of immersing for a short time is exemplified. In addition, a method of applying the anti-adhesive agent suspension to the unvulcanized rubber using an application device may be adopted, and these methods may be used in combination.

  As described above, the anti-adhesive agent for unvulcanized rubber of the present invention has excellent anti-adhesion properties and suppresses dust contamination and foaming problems. The type of rubber to which the anticuring agent for unvulcanized rubber of the present invention can be applied is not particularly limited, and may be any unvulcanized rubber. Examples of the rubber type include rubbers such as natural rubber (NR), butadiene rubber (BR), styrene butadiene rubber (SBR), IIR (butyl rubber), EPDM (ethylene propylene rubber), and a plurality of these types. And mixed rubber.

  Hereinafter, examples of the present invention will be described. Note that the present invention is not limited to these examples.

[Example 1]
The unvulcanized rubber anti-blocking agent and the aqueous dispersion of the unvulcanized rubber anti-blocking agent of this example were produced as follows.

  First, 530 g of water was placed in a reaction vessel and heated to 70 ° C. or higher. Thereafter, 10 g of potassium caprate (90% capric acid, a product obtained by reacting product No. 36356 manufactured by Yoneyama Pharmaceutical Company with caustic potassium [potassium hydroxide]) and potassium laurate (90% potassium laurate, product No. 37556, 20 g, manufactured by Yoneyama Pharmaceutical Co., Ltd., potassium stearate (90% potassium stearate, product No. 36938, manufactured by Yoneyama Pharmaceutical Co., Ltd.), Liporan LB-840 (manufactured by Lion Specialty Chemicals), and fine Surf D-1305 (manufactured by Aoki Yushi Kogyo KK) was added and mixed at 70 ° C. or higher for 2 hours. Thereafter, calcium stearate (manufactured by NOF CORPORATION) and Repcomica M-60 (manufactured by REPCO CORPORATION) were added and mixed at 70 ° C. or higher for 2 hours. The liquid obtained by cooling it to 30 ° C. or lower was used as an unvulcanized rubber anti-sticking agent of this example. Furthermore, the unvulcanized rubber anti-adhesive agent was diluted with water to 20 times (5% by mass concentration) by mass ratio to prepare a suspension. The suspension (dispersion) was used as an aqueous dispersion of the anti-adhesive for unvulcanized rubber of this example.

  The mass ratio of each of the components in this example is shown in Table 1 below. In the component (A) in Table 1 below, “fatty acid salt (C10 or less)” means the potassium caprate (fatty acid salt having 10 carbon atoms). “Fatty acid salt (C12 to C14)” means the above-mentioned potassium laurate (fatty acid salt having 12 carbon atoms). "Saturated fatty acid salt (C16 or more)" means the above-mentioned potassium stearate (fatty acid salt having 18 carbon atoms). The term “unsaturated fatty acid salt (C16 or more)” means potassium oleate (a fatty acid salt having 18 carbon atoms and being unsaturated). Components (C), (D) and (E) in Table 1 below are as described in Table 2 below.

[Examples 2 to 16, Comparative Examples 1 to 3]
An unvulcanized rubber antiblocking agent and an aqueous dispersion of an unvulcanized rubber antiblocking agent were produced in the same manner as in Example 1 except that the mass ratio of each component was changed as shown in Table 1 below.

  For the unvulcanized rubber antiblocking agent and the unvulcanized rubber antiblocking agent aqueous dispersions of Examples 1 to 17 and Comparative Examples 1 to 3, adhesion, antiadhesiveness and foaming properties were determined by the following methods. Measured and evaluated. The evaluation results are shown in Table 1 below.

<Evaluation>
The following unvulcanized NR / BR rubber was used as an evaluation rubber in the evaluation of adhesion, anti-adhesion and foaming properties shown in Table 1.

(Unvulcanized NR / BR rubber)
For a total of 100 parts by mass of 70 parts by mass of NR (RSS # 3) and 30 parts by mass of BR (manufactured by JSR Corporation, trade name "BR-01"), white carbon (manufactured by Tosoh Silica Co., Ltd.) 10 parts by mass of “Nip Seal VN-3”), 30 parts by mass of ISAF Black (trade name “Seast 6”, manufactured by Tokai Carbon Co., Ltd.) and JSRARAMA (process oil) (manufactured by Nippon Sun Oil Co., Ltd.) Name "Aroma 790"), 15 parts by mass of zinc white (3 types of zinc white, manufactured by Hakusui Tech Co., Ltd.), 1 part by mass of stearic acid (Nippon Oil Co., Ltd., camellia), and 6 PPD (large 1 part by mass, manufactured by Uchi Shinko Chemical Industry Co., Ltd., trade name “Nocrack 6C”, 1 part by mass of CBS (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., trade name: “Noxeller CZ-G”), sulfur (Tsurumi Chemical ( 1.5 parts by mass) Total 162.5 parts by weight) unvulcanized NR / BR rubber.

(1) Adhesion evaluation method The unvulcanized rubber (unvulcanized NR / BR rubber) was kneaded with an open roll at a temperature of 80 to 120 ° C., and a rubber sheet (thickness: 5 to 8 mm, 60 cm × 15 cm) was prepared. did. The rubber sheet immediately after being fed out is immersed for about 1 second in 1 L of an aqueous dispersion (temperature 40 ° C.) of an unvulcanized rubber antiblocking agent obtained in each of Examples 1 to 17 and Comparative Examples 1 to 3. did. Thereafter, the rubber sheet was quickly pulled up vertically and allowed to stand at room temperature. When the surface area of the rubber sheet is set to 100%, the uniformity of the dried anti-adhesive film (the film of the dried and solidified anti-adhesive material) and the thickness of the coated film (covered with a uniform thickness) are visually observed. It was confirmed and judged in the following five stages of 1 to 5. Those having a judgment result of 4 or 5 were evaluated as acceptable.

1: Repelling has occurred 2: The coating is a vertical striped or star-shaped coating 3: The thin coating is not a vertical striped or star-shaped coating.
4: The coating is a homogeneous coating that is not vertical stripes or pills.
5: The coating is a rather thick homogeneous coating that is not vertical stripes or burrs.

  As described above, the rubber that is unwound with an open roll at 80 to 120 ° C. and whose surface is in a high temperature state is immersed in the anti-adhesive agent suspension for a very short time (about 1 second), and the adhered anti-adhesion is obtained. Even if water evaporates rapidly from the agent suspension, it is preferable that the adhesion preventive agent remains on the rubber surface in a uniform thin film state without unevenness such as vertical stripes and pills. The higher the adhesion, the higher the adhesion resistance tends to be. In addition, the higher the adhesion, the more easily the unsatisfactory appearance of the unvulcanized rubber after the adhesion inhibitor is attached is easily suppressed.

(2) Evaluation of anti-adhesion property The unvulcanized rubber (unvulcanized NR / BR rubber) was kneaded with an open roll at a temperature of 80 to 120 ° C. and a rubber sheet (thickness: 5 to 8 mm, 60 cm × 15 cm). did. The rubber sheet immediately after being fed out was immersed for about 1 second in 1 L of the anti-adhesive agent suspension (temperature: 40 ° C.) obtained in each of Examples 1 to 17 and Comparative Examples 1 to 3. Thereafter, the rubber sheet was quickly pulled up vertically, allowed to stand vertically at room temperature, and air-dried.

Thereafter, the rubber sheet was cut into a size of 6 cm × 15 cm, and two sheets were overlapped to form a laminated state. A load of 1 t / m ² was applied vertically from one surface to the test pieces in the laminated state, and the test pieces were left at 60 ° C. for 12 hours.

  Thereafter, the test piece was returned to room temperature, and a 180 ° peel test was performed using a tensile tester [AGS-500D type, SHIMADZU], and the peel resistance (N / cm) was measured at a pulling speed of 300 mm / min. The smaller the peeling resistance is, the easier the test piece is to be peeled off, which is an index of the excellent adhesion resistance. Those having a peel resistance of 2.0 (N / cm) or less were evaluated as acceptable.

(3) Evaluation of foaming property 1 L of the aqueous dispersion (temperature 40 ° C.) of the unvulcanized rubber antiblocking agent obtained in each of Examples 1 to 17 and Comparative Examples 1 to 3 was put into a 2 L female cinder, and a pump was used. [Magnet Pump MD-15R-N] Circulation was performed, and the foam volume (mL) after 5 minutes was measured. The smaller the foam volume is, the more the index of foaming is suppressed. Those having a foam volume of 600 (mL) or less were evaluated as acceptable.

  As shown in Table 1, when the aqueous dispersion of the anti-adhesive agent for unvulcanized rubber of Examples 1 to 17 was used, all of the adhesiveness, the anti-adhesiveness, and the foaming property were good. Further, the unvulcanized rubber anti-blocking agents of Examples 1 to 17 do not contain bentonite which is a main component of a general anti-bonding agent, and other inorganic powders contain mica at 20% by mass of the whole. Contains only a small amount. For this reason, according to Examples 1 to 17, the problem of dust contamination derived from the inorganic powder was suppressed.

  On the other hand, the adhesion inhibitor for unvulcanized rubber of Comparative Example 1 containing no component (B) had extremely low adhesion and low adhesion. The HLB of the nonionic surfactant according to the Griffin method, which is too low at 7.9, was not problematic for the unvulcanized rubber anti-adhesive of Comparative Example 1, but the foaming was sufficiently suppressed. Was not. The nonionic surfactant had an HLB by Griffin's method of 18.2, which was too high, and the adhesive for unvulcanized rubber of Comparative Example 3 had low adhesion and adhesion.

Claims (5)

An anti-curing agent for unvulcanized rubber, comprising the following components (A) to (C).

(A) a fatty acid alkali metal salt (B) a salt of a fatty acid and a metal other than an alkali metal (C) a nonionic surfactant having an HLB of 9 to 18 by the Griffin method The unvulcanized rubber antiblocking agent according to claim 1, wherein the proportion of the fatty acid alkali metal salt having 16 or more carbon atoms in the component (A) is 70% by mass or more. The anti-adhesive agent for unvulcanized rubber according to claim 1 or 2, wherein the proportion of the unsaturated fatty acid alkali metal salt in the component (A) is 70% by mass or less. The anti-adhesive agent for unvulcanized rubber according to any one of claims 1 to 3, further comprising the following component (D).

(D) Non-swellable inorganic powder An unvulcanized rubber anti-adhesive agent aqueous dispersion comprising the unvulcanized rubber anti-adhesive according to any one of claims 1 to 4, and water.