Anti-adhesion composition for unvulcanized rubber and its use

Abstract

To provide an anti-tack agent composition for unvulcanized rubber with excellent water permeability and excellent wettability, and a method for producing unvulcanized rubber subjected to anti-tack treatment using the anti-tack agent composition for unvulcanized rubber.SOLUTION: An anti-tack agent composition for unvulcanized rubber includes the following components (A)-(C). The component (A), illustrated below, includes water-swellable inorganic powder (A1). The weight ratio (A1 / A) of the water-swellable inorganic powder (A1) to the component (A) is 0.5-0.9. The bulk density is 0.7-1.0 g / cm3. The component (A) is inorganic powder, the component (B) is a fatty acid alkali metal salt, and the component (C) is a surfactant excluding the component (B).SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to an anti-adhesion composition for unvulcanized rubber and its use. [Background technology]

[0002] In the production and processing of rubber products, unvulcanized rubber is sometimes stored in stacks until it is moved to the next molding or vulcanization process. In this case, an anti-adhesion agent (anti-sticking agent) is used to prevent the rubber from sticking together. Generally, anti-adhesion agents are applied to rubber surfaces in the form of an aqueous dispersion and then dried. Application methods include spraying the aqueous dispersion or immersing the rubber surface in it. As an anti-adhesion agent, a mixture of hydrophobic metal soaps or wax powders and surfactants is widely used. Because metal soaps and wax powders are hydrophobic, they readily adhere to hydrophobic rubber surfaces and exhibit good anti-adhesion properties. However, as mentioned above, anti-adhesion agents are often used in the form of aqueous dispersions, which makes it time-consuming to disperse the hydrophobic powder components in water, and if they are not uniformly dispersed, it can lead to a deterioration in wettability to the rubber. Furthermore, as described in Patent Documents 1 and 2, anti-adhesion agents in the form of water dispersion have been developed. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2009-084489 [Patent Document 2] Japanese Patent Publication No. 2017-88686 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, it was found that the anti-adhesion agents described in Patent Documents 1 and 2 lack sufficient water permeability, requiring strong mechanical force to be applied beforehand to forcibly disperse them in water, which presents problems in terms of time and cost. The object of the present invention is to provide an anti-adhesion agent composition for unvulcanized rubber that has excellent water permeability and excellent wettability, and a method for producing anti-adhesion treated unvulcanized rubber using the anti-adhesion agent composition for unvulcanized rubber. [Means for solving the problem]

[0005] As a result of diligent research to solve the above problems, the inventors of the present invention have found that the problems can be solved by using an anti-adhesion composition for unvulcanized rubber that contains specific components and has a specific bulk density. In other words, the anti-adhesion composition for unvulcanized rubber of the present invention comprises the following components (A) to (C), wherein component (A) comprises a water-swellable inorganic powder (A1), the weight ratio of the water-swellable inorganic powder (A1) to component (A) (A1 / A) is 0.5 to 0.9, and the bulk density is 0.7 to 1.0 g / cm³. 3 That is the case. Component (A): Inorganic powder Ingredient (B): Alkali metal salt of fatty acid Ingredients (C): Surfactants excluding ingredient (B)

[0006] The anti-adhesion composition for unvulcanized rubber of the present invention preferably contains 30 to 90 parts by weight of component (A), 1 to 30 parts by weight of component (B), and 1 to 30 parts by weight of component (C) per 100 parts by weight of the composition. The anti-adhesion composition for unvulcanized rubber of the present invention preferably comprises an anionic surfactant (C1) and a nonionic surfactant (C2) as component (C), wherein the weight ratio (C1 / C2) of the anionic surfactant (C1) to the nonionic surfactant (C2) is 0.8 to 10. The anti-adhesion composition for unvulcanized rubber of the present invention preferably contains a fatty acid alkali metal salt (B1) having 16 carbon atoms as component (B), and the weight ratio (B1 / B) of the fatty acid alkali metal salt (B1) to component (B) is 0.1 to 0.8. The antisticking agent composition for unvulcanized rubber of the present invention preferably contains the following component (D) and / or the following component (E). Component (D): Metal soap Component (E): Wax

[0007] The aqueous dispersion of the antisticking agent composition for unvulcanized rubber of the present invention contains the above antisticking agent composition for unvulcanized rubber and water. The method for producing the antisticking-treated unvulcanized rubber of the present invention includes a step of attaching the aqueous dispersion of the antisticking agent composition for unvulcanized rubber to the surface of the unvulcanized rubber and further volatilizing water.

Effect of the Invention

[0008] The antisticking agent composition for unvulcanized rubber of the present invention is excellent in water permeability and further excellent in wettability. Further, the antisticking agent composition for unvulcanized rubber of the present invention is excellent in antisticking property. The method for producing the antisticking-treated unvulcanized rubber of the present invention uses the above antisticking agent composition for unvulcanized rubber, and can efficiently produce an antisticking-treated unvulcanized rubber composition.

Modes for Carrying Out the Invention

[0009] The antisticking agent composition for unvulcanized rubber of the present invention (hereinafter sometimes simply referred to as the antisticking agent composition) essentially contains the following components (A) to (C). Component (A): Inorganic powder Component (B): Fatty acid alkali metal salt Component (C): Surfactant excluding component (B) Hereinafter, various components constituting the antisticking agent composition of the present invention will be described in detail.

[0010] 〔Component (A): Inorganic powder〕 The inorganic powder (hereinafter sometimes simply referred to as component (A)) is a component of a material that forms a film on the surface of unvulcanized rubber and exhibits antisticking property. Component (A) contains a water-swellable inorganic powder (A1) (hereinafter sometimes simply referred to as component (A1)). In the present invention, component (A1) means an inorganic powder having the property of absorbing water and increasing in volume.

[0011] As the component (A1), for example, bentonite, montmorillonite, saponite, hectorite, pyrophyllite, nontronite, sauconite, stevensite, magnesium aluminum silicate, anhydrous silicic acid, etc. can be mentioned, and these may be natural products or synthetic products. The above component (A1) may be used alone or in combination of two or more. Moreover, although there is no particular limitation on the component (A1), from the viewpoint of improving the anti-deposition property, it is preferable to contain at least one selected from bentonite, montmorillonite, saponite and hectorite.

[0012] The weight ratio (A1 / A) of the component (A1) to the component (A) is 0.5 to 0.9. If the weight ratio is less than 0.5, the anti-deposition property deteriorates, and if it exceeds 0.9, the dispersibility deteriorates. A1 / A is preferably 0.525 to 0.875, more preferably 0.55 to 0.85, and particularly preferably 0.575 to 0.825.

[0013] The component (A) contains an inorganic powder other than the component (A1). As the inorganic powder other than the component (A1), there is a non-water-swellable inorganic powder (A2) (hereinafter, sometimes simply referred to as the component (A2)). As the component (A2), for example, silicates such as kaolinite; carbonates such as calcium carbonate, sodium carbonate, magnesium carbonate; sulfates such as calcium sulfate, barium sulfate; metal oxides such as amorphous silica, alumina, magnesium oxide, antimony trioxide, titanium oxide, white carbon; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, iron hydroxide; red iron oxide; carbon black; graphite, etc. can be mentioned, and one kind or two or more kinds may be used in combination. Although there is no particular limitation on the component (A2), from the viewpoint of anti-deposition property, it is preferable to contain at least one selected from silicates and carbonates.

[0014] When component (A) contains component (A2), the weight ratio of component (A2 / A) to component (A) is not particularly limited, but is preferably 0.05 to 0.5, more preferably 0.1 to 0.5, even more preferably 0.125 to 0.475, particularly preferably 0.15 to 0.45, and most preferably 0.175 to 0.425. When the weight ratio is 0.05 or higher, dispersibility tends to improve, and when it is 0.5 or lower, anti-adhesion properties tend to improve.

[0015] Additionally, component (A) may contain crystalline silica. Examples of crystalline silica include quartz, cristobalite, tridymite, coesite, and stishobalite. The weight ratio of crystalline silica to component (A) (crystalline silica / A) is not particularly limited, but is preferably 0.2 or less, more preferably 0.1 or less, and especially preferably 0.05 or less. When the weight ratio is 0.2 or less, dispersibility and anti-adhesion properties tend to improve.

[0016] The average particle size of component (A) is not particularly limited, but is preferably 0.1 to 200 μm, more preferably 0.1 to 100 μm, even more preferably 0.1 to 50 μm, particularly preferably 0.1 to 40 μm, and most preferably 0.1 to 30 μm. When the average particle size is within the above range, adhesion to unvulcanized rubber tends to improve. The average particle size of component (A) in this invention was measured using a dry-type laser diffraction particle size distribution analyzer (Mastersizer 3000, Malvern) and the dry measurement method. The average particle size was determined using the D50 value obtained by volume-based measurement.

[0017] The bulk density of component (A) is not particularly limited, but is preferably 0.3 to 1.1 g / cm³ in order to improve its permeability to water. 3 More preferably 0.31 to 1.09 g / cm³ 3 More preferably 0.32 to 1.08 g / cm³ 3 Particularly preferred is 0.33 to 1.07 g / cm³ 3 Most preferably 0.34 to 1.06 g / cm³ 3 That is the case. The bulk density of this invention is the loose bulk density, and is determined by the method described in the examples.

[0018] The content of component (A) per 100 parts by weight of the anti-adhesion agent composition is not particularly limited, but is preferably 30 to 90 parts by weight, more preferably 35 to 85 parts by weight, and especially preferably 40 to 80 parts by weight. When the content is 30 parts by weight or more, the anti-adhesion properties tend to improve, and when it is 90 parts by weight or less, the wettability tends to improve.

[0019] [Component (B): Alkali metal salt of fatty acid] The fatty acid alkali metal salt (hereinafter sometimes simply referred to as component (B)) prevents component (A) from becoming a granular powder, and because component (B) itself dissolves and disperses easily in water, it enhances water penetration. Furthermore, it also has the effect of adhering to the rubber surface and exhibiting anti-adhesion properties. The number of carbon atoms in component (B) is not particularly limited, but is preferably 6 to 22, more preferably 8 to 20, and even more preferably 10 to 18.

[0020] The fatty acids constituting component (B) can be straight-chain or branched saturated or unsaturated fatty acids. For example, single fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid can be used, as well as natural fatty acids such as palm kernel fatty acid, palm stearate fatty acid, coconut oil fatty acid, and beef tallow fatty acid. These may be used individually or in combination of two or more. Furthermore, as for component (B), examples include potassium salts, sodium salts, lithium salts, rubinium salts, cesium salts, etc., and one or more of these may be used in combination.

[0021] Component (B) is not particularly limited, but it is preferable to include an alkali metal salt of a 16-carbon fatty acid (B1) (hereinafter sometimes simply referred to as component (B1)) in order to enhance water permeability and adhesion resistance. When component (B) contains component (B1), the weight ratio of component (B1 / B) to component (B) is not particularly limited, but is preferred in the following order: (1) 0.1 to 0.8, (2) 0.12 to 0.78, (3) 0.14 to 0.76, (4) 0.16 to 0.74, (5) 0.18 to 0.72, and (6) 0.20 to 0.70 (the higher the number in parentheses, the more preferable it is). When the weight ratio is 0.1 or higher, the anti-adhesion properties tend to improve, and when it is 0.8 or lower, the water permeability tends to improve.

[0022] The content of component (B) per 100 parts by weight of the anti-adhesion agent composition is not particularly limited, but is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, and most preferably 3 to 20 parts by weight.

[0023] [Component (C): Surfactants excluding component (B)] The surfactants other than component (B) described above (hereinafter sometimes simply referred to as component (C)) are components that enhance the water penetration of the anti-adhesion composition and assist in the wettability and adhesion to unvulcanized rubber. Component (C) may include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and one or more of these may be used in combination.

[0024] Examples of nonionic surfactants include: decyl ether with 3 moles of polyoxyethylene, decyl ether with 3 moles of polyoxyethylene and 1 mole of polyoxypropylene, decyl ether with 5 moles of polyoxyethylene, decyl ether with 7 moles of polyoxyethylene, isodecyl ether with 3 moles of polyoxyethylene, isodecyl ether with 3 moles of polyoxyethylene and 1 mole of polyoxypropylene, isodecyl ether with 5 moles of polyoxyethylene, isodecyl ether with 7 moles of polyoxyethylene, lauryl ether with 3 moles of polyoxyethylene, lauryl ether with 3 moles of polyoxyethylene and 1 mole of polyoxypropylene, lauryl ether with 5 moles of polyoxyethylene, lauryl ether with 7 moles of polyoxyethylene, tridecyl ether with 3 moles of polyoxyethylene, tridecyl ether with 3 moles of polyoxyethylene and 1 mole of polyoxypropylene, tridecyl ether with 5 moles of polyoxyethylene, tridecyl ether with 7 moles of polyoxyethylene, and polyoxyethylene Polyoxyalkylene alkyl ethers such as isotridecyl ether with 3 moles of polyoxyethylene added, isotridecyl ether with 3 moles of polyoxyethylene and 1 mole of polyoxypropylene added, isotridecyl ether with 5 moles of polyoxyethylene added, isotridecyl ether with 7 moles of polyoxyethylene added, myristyl ether with 3 moles of polyoxyethylene added, myristyl ether with 3 moles of polyoxyethylene and 1 mole of polyoxypropylene added, myristyl ether with 5 moles of polyoxyethylene added, myristyl ether with 7 moles of polyoxyethylene added, cetyl ether with 3 moles of polyoxyethylene added, cetyl ether with 3 moles of polyoxyethylene and 1 mole of polyoxypropylene added, cetyl ether with 5 moles of polyoxyethylene added, cetyl ether with 7 moles of polyoxyethylene added; polyoxyalkylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether; polyoxyalkylene fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monooleate;Examples include polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate; polyoxyalkylene alkylamines; fatty acid alkanolamides; polyoxyalkylene fatty acid amides; polyoxyalkylene hydrogenated castor oil; polyoxyalkylene sorbitol fatty acid esters; polyglycerin fatty acid esters; alkylglycerin ethers; polyoxyalkylene cholesteryl ethers; alkyl polyglucosides; sucrose fatty acid esters; and oxyethylene-oxypropylene block polymers, which may be used individually or in combination of two or more.

[0025] Examples of anionic surfactants include alkyl sulfate esters such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium stearyl sulfate, and sodium cetyl sulfate; polyoxyalkylene alkyl ether acetates such as sodium polyoxyethylene tridecyl ether acetate; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; polyoxyalkylene alkyl ether sulfates; long-chain sulfosuccinates such as sodium 2-ethylhexyl sulfosuccinate; N-acyl sarcosinates such as sodium oleoyl sarcosinate and sodium lauroyl sarcosinate; and stearoyl methyl Examples include higher fatty acid amide sulfonates such as sodium taurate, sodium lauroyl methyltaurate, sodium myristoyl methyltaurate, and sodium palmitoyl methyltaurate; alkyl phosphates such as sodium monostearyl phosphate; polyoxyalkylene alkyl ether phosphate salts such as sodium polyoxyethylene oleyl ether phosphate and sodium polyoxyethylene stearyl ether phosphate; and long-chain N-acyl glutamates such as sodium N-lauroyl glutamate monosodium and disodium N-stearoyl-L-glutamate. One or more of these may be used in combination.

[0026] Examples of cationic surfactants include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, and cetyltrimethylammonium bromide; dialkyldimethylammonium salts; trialkylmethylammonium salts; and alkylamine salts. One or more of these may be used in combination. Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants such as 2-undecyl-N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium and 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt; betaine-based amphoteric surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauryldimethylaminoacetic acid betaine, and coconut oil fatty acid amidopropyl betaine; and amino acid-type amphoteric surfactants such as N-laurylglycine, N-lauryl β-alanine, and N-stearyl β-alanine. One or more of these may be used in combination.

[0027] Component (C) preferably contains an anionic surfactant (C1) and a nonionic surfactant (C2) in order to enhance water permeability and wettability. Hereinafter, the anionic surfactant (C1) may simply be referred to as component (C1), and the nonionic surfactant (C2) may simply be referred to as component (C1). When component (C) contains components (C1) and (C2), the weight ratio (C1 / C2) of component (C1) to component (C2) is not particularly limited, but is preferred in the following order: (1) 0.8 to 10, (2) 0.9 to 9.9, (3) 1.0 to 9.8, (4) 1.1 to 9.7, (5) 1.2 to 9.6, (6) 1.3 to 9.5, and (7) 1.4 to 9.4 (the higher the number in parentheses, the more preferable). When the weight ratio is 0.8 or higher, the permeability to water tends to improve, and when it is 10 or lower, the wettability tends to improve.

[0028] Furthermore, the HLB of component (C2) by the Griffin method is not particularly limited, but is preferably 3 to 13, more preferably 4 to 12, even more preferably 5 to 11, and especially preferably 6 to 10. When the HLB is 3 or higher, the permeability to water tends to improve, and when it is 13 or lower, the wettability tends to improve. Here, HLB by the Griffin method is a value that can be calculated based on the molecular structure using the method described below (I). In other words, HLB by the Griffin method takes a value from 0 to 20, with a smaller value indicating lipophilicity and a larger value indicating hydrophilicity. HLB = 20 × (Sum of formula weights of hydrophilic parts / Molecular weight) (I)

[0029] Component (C2) may contain a compound represented by the following general formula (1), and the HLB of the compound by the Griffin method may be 3 to 13. RO-(AO)nH (1)

[0030] In general formula (1), R is an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be linear or branched. Furthermore, the aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. In general formula (1), AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is the average number of moles of AO added. An example of an oxyalkylene group having 2 to 4 carbon atoms is a polymerization unit formed by the addition of an alkylene oxide having 2 to 4 carbon atoms. If multiple types of oxyalkylene groups are included, these groups may be arranged in a block-like manner or randomly.

[0031] The content of component (C) per 100 parts by weight of the anti-adhesion agent composition for unvulcanized rubber is not particularly limited, but is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, and especially preferably 3 to 20 parts by weight. When the content is 1 part by weight or more, the permeability to water tends to improve, and when the content is 30 parts by weight or less, the anti-adhesion properties tend to improve.

[0032] The anti-adhesion composition of the present invention may further contain the following components (D) and / or (E). Ingredient (D): Metal soap Ingredient (E): Wax

[0033] [Ingredient (D): Metal soap] Metallic soap (hereinafter sometimes simply referred to as component (D)) is a component that adheres to the surface of unvulcanized rubber, reduces friction between unvulcanized rubbers, and improves adhesion resistance. Examples of component (D) include magnesium laurate, calcium laurate, zinc laurate, magnesium myristate, calcium myristate, zinc myristate, magnesium palmitate, calcium palmitate, zinc palmitate, magnesium stearate, calcium stearate, zinc stearate, aluminum trioctadecanoate, aluminum dioctadecanoate, aluminum monooctadecanoate, calcium octadecanoate, zinc octadecanoate, magnesium octadecanoate, and barium octadecanoate. Component (D) is not particularly limited, but it is preferable that it be at least one selected from magnesium stearate, calcium stearate, and zinc stearate, as this has a high effect in reducing friction between unvulcanized rubbers.

[0034] [Ingredient (E): Wax] The wax (hereinafter sometimes simply referred to as component (E)) is a component that adheres to the surface of unvulcanized rubber, reduces friction between unvulcanized rubbers, and improves adhesion, similar to component (D). Examples of component (E) include particles of plant-based waxes, animal-based waxes, mineral waxes, petroleum waxes, synthetic hydrocarbon waxes, modified waxes, hydrogenated waxes, fatty acid amides, and phthalic acid imide anhydride, and one or more of these may be used in combination.

[0035] Examples of plant-based waxes include candelilla wax, carnauba wax, rice wax, wood wax, jojoba oil, sugar wax, bayberry wax, ocury wax, and esparto wax. Examples of animal-derived waxes include beeswax, lanolin, whale wax, insect wax, and shellac wax. Examples of mineral-based waxes include montan wax, ozokerite, and ceresin. Examples of petroleum waxes include paraffin wax, microcrystalline wax, and petrolactum. Examples of synthetic hydrocarbon waxes include Fischer-Tropsch wax and polyethylene wax. Examples of modified waxes include montan wax derivatives, paraffin wax derivatives, and microcrystalline wax derivatives.

[0036] Examples of hydrogenated waxes include hydrogenated castor oil, 12-hydroxystearic acid, 12-hydroxystearic acid amide, N-hydroxyethyl-12-hydroxystearylamide, N,N'-ethylene-bis-12-hydroxystearylamide, N,N'-hexamethylene-bis-12-hydroxystearylamide, N,N'-xylylene-bis-12-hydroxystearylamide, methyl-12-hydroxystearate, propylene glycol-mono-12-hydroxystearate, and ethylene glycol-mono-12-hydroxystearate. Examples of fatty acid amides include lauric acid amide, stearic acid amide, oleic acid amide, erucic acid amide, N,N'-xylylenebistearic acid amide, coconut oil fatty acid monoethanolamide, N-oleyl stearic acid amide, and N,N'-dioleyl adipate amide.

[0037] The total content of components (D) and (E) per 100 parts by weight of the anti-adhesion agent composition is not particularly limited, but is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, and most preferably 3 to 20 parts by weight. When the content is 1 part by weight or more, the anti-adhesion properties tend to improve, and when the content is 30 parts by weight or less, the permeability to water tends to improve.

[0038] The anti-adhesion composition of the present invention may contain other components (hereinafter simply referred to as "other components") in addition to components (A) to (E) described above. While there are no particular limitations on the other components, examples include water-soluble polymers, polyhydric alcohols, defoaming agents, and preservatives.

[0039] [Water-soluble polymer] Water-soluble polymers are components that impart viscosity to the aqueous dispersion of the anti-adhesion agent composition, improving its adhesion to the surface of unvulcanized rubber. Examples of water-soluble polymers include starches such as oxidized starch, acetic acid starch, phosphate starch, carboxymethyl starch, carboxyethyl starch, hydroxyethyl starch, positive starch, cyanoethylated starch, and dialdehyde starch; mannan; alginic acids such as alginic acid, sodium alginate, propylene glycol alginate, triethanolamine alginate, and ammonium alginate; methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and hydroxyethylmethylcellulose. Examples include cellulose ethers such as cellulose, hydroxyethyl ethylcellulose, and carboxymethylcellulose; natural gums such as tarakanto gum, gum arabic, guar gum, xanthan gum, British gum, glucomannan, gellan gum, tara gum, locust bean gum, and carrageenan; sodium polyacrylate; polyvinyl alcohol; polyethylene glycol; polyethylene oxide; water-soluble acrylic resin; water-soluble urethane resin; water-soluble melamine resin; water-soluble epoxy resin; water-soluble butadiene resin; water-soluble phenolic resin, etc., and one or more of these may be used in combination.

[0040] [Polyhydric alcohols] Polyhydric alcohols adhere to the surface of unvulcanized rubber, providing lubrication between the unvulcanized rubber layers and reducing friction between them. Examples of polyhydric alcohols include glycerin, 1,3-butanediol, propylene glycol, dipropylene glycol, pentylene glycol, neopentyl glycol, hexylene glycol, polyethylene glycol, erythritol, pentaerythritol, dipentaerythritol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, xylitol, sorbitol, mannitol, maltitol, maltotriose, glucose, sucrose, fructose, maltose, etc., and one or more of these may be used in combination.

[0041] [Antifoaming agent] Examples of defoaming agents include: silicone-based defoaming agents such as polymethylsiloxane and polyether-modified silicone; oil-based defoaming agents such as castor oil, sesame oil, linseed oil, and animal and vegetable oils; fatty acid-based defoaming agents such as stearic acid, oleic acid, and palmitic acid; fatty acid ester-based defoaming agents such as isoamyl stearate, distearyl succinate, ethylene glycol distearate, and butyl stearate; and polyoxyalkylene monohydrate alcohols such as di-t-amylphenoxyethanol, 3-heptanol, and 2-ethylhexanol. Examples of antifoaming agents include ethanol-based antifoamers; ether-based antifoamers such as di-t-amylphenoxyethanol, 3-heptylcellosolve, nonylcellosolve, and 3-heptylcarbitol; phosphate ester antifoamers such as tributylphosphate and tris(butoxyethyl)phosphate; amine-based antifoamers such as diamylamine; amide-based antifoamers such as polyalkyleneamide and acylate polyamine; sulfate ester antifoamers such as sodium lauryl sulfate; polyoxyalkylene antifoamers; and mineral oils. One or more of these may be used in combination.

[0042] [Preservatives] Examples of preservatives include thiazoles such as thiazole and 2-mercaptothiazole; thiocyanates such as methylene bisthiocyanate and ammonium thiocyanate; sulfimides such as o-benzoix sulfimide and phenylmercuric-o-benzoix sulfimide; alkyldialkylthiocarbamates such as methyldimethylthiocarbamate and ethyldiethyldithiocarbamate; thiraum sulfides such as tetramethylthiraum sulfide and tetraethylthiraum sulfide; thiraum disulfides such as tetramethylthiraum disulfide and tetraethylthiraum disulfide; dithiocarbamates such as ferric diethyldithiocarbamate and reed dimethyldithiocarbamate; sulfamides such as o-toluenesulfonamide and benzenesulfonanilide; and 1-aminonaphthyl-4-sulfonic acid, 1-amino Examples include aminosulfonic acids such as -2-naphthol-4-sulfonic acid; phenols such as pentachlorophenol and o-phenylphenol and their alkali metal salts; chloride quinones such as tetrachloro-p-benzoquinone and 2,3-dichloro-1,4-naphthoquinone; nitro group-containing compounds such as dinitrocaprylphenylcrotonate and dinitro-o-cresol; triazines such as 1,3,5-trihydroxyethylhexahydro-1,3,5-triazine and 1,3,5-triethylhexahydro-1,3,5-triazine; organic mercury compounds such as phenylmercuric phthalate and o-hydroxyphenylmercuric chloride; amines such as p-aminoazobenzene and diphenylamine; amides such as cinnamanilide; and iodine-containing compounds such as 1,3-diiodo-2-propanol. One or more of these may be used in combination.

[0043] [Anti-adhesion agent composition for unvulcanized rubber] The bulk density of the anti-adhesion composition of the present invention is 0.70 to 1.0 g / cm³. 3 That is the case. The anti-adhesion composition contains the above components (A) to (C) as essential components and has a bulk density within the above range, thereby exhibiting excellent water penetration and excellent wettability. The bulk density of the anti-adhesion agent composition is preferably 0.71 to 0.99 g / cm³.3 , more preferably 0.72 to 0.98 g / cm 3 , still more preferably 0.73 to 0.97 g / cm 3 , particularly preferably 0.74 to 0.96 g / cm 3 , most preferably 0.75 to 0.95 g / cm 3 . The bulk density of the anti-adhesive agent composition for unvulcanized rubber is determined by the method described in the examples. Further, from the viewpoint of achieving the effects of the present application, the anti-adhesive agent composition of the present invention is preferably in powder form.

[0044] [Method for producing an anti-adhesive agent composition for unvulcanized rubber] Regarding the anti-adhesive agent composition of the present invention, the production method thereof is not particularly limited with respect to the mixing order, the mixing device to be used, etc., as long as it includes a step of mixing components (A) to (C) as essential components and, if necessary, component (D), component (E), and other components. Examples of the mixing device include powder mixers such as ribbon mixers and Nauta mixers.

[0045] [Aqueous dispersion of an anti-adhesive agent composition for unvulcanized rubber and its production method] The aqueous dispersion of the anti-adhesive agent composition for unvulcanized rubber of the present invention is not particularly limited, but is an aqueous dispersion containing the above anti-adhesive agent composition for unvulcanized rubber and water, in which the anti-adhesive agent composition is dispersed in water.

[0046] In the aqueous dispersion of the anti-adhesive agent composition for unvulcanized rubber of the present invention, the production method may be, for example, a method of mixing and dispersing the above anti-adhesive agent composition for unvulcanized rubber in water. The concentration of the anti-adhesive agent composition in the aqueous dispersion of the anti-adhesive agent composition for unvulcanized rubber of the present invention is not particularly limited, but is preferably 0.01 to 10% by weight, more preferably 0.05 to 7.5% by weight, and still more preferably 0.1 to 5.0% by weight. When the concentration is 0.01% by weight or more, the anti-adhesive property tends to improve, and when it is 10% by weight or less, the drying property tends to improve.

[0047] [Method for producing an unvulcanized rubber treated with an anti-adhesive agent] The present invention relates to a method for producing anti-adhesion treated unvulcanized rubber, which includes a step of applying the above-mentioned anti-adhesion composition for unvulcanized rubber to the surface of the unvulcanized rubber. Here, the unvulcanized rubber may be molded.

[0048] In the processing step, a wet method is preferred, that is, a method using an aqueous dispersion in water as the anti-adhesion agent composition for unvulcanized rubber. When performing the processing step using a wet method, examples include spraying the anti-adhesion agent composition for unvulcanized rubber or its aqueous dispersion, spraying it onto the rubber in a fine stream, or immersing it in an aqueous dispersion. Among these, immersion in an aqueous dispersion is preferred because it allows for uniform application of the anti-adhesion agent composition for unvulcanized rubber. Next, drying may be carried out after the aqueous dispersion is applied. There are no particular limitations on the drying method, but it is preferable to use a method that forces drying by blowing hot air using a hot air fan or blow heater.

[0049] The unvulcanized rubber used in the method for producing anti-adhesion treated unvulcanized rubber of the present invention is usually heated to 100-180°C, and the unvulcanized rubber can also be cooled in the immersion method in an aqueous dispersion. The temperature of the aqueous dispersion is not particularly limited, but it is preferably 0-60°C. Next, a step may be taken to dry the unvulcanized rubber after the aqueous dispersion has been applied. There are no particular limitations on the drying method, but from an economic standpoint, it is preferable to use a method that forces drying by blowing hot air using a hot air fan or blow heater.

[0050] In the processing step, a dry method may be used, that is, an anti-adhesion agent composition that is not in the form of an aqueous dispersion. When the anti-adhesion treated unvulcanized rubber produced by the above manufacturing method is stored in stacks between processes, it is possible to prevent the unvulcanized rubber pieces from sticking together. [Examples]

[0051] The present invention will be specifically described below with reference to examples and comparative examples. The present invention is not limited to these examples. The physical properties in the examples and comparative examples were evaluated as follows. Examples 3, 4, and 21 are for reference only.

[0052] [bulk density] The bulk density of component (A) and the anti-adhesion agent composition for unvulcanized rubber was determined using a multi-functional powder property measuring instrument, the Multi-Tester (MT-1001k model / manufactured by Seishin Corporation), by measuring the loose bulk density (g / cm³). 3 The following measurements were taken: A funnel, sieve (mesh opening 710 μm), and sieve spacer were stacked on top of the feeder unit in that order and secured with a stopper. A cell container (made of stainless steel, dimensions: 50.5 mm (inner diameter) x 50 mm (height), internal volume: 100 cm³) was placed on the sample stand. 3 A sample was placed in the sample unit, and the sample was introduced while the feeder was vibrated to fill the cell with the sieved sample, which was then leveled off with a leveling plate. The loose bulk density ρ (g / cm³) of each sample was determined. 3 The measurement was performed using the following formula. ρ = (W1 - W0) / V1 V1: Cell container capacity (cm 3 ) W0: Weight of the cell container (g) W1: Weight of the cell container after sample filling (total weight of the cell container and sample) (g)

[0053] [Water permeability] 294g of water, heated to 20°C, was placed in a 300ml glass beaker, and 6g of an anti-adhesion agent composition for unvulcanized rubber was gently added and allowed to stand. After 5 minutes, the floating anti-adhesion agent composition for unvulcanized rubber was collected, and its weight and moisture content were measured to calculate the weight (W) that floated and did not permeate. The permeability was calculated using the obtained W, and the permeability to water was evaluated as follows. Dispersion rate (%)=(6-W) / 6×100 Dispersion rate of 90% or higher: Excellent water permeability (indicator ◎) Dispersion rate of 70% or more but less than 90%: Good water permeability (indicator ○) Dispersion rate between 40% and less than 70%: Poor water permeability (indicator △) Dispersion rate less than 40%: Very poor water permeability (indicator ×)

[0054] [Wettability] The dispersion obtained from the water permeability test described above, after removing undispersed material, was used. The water removed along with the undispersed material was replenished. The dispersion was stirred with a magnetic stirrer for more than 30 minutes in a warm bath heated to 45°C to obtain a homogeneous dispersion. NR / BR rubber test specimens (natural rubber / butadiene rubber; 0.5 cm thick x 5 cm long x 3 cm wide) heated to 100°C were immersed in a dispersion at 45°C and immediately removed. The wettability of the unvulcanized rubber surface was then evaluated as follows. The entire surface of the unvulcanized rubber is wet: Wettability is good (indicator is ○) Some areas of the unvulcanized rubber surface are repelled: Wettability is slightly poor (indicator is △) The entire surface of the unvulcanized rubber is repelling: Wettability is poor (indicator is ×)

[0055] [Adhesion resistance] The dispersion used for the wettability evaluation described above was used. An NR / BR test specimen (natural rubber / butadiene rubber; 0.5 cm thick x 5 cm long x 3 cm wide) heated to 100°C was immersed in the dispersion heated to 45°C and immediately removed. Two immersed rubber test specimens were prepared, air-dried, and then stacked. A pressure of 1000 kg / m² was applied. 2 The specimens were subjected to a load and left in a 40°C constant temperature chamber for 24 hours. After removing the specimens from the chamber, they were air-cooled to room temperature, and the peel resistance (N / cm) was measured using a tensile testing machine at a speed of 100 mm / min. The adhesion resistance was evaluated as follows based on the measured peel resistance. Peel resistance of 1 N / cm or less: Excellent adhesion (unvulcanized rubber can be easily separated from each other; the indicator is ◎) Peel resistance greater than 1 N / cm and less than 2 N / cm: Good adhesion resistance (unvulcanized rubber can be peeled apart without load; the indicator is ○) Peel resistance between 2N / cm and 3N / cm: Poor adhesion resistance (high load when separating unvulcanized rubber pieces, resulting in low adhesion resistance; index is △) Peel resistance exceeding 3 N / cm: Very poor adhesion (the rubbers adhere tightly to each other, making separation difficult. Adhesion resistance is very low; the indicator is ×)

[0056] (Example 1) A composition of anti-adhesion agent for unvulcanized rubber was obtained by uniformly mixing 50g of bentonite, 20g of kaolinite, 10g of calcium carbonate, 7g of sodium caprate, 3g of sodium palmitate, 9g of dioctyl sulfosuccinate, and 1g of POE(3)sec-alkyl(C12-C14) ether. Next, 6 g of the obtained anti-adhesion agent composition was added to 294 g of tap water, and its water penetration, wettability, and anti-adhesion properties were evaluated. The evaluation results are shown in Table 1, and it exhibited excellent water penetration and wettability, as well as excellent anti-adhesion properties.

[0057] (Example 2~ 28 ) Example 2~ 28 Now, Table 1 ~2 The evaluation was carried out in the same manner as in Example 1, except that the composition was changed as shown. The evaluation results are shown in Tables 1 and 2.

[0058] (Comparative Example 1) A composition of anti-adhesion agent for unvulcanized rubber was obtained by uniformly mixing 5g of bentonite, 65g of kaolinite, 10g of calcium carbonate, 7g of sodium caprate, 3g of sodium palmitate, 9g of dioctyl sulfosuccinate, and 1g of POE(3)sec-alkyl(C12-C14) ether. Next, 6 g of the obtained anti-adhesion agent composition was added to 294 g of tap water, and its water penetration, wettability, and anti-adhesion properties were evaluated. The evaluation results are shown in Table 2, and the water penetration and wettability were poor, while the anti-adhesion properties were very poor.

[0059] (Comparative Examples 2-7) Comparative Examples 2-7 were evaluated in the same manner as Comparative Example 1, except that the composition was changed as shown in Table 2. In Tables 1 and 2, POE(m) refers to polyoxyethylene (number of repeating units of oxyethylene: m).

[0060] [Table 1]

[0061] [Table 2]

[0062] As can be seen from Tables 1-2, the anti-adhesion compositions for unvulcanized rubber of Examples 1-28 are anti-adhesion compositions for unvulcanized rubber comprising an inorganic powder (A) containing a specific amount of water-swellable inorganic powder (A1), an alkali metal fatty acid salt (B), and a surfactant (C) excluding the alkali metal fatty acid salt (B), and the bulk density of the composition is 0.7-1.0 g / cm³. 3 As such, it has excellent water permeability and, furthermore, excellent wettability. On the other hand, as can be seen from Table 2, when the water-swellable inorganic powder (A1) is not present in a specific amount (Comparative Example 1), when inorganic powder (A) is not present (Comparative Examples 2 and 3), when fatty acid alkali metal salt (B) is not present (Comparative Example 4), when surfactants other than fatty acid alkali metal salt (C) are not present (Comparative Example 5), the bulk density of the anti-adhesion agent composition for unvulcanized rubber is 0.5 to 0.9 g / cm³. 3 Outside this range (Comparative Examples 6 and 7), at least one of the properties of water permeability and wettability is not good. [Industrial applicability]

[0063] The anti-adhesion composition for unvulcanized rubber of the present invention is used in the production and processing of unvulcanized rubber products and can prevent rubber from sticking together when the unvulcanized rubber is stored in stacks until it is moved to the next process such as molding or vulcanization. In this case, it has excellent water permeability and wettability, which enables improved productivity of rubber products.

Claims

1. An anti-adhesion composition for unvulcanized rubber comprising the following components (A) to (C), The following component (A) contains a water-swellable inorganic powder (A1), and the weight ratio (A1 / A) of the water-swellable inorganic powder (A1) to the following component (A) is 0.5 to 0.

71. The content of component (A) is 40 to 90 parts by weight per 100 parts by weight of the composition, the content of component (B) is 1 to 30 parts by weight, and the content of component (C) is 1 to 20 parts by weight. The loosening bulk density of the aforementioned anti-adhesion composition for unvulcanized rubber is 0.7 to 1.0 g / cm³. ３ An anti-adhesion composition for unvulcanized rubber. Component (A): Inorganic powder Ingredient (B): Alkali metal salt of fatty acid Ingredient (C): Surfactants excluding ingredient (B)

2. The anti-adhesion composition for unvulcanized rubber according to claim 1, wherein the content of component (A) is 65 to 90 parts by weight, the content of component (B) is 1 to 15 parts by weight, and the content of component (C) is 1 to 20 parts by weight.

3. The anti-adhesion composition for unvulcanized rubber according to claim 1 or 2, wherein the component (C) comprises an anionic surfactant (C1) and a nonionic surfactant (C2), and the weight ratio (C1 / C2) of the anionic surfactant (C1) to the nonionic surfactant (C2) is 0.8 to 10.

4. The anti-adhesion composition for unvulcanized rubber according to any one of claims 1 to 3, wherein component (B) comprises a fatty acid alkali metal salt (B1) having 16 carbon atoms, and the weight ratio (B1 / B) of the fatty acid alkali metal salt (B1) to component (B) is 0.1 to 0.

8.

5. An anti-adhesion composition for unvulcanized rubber according to any one of claims 1 to 4, comprising the following component (D) and / or the following component (E), wherein the total content of component (D) and component (E) per 100 parts by weight of the composition is 1 to 30 parts by weight. Ingredient (D): Metal soap Ingredient (E): Wax

6. An aqueous dispersion of the anti-adhesion agent composition for unvulcanized rubber according to any one of claims 1 to 5, and water.

7. A method for producing anti-adhesion treated unvulcanized rubber, comprising the steps of applying an aqueous dispersion of the anti-adhesion composition for unvulcanized rubber described in claim 6 to the surface of the unvulcanized rubber, and further volatilizing the water.

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