JP2023144369A - Anti-tack agent composition for unvulcanized rubber and use thereof - Google Patents

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

The present invention relates to an anti-adhesive composition for unvulcanized rubber and its use.

In the production and processing process of rubber products, unvulcanized rubber is sometimes stored in piles until it is transferred to the next process such as molding or vulcanization, and in this case, adhesion prevention is used to prevent the rubber from sticking together. (anti-adhesion agent) is used.
Generally, anti-adhesion agents are applied in the form of an aqueous dispersion to a rubber surface and dried. The coating method includes spraying an aqueous dispersion or dipping in an aqueous dispersion.
As the anti-adhesion agent, a mixture of hydrophobic metal soap or wax powder and a surfactant is widely used. Since metal soap and wax powder are hydrophobic, they easily adhere to the same hydrophobic rubber surface and exhibit good anti-adhesion properties. However, as mentioned above, anti-adhesive agents are often used in the form of aqueous dispersions, so it takes time and effort to disperse the hydrophobic powder components in water, and if they are not uniformly dispersed. , there is a problem that the wettability to rubber deteriorates.
Further, as in Patent Document 1 and Patent Document 2, anti-adhesive agents in the form of dispersion in water have been developed.

Japanese Patent Application Publication No. 2009-084489 JP2017-88686A

However, the anti-adhesion agents described in Patent Document 1 and Patent Document 2 lack water permeability, so it is necessary to apply strong mechanical force in advance to forcefully disperse them into water. It was confirmed that there were problems in terms of time and money.
The object of the present invention is to provide an anti-adhesive composition for unvulcanized rubber that has excellent permeability to water and excellent wettability, and an anti-adhesive composition for unvulcanized rubber that can be performed using the anti-adhesive composition for unvulcanized rubber. An object of the present invention is to provide a method for producing unvulcanized rubber that has been subjected to adhesion treatment.

As a result of intensive studies to solve the above problems, the inventors of the present invention found that the problems can be solved by using an anti-adhesive composition for unvulcanized rubber that contains specific components and has a specific bulk density.
That is, the anti-adhesion agent composition for unvulcanized rubber of the present invention contains the following components (A) to (C), where the following component (A) contains a water-swellable inorganic powder (A1), and the following component ( The weight ratio (A1/A) of the water-swellable inorganic powder (A1) to A) is 0.5 to 0.9, and the bulk density is 0.7 to 1.0 g/cm ³ .
Component (A): Inorganic powder Component (B): Fatty acid alkali metal salt Component (C): Surfactant other than component (B)

In the anti-adhesive composition for unvulcanized rubber of the present invention, the content of the component (A) is 30 to 90 parts by weight based on 100 parts by weight of the composition, and the content of the component (B) is 1 to 90 parts by weight. It is preferable that the amount of component (C) is 30 parts by weight and the content of component (C) is 1 to 30 parts by weight.
In the anti-adhesive composition for unvulcanized rubber of the present invention, the component (C) contains an anionic surfactant (C1) and a nonionic surfactant (C2), and the nonionic surfactant (C2) ) The weight ratio (C1/C2) of the anionic surfactant (C1) to (C1) is preferably 0.8 to 10.
In the anti-adhesive composition for unvulcanized rubber of the present invention, the component (B) contains a fatty acid alkali metal salt (B1) having 16 carbon atoms, and the fatty acid alkali metal salt (B1) is It is preferable that the weight ratio (B1/B) is 0.1 to 0.8.
The anti-adhesion 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

The aqueous dispersion of the anti-adhesion agent composition for unvulcanized rubber of the present invention contains the above-mentioned anti-adhesion agent composition for unvulcanized rubber and water.
The method for producing unvulcanized rubber subjected to adhesion prevention treatment of the present invention includes adhering an aqueous dispersion of the above-mentioned adhesion prevention agent composition for unvulcanized rubber to the surface of unvulcanized rubber, and further volatilizing the water. Including process.

The anti-adhesion agent composition for unvulcanized rubber of the present invention has excellent water permeability and further excellent wettability. Further, the anti-adhesive composition for unvulcanized rubber of the present invention has excellent anti-adhesive properties.
The method for producing unvulcanized rubber subjected to anti-adhesion treatment of the present invention uses the above-mentioned anti-adhesion agent composition for unvulcanized rubber, and efficiently produces an unvulcanized rubber composition subjected to anti-adhesion treatment. can.

The anti-adhesive composition for unvulcanized rubber of the present invention (hereinafter sometimes simply referred to as anti-adhesive composition) essentially contains the following components (A) to (C).
Component (A): Inorganic powder component (B): Fatty acid alkali metal salt component (C): Surfactant other than component (B) Below, various components constituting the anti-adhesive composition of the present invention will be explained in detail. .

[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 anti-adhesion properties.
Component (A) contains water-swellable inorganic powder (A1) (hereinafter sometimes simply referred to as component (A1)). In the present invention, component (A1) refers to an inorganic powder having the property of absorbing water and increasing its volume.

Component (A1) includes, for example, bentonite, montmorillonite, saponite, hectorite, pidelite, nontronite, saucosite, stevensite, magnesium aluminum silicate, silicic anhydride, etc., and these are natural products. It may also be a synthetic material. The above component (A1) may be used alone or in combination of two or more.
In addition, component (A1) is not particularly limited, but preferably contains at least one selected from bentonite, montmorillonite, saponite, and hectorite from the viewpoint of improving anti-adhesion properties.

The weight ratio (A1/A) of component (A1) to component (A) is 0.5 to 0.9. If the weight ratio is less than 0.5, anti-adhesion properties will be reduced, and if it exceeds 0.9, dispersibility will be reduced. A1/A is preferably 0.525 to 0.875, more preferably 0.55 to 0.85, particularly preferably 0.575 to 0.825.

Component (A) contains inorganic powder other than component (A1). Examples of inorganic powders other than component (A1) include non-water-swellable inorganic powder (A2) (hereinafter sometimes simply referred to as component (A2)).
Component (A2) includes, for example, silicates such as kaolinite; carbonates such as calcium carbonate, sodium carbonate, and magnesium carbonate; sulfates such as calcium sulfate and barium sulfate; amorphous silica, alumina, magnesium oxide, and Metal oxides such as antimony oxide, titanium oxide, white carbon; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, iron hydroxide; red iron oxide; carbon black; graphite, etc., and one or more of them may be used. May be used together.
Component (A2) is not particularly limited, but preferably contains at least one selected from silicates and carbonates from the viewpoint of anti-adhesion properties.

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

Moreover, 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, particularly preferably 0.05 or less. It is. When the weight ratio is 0.2 or less, the dispersibility and adhesion prevention properties tend to improve.

The average particle diameter 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. , most preferably 0.1 to 30 μm. When the average particle diameter is within the above range, adhesion to unvulcanized rubber tends to improve.
The average particle diameter of component (A) in the present invention was measured by a dry measurement method using a dry laser diffraction particle size distribution analyzer (Mastersizer 3000, manufactured by Malvern). For the average particle diameter, the D50 value based on volume-based measurement was adopted.

The bulk specific gravity of component (A) is not particularly limited, but from the viewpoint of improving water permeability, it is preferably 0.3 to 1.1 g/cm ³ , more preferably 0.31 to 1.09 g/cm 3 . cm ³ , more preferably 0.32 to 1.08 g/cm ³ , particularly preferably 0.33 to 1.07 g/cm ³ , and most preferably 0.34 to 1.06 g/cm ³ .
The bulk density of the present invention is a loose bulk density and is obtained by the method described in the Examples.

The content of component (A) with respect to 100 parts by weight of the anti-adhesive composition is not particularly limited, but is preferably 30 to 90 parts by weight, more preferably 35 to 85 parts by weight, particularly preferably 40 to 80 parts by weight. be. When the content is 30 parts by weight or more, adhesion prevention properties tend to improve, and when the content is 90 parts by weight or less, wettability tends to improve.

[Component (B): Fatty acid alkali metal salt]
Fatty acid alkali metal salts (hereinafter sometimes simply referred to as component (B)) prevent component (A) from forming joint powder, and since component (B) itself is easily dissolved and dispersed in water, it prevents it from penetrating into water. enhance sexuality. Furthermore, it also has the effect of adhering to the rubber surface and exhibiting adhesion prevention properties.
The number of carbon atoms in component (B) is not particularly limited, but is preferably 6 to 22, more preferably 8 to 20, even more preferably 10 to 18.

The fatty acid constituting component (B) can be a linear or branched saturated or unsaturated fatty acid, such as single fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid. Natural fatty acids such as , palm kernel fatty acid, palm stearin fatty acid, coconut oil fatty acid, beef tallow fatty acid, etc. can be used. These may be used alone or in combination of two or more.
In addition, examples of component (B) include potassium salts, sodium salts, lithium salts, rubinium salts, cesium salts, etc., and one type or two or more types may be used in combination.

Component (B) is not particularly limited, but from the viewpoint of improving water permeability and adhesion resistance, it is a fatty acid alkali metal salt having 16 carbon atoms (B1) (hereinafter sometimes simply referred to as component (B1)). It is preferable to include.
When component (B) contains component (B1), the weight ratio (B1/B) of component (B1) to component (B) is not particularly limited, but (1) 0.1 to 0.8, ( 2) 0.12-0.78, (3) 0.14-0.76, (4) 0.16-0.74, (5) 0.18-0.72, (6) 0.20- Preferably in the order of 0.70 (the larger the number in parentheses is, the more preferable it is). When the weight ratio is 0.1 or more, anti-adhesion properties tend to improve, and when it is 0.8 or less, water permeability tends to improve.

The content of component (B) with respect to 100 parts by weight of the anti-adhesive composition is not particularly limited, but is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, particularly preferably 3 to 20 parts by weight. be.

[Component (C): Surfactant other than component (B)]
Surfactants other than component (B) explained above (hereinafter sometimes simply referred to as component (C)) not only increase the water permeability of the anti-adhesive composition, but also improve the wettability of unvulcanized rubber. It is an ingredient that assists in adhesiveness and adhesion.
Component (C) includes nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and one type or two or more types may be used in combination.

Examples of nonionic surfactants include decyl ether with 3 moles of polyoxyethylene added, decyl ether with 3 moles of polyoxyethylene and 1 mole of polyoxypropylene added, decyl ether with 5 moles of polyoxyethylene added, and polyoxyethylene. Decyl ether with 7 moles added, isodecyl ether with 3 moles added polyoxyethylene, isodecyl ether with 3 moles added polyoxyethylene and 1 mole added polyoxypropylene, isodecyl ether with 5 moles added polyoxyethylene, polyoxyethylene Isodecyl ether with 7 moles added, lauryl ether with 3 moles added polyoxyethylene, lauryl ether with 3 moles added polyoxyethylene and 1 mole added polyoxypropylene, lauryl ether with 5 moles added polyoxyethylene, 7 moles polyoxyethylene Lauryl ether with addition, 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, 7 moles of polyoxyethylene tridecyl ether of addition, isotridecyl ether of addition of 3 moles of polyoxyethylene, isotridecyl ether of addition of 3 moles of polyoxyethylene and addition of 1 mole of polyoxypropylene, isotridecyl ether of addition of 5 moles of polyoxyethylene, Isotridecyl ether with 7 moles of oxyethylene, myristyl ether with 3 moles of polyoxyethylene, myristyl ether with 3 moles of polyoxyethylene and 1 mole of polyoxypropylene, myristyl ether with 5 moles of polyoxyethylene, polyoxy Myristyl ether with 7 moles of ethylene, cetyl ether with 3 moles of polyoxyethylene, cetyl ether with 3 moles of polyoxyethylene and 1 mole of polyoxypropylene, cetyl ether with 5 moles of polyoxyethylene, 7 moles of polyoxyethylene Polyoxyalkylene alkyl ethers such as cetyl ether; polyoxyalkylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether; polyoxyethylene monolaurate, polyoxyethylene monooleate, etc. Oxyalkylene fatty acid ester; polyoxyalkylene sorbitan fatty acid ester such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate; polyoxyalkylene alkyl amine; fatty acid alkanolamide; polyoxyalkylene fatty acid amide; polyoxyalkylene hydrogenated castor oil ; polyoxyalkylene sorbitol fatty acid ester; polyglycerin fatty acid ester; alkylglycerin ether; polyoxyalkylene cholesteryl ether; alkyl polyglucoside; sucrose fatty acid ester; oxyethylene-oxypropylene block polymer, etc., one type or two or more types. may be used together.

Examples of anionic surfactants include alkyl sulfate ester salts 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; dodecyl Alkylbenzene sulfonates such as sodium benzenesulfonate; polyoxyalkylene alkyl ether sulfates; long chain sulfosuccinates such as Na 2-ethylhexyl sulfosuccinate; N-acyl sarcosine salts such as oleoyl sarcosine Na, lauroyl sarcosine Na, etc. ; Higher fatty acid amide sulfonates such as stearoyl methyl taurine Na, lauroyl methyl taurine Na, myristoyl methyl taurine Na, and palmitoyl methyl taurine Na; alkyl phosphates such as monostearyl sodium phosphate; polyoxyethylene oleyl ether sodium phosphate; Examples include polyoxyalkylene alkyl ether phosphate ester salts such as sodium polyoxyethylene stearyl ether phosphate; long chain N-acyl glutamates such as monosodium sodium N-lauroyl glutamate and disodium N-stearoyl-L-glutamate. , may be used alone or in combination of two or more.

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

Component (C) preferably contains an anionic surfactant (C1) and a nonionic surfactant (C2) from the viewpoint of increasing water permeability and wettability. Hereinafter, the anionic surfactant (C1) may be simply 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 (1) 0.8 to 10 , (2) 0.9-9.9, (2) 1.0-9.8, (3) 1.1-9.7, (4) 1.2-9.6, (5) 1. 3 to 9.5, and (6) 1.4 to 9.4 (the larger the number in parentheses, the more preferable). When the weight ratio is 0.8 or more, water permeability tends to improve, and when it is 10 or less, wettability tends to improve.

Further, the HLB of component (C2) according to the Griffin method is not particularly limited, but is preferably 3 to 13, more preferably 4 to 12, still more preferably 5 to 11, particularly preferably 6 to 10. When the HLB is 3 or more, water permeability tends to improve, and when it is 13 or less, wettability tends to improve.
Here, HLB according to the Griffin method is a value that can be calculated by the following (I) based on the molecular structure. That is, HLB by the Griffin method takes a numerical value from 0 to 20, and the smaller the numerical value is, the more lipophilic it is, and the larger the numerical value is, the more hydrophilic it is.
HLB=20×(sum of formula weights of hydrophilic parts/molecular weight) (I)

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

In general formula (1), R is an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be linear or branched. Further, the aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.
In the 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. The oxyalkylene group having 2 to 4 carbon atoms is, for example, a polymerized unit formed by adding an alkylene oxide having 2 to 4 carbon atoms. When multiple types of oxyalkylene groups are included, these groups may be arranged in a block shape or randomly arranged.

The content of component (C) with respect to 100 parts by weight of the anti-adhesive 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, particularly preferably 3 parts by weight. ~20 parts by weight. When the content is 1 part by weight or more, water permeability tends to improve, and when the content is 30 parts by weight or less, anti-adhesion properties tend to improve.

The anti-adhesion agent composition of the present invention may further contain the following component (D) and/or component (E).
Component (D): Metal soap Component (E): Wax

[Component (D): Metal soap]
Metal soap (hereinafter sometimes simply referred to as component (D)) is a component that adheres to the surface of unvulcanized rubber, reduces friction between unvulcanized rubber, and improves adhesion prevention.
Component (D) includes, for example, 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 triotadecanoate, aluminum dioctadecanoate, aluminum monooctadecanoate, calcium octadecanoate, zinc octadecanoate, magnesium octadecanoate, barium octadecanoate, and the like.
Component (D) is not particularly limited, but it is preferable that it is at least one selected from magnesium stearate, calcium stearate, and zinc stearate because it has a high effect of reducing friction between unvulcanized rubbers.

[Component (E): Wax]
Wax (hereinafter sometimes simply referred to as component (E)), like component (D), is a component that adheres to the surface of unvulcanized rubber, reduces friction between unvulcanized rubber, and improves anti-stick properties. It is.
Examples of component (E) include particles of vegetable wax, animal wax, mineral wax, petroleum wax, synthetic hydrocarbon wax, modified wax, hydrogenated wax, fatty acid amide, and phthalic anhydride. , may be used alone or in combination of two or more.

Examples of vegetable waxes include candelilla wax, carnauba wax, rice wax, Japanese wax, horsetail oil, sugar wax, bayberry wax, ochuri wax, and esparto wax.
Examples of animal waxes include beeswax, lanolin, spermaceti, insect wax, shellac wax, and the like.
Examples of the mineral wax include montan wax, ozokerite, ceresin, and the like.
Examples of petroleum waxes include paraffin wax, microcrystalline wax, and petrolactam.
Examples of the synthetic hydrocarbon wax include Fischer-Tropsch wax and polyethylene wax.
Examples of the modified wax include montan wax derivatives, paraffin wax derivatives, microcrystan wax derivatives, and the like.

Examples of the hydrogenated wax include hydrogenated castor oil, 12-hydroxystearic acid, 12-hydroxystearamide, 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, Examples include 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'-xylylene bisstearic acid amide, coconut oil fatty acid monoethanolamide, N-oleyl stearic acid amide, Examples include N,N'-dioleyladipic acid amide.

The total content of component (D) and component (E) based on 100 parts by weight of the anti-adhesive composition is not particularly limited, but is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, especially Preferably it is 3 to 20 parts by weight. When the content is 1 part by weight or more, anti-adhesion properties tend to improve, and when the content is 30 parts by weight or less, water permeability tends to improve.

The anti-adhesive composition of the present invention may contain other components (hereinafter sometimes simply referred to as "other components") other than the components (A) to (E) explained above. Other components include, but are not particularly limited to, water-soluble polymers, polyhydric alcohols, antifoaming agents, preservatives, and the like.

[Water-soluble polymer]
The water-soluble polymer is a component that imparts viscosity to the aqueous dispersion of the anti-adhesive composition and improves its adhesion to the unvulcanized rubber surface.
Examples of water-soluble polymers include starches such as oxidized starch, starch acetate, starch phosphate, carboxymethyl starch, carboxyethyl starch, hydroxyethyl starch, positive starch, cyanoethylated starch, dialdehyde starch; mannan; alginic acid, alginic acid Alginic acids such as sodium, propylene glycol alginate, triethanolamine alginate, and ammonium alginate; Cellulose ethers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxyethylethylcellulose, and carboxymethylcellulose; Natural gums such as taracanth gum, arabic gum, guar gum, xanthan gum, British gum, glucomannan, gellan gum, tara gum, locust bean gum, carrageenan; Sodium polyacrylate; Polyvinyl alcohol; Polyethylene glycol; Polyethylene oxide; Water-soluble acrylic resin; Water-soluble Examples include water-soluble urethane resins; water-soluble melamine resins; water-soluble epoxy resins; water-soluble butadiene resins; water-soluble phenol resins; one type or two or more types may be used in combination.

[Polyhydric alcohol]
Polyhydric alcohol is a component that adheres to the surface of unvulcanized rubber, provides lubricity between the unvulcanized rubbers, and reduces friction between the unvulcanized rubbers.
Examples of polyhydric alcohols include glycerin, 1,3-butanediol, propylene glycol, dipropylene glycol, pentylene glycol, neopentyl glycol, hexylene glycol, polyethylene glycol, erythritol, pentaerythritol, dipentaerythritol, and trimethylol. Examples include ethane, trimethylolpropane, ditrimethylolpropane, xylitol, sorbitol, mannitol, maltitol, maltotriose, glucose, sucrose, fructose, maltose, etc., and one type or two or more types may be used in combination.

[Defoaming agent]
Examples of antifoaming agents include silicone antifoaming agents such as polymethylsiloxane and polyether-modified silicone; oil-based antifoaming agents such as castor oil, sesame oil, linseed oil, and animal and vegetable oils; stearic acid, oleic acid, and palmitic acid. Fatty acid antifoaming agents such as isoamyl stearate, distearyl succinate, ethylene glycol distearate, butyl stearate; Polyoxyalkylene monohydric alcohol di-t-amylphenoxyethanol, 3 -Alcoholic antifoaming agents such as heptanol and 2-ethylhexanol; Ether antifoaming agents such as di-t-amylphenoxyethanol 3-heptylcellosolvebunonylcellosolve 3-heptylcarbitol;tributyl phosphate and tris(butoxyethyl)phosphate Phosphate defoaming agents such as; Amine defoaming agents such as diamylamine; Amide defoaming agents such as polyalkylene amide and acylate polyamine; Sulfate defoaming agents such as sodium lauryl sulfate; Polyoxyalkylene Antifoaming agents include mineral oil and the like, and one type or two or more types may be used in combination.

〔Preservative〕
Examples of preservatives include thiazoles such as thiazole and 2-mercaptothiazole; thiocyanates such as methylene bisthiocyanate and ammonium thiocyanate; sulfimides such as o-benzoic sulfimide and phenylmercuric-o-benzoic sulfimide. ; Alkyldialkylthiocarbamates such as methyl dimethylthiocarbamate and ethyl diethyl dithiocarbamate; Thiraum sulfides such as tetramethyl thiraum sulfide and tetraethyl thiraum sulfide; Thiraum disulfides such as tetramethyl thiraum disulfide and tetraethyl thiraum disulfide Dithiocarbamates such as ferric diethyldithiocarbamate and lead dimethyldithiocarbamate; Sulfamides such as o-toluenesulfonamide and benzenesulfonanilide; 1-aminonaphthyl-4-sulfonic acid, 1-amino-2-naphthol-4 -Aminosulfonic acids such as sulfonic acid; Phenols such as pentachlorophenol and o-phenylphenol and their alkali metal salts; Chlorinated quinones such as tetrachloro-p-benzoquinone and 2,3-dichloro-1,4-naphthoquinone Nitro group-containing compounds such as dinitrocaprylphenylcrotonate and dinitro-o-cresol; 1,3,5-trihydroxyethylhexahydro-1,3,5-triazine, 1,3,5-triethylhexahydro - Triazines such as 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; Examples include iodine-containing compounds such as 1,3-diiodo-2-propanol, and one type or two or more types may be used in combination.

[Anti-adhesive composition for unvulcanized rubber]
The bulk density of the anti-adhesive composition of the present invention is 0.70 to 1.0 g/cm ³ .
Since the anti-adhesive composition essentially contains the above components (A) to (C) and has a bulk density within the above range, it has excellent water permeability and further excellent wettability.
The bulk density of the anti-adhesive composition is preferably 0.71 to 0.99 g/cm ³ , more preferably 0.72 to 0.98 g/cm ³ , even more preferably 0.73 to 0.97 g/cm ³ , particularly preferably from 0.74 to 0.96 g/cm ³ , most preferably from 0.75 to 0.95 g/cm ³ . The bulk density of the anti-adhesive composition for unvulcanized rubber is determined by the method described in Examples.
Further, the anti-adhesive composition of the present invention is preferably in powder form in order to achieve the effects of the present invention.

[Method for producing anti-adhesive composition for unvulcanized rubber]
Regarding the anti-adhesive composition of the present invention, the manufacturing method includes a step of mixing components (A) to (C) as essential, and component (D), component (E), and other components as necessary. If so, there are no particular limitations on the mixing order or the mixing device to be used. Examples of the mixing device include powder mixers such as a ribbon mixer and a Nauta mixer.

[Aqueous dispersion of anti-adhesive composition for unvulcanized rubber and method for producing the same]
The aqueous dispersion of the anti-adhesive composition for unvulcanized rubber of the present invention is not particularly limited; It is a dispersed water dispersion.

The aqueous dispersion of the anti-adhesive composition for unvulcanized rubber of the present invention may be produced, for example, by mixing and dispersing the anti-adhesive composition for unvulcanized rubber in water.
The concentration of the anti-adhesive composition in the aqueous dispersion of the anti-adhesive 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% by weight. ~7.5% by weight, more preferably 0.1~5.0% by weight. When the concentration is 0.01% by weight or more, anti-adhesion properties tend to improve, and when the concentration is 10% by weight or less, drying properties tend to improve.

[Method for manufacturing anti-adhesion treated unvulcanized rubber]
The method for producing unvulcanized rubber subjected to anti-adhesion treatment of the present invention includes a treatment step of adhering the anti-adhesion agent composition for unvulcanized rubber to the surface of unvulcanized rubber. Here, the unvulcanized rubber is preferably one that has been molded.

In the treatment step, a wet method, that is, a method using an aqueous dispersion dispersed in water as an anti-adhesive composition for unvulcanized rubber is preferred.
When carrying out the treatment step by a wet method, examples include a method of spraying an anti-adhesive composition for unvulcanized rubber or its aqueous dispersion, a method of spraying the rubber with a trickle, a method of immersing it in an aqueous dispersion, etc. It will be done. Among these, the method of immersing in an aqueous dispersion is preferred because it allows the anti-adhesive composition for unvulcanized rubber to be uniformly adhered.
Drying may then be carried out after applying the aqueous dispersion. The drying method is not particularly limited, but it is preferable to use a method of forced drying by blowing hot air using a hot air blower or blow heater.

The unvulcanized rubber used in the method for producing unvulcanized rubber treated with anti-stick treatment of the present invention is usually heated to 100 to 180°C, and in the method of immersing it in an aqueous dispersion, the unvulcanized rubber is heated to 100 to 180°C. It is also possible to cool the rubber. The temperature of the aqueous dispersion is not particularly limited, but is preferably 0 to 60°C.
Next, a step of drying the unvulcanized rubber may be performed after the aqueous dispersion is attached. The drying method is not particularly limited, but from an economic point of view, it is preferable to use a method of forced drying by blowing hot air using a hot air blower or a blow heater.

In the treatment step, a dry method may be used, ie, an anti-adhesive composition that is not in the form of an aqueous dispersion may be used.
When the anti-adhesive unvulcanized rubber produced by the above production method is stacked and stored before proceeding to the next step, it is possible to prevent the unvulcanized rubber from adhering to each other.

The present invention will be specifically explained below by showing Examples and Comparative Examples. The present invention is not limited to these examples. Evaluation of each physical property in Examples and Comparative Examples was performed as follows.

[The bulk density]
The bulk density of the component (A) and the anti-adhesive composition for unvulcanized rubber was measured using a multi-functional powder physical property measuring device Multitester (Model MT-1001k/manufactured by Seishin Enterprise Co., Ltd.). (g/cm ³ ) was measured. A funnel, a sieve (openings: 710 μm), and a sieve spacer were stacked on top of the feeder unit in this order and fixed with a stopper. Place a cell container (made of SUS, dimensions: 50.5 mm (inner diameter) x 50 mm (height), internal volume: 100 cm ³ ) on the sample stand, put the sample into the sample unit, vibrate the feeder, and sieve out the sample. The cells were filled with a cloth and scraped with a scraping board. The loose bulk density ρ (g/cm ³ ) of each sample was measured using the following formula.
ρ=(W ₁ -W ₀ )/V ₁
V ₁ : Capacity of cell container (cm ³ )
W ₀ : Weight of cell container (g)
W ₁ : Weight of cell container after sample filling (total weight of cell container and sample) (g)

[Water permeability]
In a 300 ml glass beaker, 294 g of water adjusted to 20° C. was placed, and 6 g of the anti-adhesive composition for unvulcanized rubber was gently added thereto, and the mixture was allowed to stand still. After 5 minutes had elapsed, the floating anti-adhesive composition for unvulcanized rubber was collected, the weight and water content were measured, and the weight (W) of floating and non-penetrating composition was calculated. 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 is 90% or more: Very good permeability to water (index ◎)
Dispersion rate is 70% or more and less than 90%: Good permeability to water (index ○)
Dispersion rate is 40% or more and less than 70%: Water permeability is poor (index △)
Dispersion rate less than 40%: Water permeability is very poor (index ×)

[Wettability]
The dispersion obtained in the above water permeability test after removing undispersed matter was used. The moisture removed at the same time as the undispersed material was supplemented. The dispersion liquid was stirred for 30 minutes or more using a magnetic stirrer in a hot bath whose temperature was adjusted to 45°C to obtain a uniform dispersion liquid.
An NR/BR rubber test piece (natural rubber/butadiene rubber; thickness 0.5 cm x length 5 cm x width 3 cm) heated to 100°C was immersed in the 45°C dispersion and immediately pulled up. The wettability of the unvulcanized rubber surface was evaluated as follows.
The entire surface of unvulcanized rubber is wet: Good wettability (indicator is ○)
Part of the unvulcanized rubber surface is repellent: wettability is slightly poor (index is △)
The entire unvulcanized rubber surface is repellent: poor wettability (indicator is ×)

[Anti-adhesion]
The dispersion liquid used in the above wettability evaluation was used. An NR/BR test piece (natural rubber/butadiene rubber; thickness 0.5 cm x length 5 cm x width 3 cm) heated to 100°C was immersed in a dispersion liquid whose temperature was controlled to 45°C and immediately pulled out. Two immersed rubber test pieces were prepared, air-dried, stacked, and left in a constant temperature bath at 40° C. for 24 hours under a load of 1000 kg/m ² . The test piece taken out from the thermostatic bath was air-cooled to room temperature, and the peel resistance (N/cm) was measured using a tensile tester at a speed of 100 mm/min. Based on the measured peel resistance, the anti-adhesion properties were evaluated as follows.
Peeling resistance is 1 N/cm or less: Very good anti-adhesion property (unvulcanized rubber can be easily peeled off from each other, the index is ◎)
Peeling resistance is more than 1 N/cm and less than 2 N/cm: Good anti-adhesion property (unvulcanized rubber can be peeled off from each other without load, index is ○)
Peeling resistance is 2 N/cm or more and 3 N/cm or less: Adhesion prevention is poor (the load when peeling unvulcanized rubber is large, the adhesion prevention is low, the index is △)
Peeling resistance exceeds 3 N/cm: Very poor adhesion prevention (rubbers adhere to each other and it is difficult to peel off. Adhesion prevention is very low, index is ×)

(Example 1)
50 g of bentonite, 20 g of kaolinite, 10 g of calcium carbonate, 7 g of Na caprate, 3 g of Na palmitate, 9 g of dioctyl sulfosuccinate, and 1 g of POE (3) sec-alkyl (C12-C14) ether were mixed uniformly to form unvulcanized rubber. An anti-adhesive composition was obtained.
Next, 6 g of the obtained anti-adhesive composition was added to 294 g of tap water, and water permeability, wettability, and anti-adhesive properties were evaluated. The evaluation results are shown in Table 1, showing excellent water permeability and wettability, and excellent anti-adhesion properties.

(Examples 2 to 26)
Examples 2 to 26 were evaluated in the same manner as in Example 1, except that the composition was changed as shown in Table 1. The evaluation results are shown in Tables 1 and 2.

(Comparative example 1)
5 g of bentonite, 65 g of kaolinite, 10 g of calcium carbonate, 7 g of sodium caprate, 3 g of Na palmitate, 9 g of dioctyl sulfosuccinate, and 1 g of POE (3) sec-alkyl (C12-C14) ether were mixed uniformly and unvulcanized. An anti-adhesion agent composition for rubber was obtained.
Next, 6 g of the obtained anti-adhesive composition was added to 294 g of tap water, and water permeability, wettability, and anti-adhesive properties were evaluated. The evaluation results are shown in Table 2, and the water permeability and wettability were poor, and the anti-adhesion property was very poor.

(Comparative Examples 2 to 7)
Comparative Examples 2 to 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) means polyoxyethylene (number of repeating units of oxyethylene: m).

As can be seen from Tables 1 and 2, the anti-adhesive compositions for unvulcanized rubber of Examples 1 to 28 are composed of an inorganic powder (A) containing a specific amount of a water-swellable inorganic powder (A1) and a fatty acid alkali. An anti-adhesive composition for unvulcanized rubber comprising a metal salt (B) and a surfactant (C) other than a fatty acid alkali metal salt (B), the composition having a bulk density of 0.7 to 1. When it is .0 g/cm ³ , it has excellent water permeability and also excellent wettability.
On the other hand, as can be seen from Table 2, when the water-swellable inorganic powder (A1) does not have a specific content (Comparative Example 1), when it does not contain the inorganic powder (A) (Comparative Examples 2 and 3), when the water-swellable inorganic powder (A1) is When the alkali metal salt (B) is not included (Comparative Example 4), when the surfactant (C) other than the fatty acid alkali metal salt is not included (Comparative Example 5), the bulk of the anti-adhesive composition for unvulcanized rubber When the density is outside the range of 0.5 to 0.9 g/cm ³ (Comparative Examples 6 and 7), at least one of water permeability and wettability is not excellent.

The anti-adhesive composition for unvulcanized rubber of the present invention is used in the production and processing process of unvulcanized rubber products, and is accumulated while unvulcanized rubber is transferred to the next process such as molding and vulcanization. This prevents the rubber from sticking together when stored. At that time, it has excellent water permeability and wettability, making it possible to improve the productivity of rubber products.

Claims (7)

Contains 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 0.9. and
An anti-adhesive composition for unvulcanized rubber having a bulk density of 0.7 to 1.0 g/cm ³ .
Component (A): Inorganic powder Component (B): Fatty acid alkali metal salt Component (C): Surfactant other than component (B) The content of the component (A) is 30 to 90 parts by weight, the content of the component (B) is 1 to 30 parts by weight, and the content of the component (C) is 1 to 30 parts by weight, based on 100 parts by weight of the composition. The anti-adhesive composition for unvulcanized rubber according to claim 1, wherein the amount is 1 to 30 parts by weight. The component (C) contains an anionic surfactant (C1) and a nonionic surfactant (C2), and the weight ratio of the anionic surfactant (C1) to the nonionic surfactant (C2) ( The anti-adhesive composition for unvulcanized rubber according to claim 1 or 2, wherein C1/C2) is 0.8 to 10. The component (B) contains 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 the component (B) is 0.1 to 0.8. The anti-adhesive composition for unvulcanized rubber according to any one of claims 1 to 3. The anti-adhesive composition for unvulcanized rubber according to any one of claims 1 to 4, comprising the following component (D) and/or the following component (E).
Component (D): Metal soap Component (E): Wax An aqueous dispersion of the anti-adhesive composition for unvulcanized rubber, comprising the anti-adhesive composition for unvulcanized rubber according to any one of claims 1 to 5 and water. An anti-adhesive treated unvulcanized rubber comprising the step of adhering an aqueous dispersion of the anti-adhesive composition for unvulcanized rubber according to claim 6 to the surface of the unvulcanized rubber, and further volatilizing water. manufacturing method.