JP2021138923A - Adhesion inhibitor composition for unvulcanized rubber and use thereof - Google Patents

Abstract

To provide: an adhesion inhibitor composition for unvulcanized rubber, having an excellent adhesion inhibition property and having a problem of dust generation by its falling greatly reduced; and a method for producing unvulcanized rubber which has been subjected to an adhesion inhibition treatment performed by using the adhesion inhibitor composition for unvulcanized rubber.SOLUTION: Provided is an adhesion inhibitor composition for unvulcanized rubber, comprising: an inorganic component containing a silicate as an essential ingredient; and a surfactant. The silicate contains at least one selected from iron oxide and iron sulfide, and a total of weight ratios of the iron oxide and the iron sulfide relative to a total of the silicate, the iron oxide, and the iron sulfide is less than 3 wt%. The surfactant contains an anionic surfactant (A) and a nonionic surfactant (B), and a weight ratio (A/B) represented by [weight of (A)]/[weight of (B)] is 0.1 to 1.SELECTED DRAWING: None

Description

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

In the production and processing process of rubber products, unvulcanized rubber may be stacked and stored until the process shifts to the next molding or vulcanization process. In this case, adhesion prevention is performed for the purpose of preventing rubber adhesion. An agent (adhesive agent) is used.
As the adhesive, an adhesive containing an inorganic powder and a surfactant as main components is widely used, and these are generally applied to a rubber surface in the form of an aqueous dispersion and dried. .. As a coating method, an aqueous dispersion is sprayed or immersed in the aqueous dispersion.

However, there is a problem that dust generated when such an adhesive is applied to rubber pollutes the working environment. After the adhesive is attached to the rubber surface, there is a problem that powder falls off and dust is generated before moving to the next step such as molding or vulcanization. Adhesive agents are basically foreign substances for rubber products, and even a small amount of foreign substances can have a large effect on the physical properties of rubber products. desirable. There is also a means of installing a local exhaust system as a method of suppressing pollution of the work environment due to the generation of dust, but it requires capital investment costs and is not a fundamental solution. For this reason, it is desired to develop an anti-adhesive agent having less dust scattering and excellent anti-adhesion property.

Patent Document 1 discloses an anti-wearing composition comprising a water-soluble polymer having a film-forming property and an anionic surfactant or a nonionic active agent. This anti-wear composition is characterized in that it does not use powder of inorganic particles, and can reduce dust scattering after the anti-adhesion treatment. However, in order to exhibit sufficient adhesiveness, it is necessary to use it at a high concentration, and in that case, the water retention of the water-soluble polymer becomes remarkably high, and after applying the adhesive composition. The drying process takes time and reduces productivity.
Patent Document 2 discloses a method of applying a composition obtained by dispersing a fatty acid soap having a limited number of carbon atoms and metal ions, a metal soap, and a specific surfactant in water on a rubber surface to prevent adhesion. Since no inorganic powder is used, there is no problem of dust scattering, but the adhesion is inferior. Further, in order to exert a sufficient effect of preventing adhesion, it is necessary to use it at a high concentration, and in that case, there is a problem that the physical properties of the vulcanized rubber are deteriorated, so that the usage method is limited and versatility is achieved. Is scarce.
As described above, an anti-adhesive agent that solves the scattering of dust has been developed, but at the same time, there has been no development of an anti-adhesive agent that exhibits sufficient anti-adhesiveness.

Japanese Unexamined Patent Publication No. 62-32127 Japanese Unexamined Patent Publication No. 49-18780

An object of the present invention is to use an adhesive composition for unvulcanized rubber, which has excellent adhesion resistance and significantly reduces dust generation due to falling off, and an adhesive composition for unvulcanized rubber. It is an object of the present invention to provide a method for producing an unvulcanized rubber which has been subjected to an anti-adhesion treatment.

As a result of diligent studies to solve the above problems, the present inventor has found that the weight ratio of the iron oxide and the iron sulfide to the total of the silicate, iron oxide and iron sulfide is in a specific range, and the anionic surfactant (anionic surfactant ( It has been found that the above problems can be solved if the adhesive composition contains A) and the nonionic surfactant (B) in a specific ratio.

That is, the adhesive composition for unsulfurized rubber of the present invention is an adhesive composition for unsulfurized rubber containing an inorganic component and a surfactant, and the inorganic component is oxidized with silicate. Essentially containing at least one selected from iron and iron sulfide, the total weight ratio of the iron oxide and the iron sulfide to the total of the silicate, the iron oxide and the iron sulfide is less than 2% by weight. , The surfactant contains an anionic surfactant (A) and a nonionic surfactant (B), and the weight ratio (A / B) represented by the weight of (A) / the weight of (B) is 0.1. ~ 1.

It is preferable to further contain carbonate and / or metal soap.
It is preferable that the anionic surfactant (A) contains a fatty acid soap.

The method for producing an anti-vulcanized rubber of the present invention includes a treatment step of adhering the above-mentioned adhesive composition for unvulcanized rubber to the surface of the molded unvulcanized rubber.

The adhesive composition for unvulcanized rubber of the present invention is excellent in adhesiveness and can significantly reduce the generation of dust due to falling off.
In the method for producing an anti-vulcanized rubber of the present invention, an unvulcanized rubber having excellent adhesion on the rubber surface can be efficiently produced, and at that time, an adhesive composition for unvulcanized rubber can be produced. The generation of dust due to falling off the surface is greatly reduced.

[Adhesive composition for unvulcanized rubber]
The adhesive composition for unvulcanized rubber of the present invention is an adhesive composition for unvulcanized rubber containing an inorganic component essential for silicate and a surfactant.
Hereinafter, the following components will be described in detail.

[Inorganic component]
The inorganic component is a component of a material that exhibits adhesiveness by forming a film on the surface of unvulcanized rubber. In the adhesive composition for unvulcanized rubber of the present invention, the inorganic component contains silicate as an essential component. contains.
A silicate is generally a structure formed by connecting silicic acid tetrahedrons formed by inserting one silicon atom into a gap in the middle of a triangular pyramid formed of four oxygen atoms. Silicates are further classified into nesosilicates, solo silicates, cyclosilicates, inosilicates, phyllosilicates, tect silicates, etc. according to the silicate tetrahedron connection method, and the silicates for unsulfurized rubber of the present invention. In the coating composition, one kind or two or more kinds of these silicates may be used in combination.
Nesosilicates are classified as stand-alone linkage type silicates, and have a basic composition having a structure represented by the chemical formula _{(SiO 4} ) ^4-. The nesosilicate is not particularly limited, but for example, sillimanite such as forsterite, firealite, and manganese olivine; humite; garnet such as pyrope, almandine, spessartine, glossler, andradite, and gadolinite; , Gadolinite such as sillimanite, and these may be used alone or in combination of two or more.
Solo silicates are classified as complex linking silicates and have at least one selected from the structures represented by the chemical formulas _{(Si 2} O ₇ ) ^6- and (Si ₅ O ₁₆ ) ^{12- as the basic composition.} do. The nesosilicate is not particularly limited, and examples thereof include green lene stones such as zoisite and clinozoysite; melilite such as ochermanite and gelenite; pumpellyite such as vesbianite, and one or more of these. May be used together.

Cyclosilicates are classified as cyclically linked silicates and are based on the structures represented by the chemical formulas _{(Si 3} O ₉ ) ^6- , (Si ₄ O ₁₂ ) ^8- , and (Si ₆ O ₁₈ ) ^12-. The composition. The nesosilicate is not particularly limited, and examples thereof include Benitoite; Axinite; Beryl; Iron tourmaline, Magnesio-foit stone, Elbaite and other electric stones; Osumilite and the like. Seeds or two or more may be used together.
Inosilicates are classified as single chain silicates, (Si ₂ O ₆ ) ^4- , (Si ₃ O ₉ ) ^6- , (Si ₄ O ₁₁ ) ^6- , (Si ₅ O ₁₅ ). ^The basic composition is a structure represented by the chemical formulas of 10- and (Si ₇ O ₂₁ ) ^14-. The inosilicate is not particularly limited, and examples thereof include pyroxenes such as diopside, clinoenstatite, enstatite, acumite, and spodium; anthophyllite, tremolite, glaucoma, and amphibole such as roadnite. These may be used alone or in combination of two or more.

Philosilicates are classified as layered silicates and have a basic composition of a structure represented by the chemical formula of _{SiO 2.} The phyllosilicate is not particularly limited, but for example, smectites such as montmorillonite, biderite, nontronite, saponite, hectrite, saconite, and stivuncite; vermiculite such as divermiculite and tribermiculite; haloysite, kaolin, and ende. Kaolinites such as light, deckite, nacrite, and chrysotile; talc; mica such as tetrasilic mica; pyrophyllite; margarite; clintite; mica minerals such as white mica, black mica, gold mica, synthetic mica, and fluorine mica. Paragolite; Vermiculite; Lepidrite; Jamon stones such as antigolite; Green mudstones such as donpasite, vermiculite, cookite, clinochloa, chamosite, chlorite, nantit; These may be used alone or in combination of two or more.

Tect silicates are classified as network-linked silicates, and have a basic composition having a structure represented by the chemical formula of _{SiO 2.} The tect silicate is not particularly limited, and examples thereof include feldspars such as sanidine, part-time job, anausite, and nepheline; leucites, zeolites such as heulandite, and scapolite; Two or more types may be used in combination.
The silicate contained in the inorganic component used in the present invention preferably contains a phyllosilicate, and can form a film having good water dispersibility and excellent adhesion. Among them, it is preferable that the phyllosilicate is at least one selected from smectite, kaolinite, talc and mica because it forms a film having excellent adhesion resistance.
When smectite comes into contact with water, water molecules hydrate and swell in commutative cations between layers one after another, so that smectite can be effectively dispersed in water. Therefore, it is more preferable that the phyllosilicate is smectite because it has excellent dispersibility when blended with water and the film property is improved. Further, among smectites, montmorillonite is preferable because it has particularly remarkable water swelling property.

Montmorillonite is a diocteohedral hydrous layered silicate mineral containing sodium, calcium, potassium, magnesium, hydrogen ions and the like as exchange cations. These cations have the property of being easily exchanged and also have the property of being able to easily take in water. When the exchange cation is a sodium ion, it is easy to take in water molecules by hydration power, the layer spacing is increased, and the swelling is remarkable.

Generally, a layered clay mineral containing montmorillonite as a main component is called bentonite. Bentonite is given as an example of an inorganic component, and can be easily adsorbed on the surface of unvulcanized rubber to form a film. Since the bentonite film is excellent in adhesiveness and slipperiness, it is more preferable that the silicate in the adhesive composition for unvulcanized rubber of the present invention contains bentonite as an essential component. Further, when bentonite contains sodium bentonite with high purity, the water swelling effect is remarkably preferable.

The amount of the silicate contained in the non-vulverized rubber adhesive composition of the present invention is not particularly limited, but is preferably 30 to 90 when the total amount of the inorganic component and the surfactant is 100 parts by weight. It is by weight, more preferably 32.5 to 87.5 parts by weight, still more preferably 35 to 85 parts by weight, and particularly preferably 37.5 to 82.5 parts by weight. When the content of the silicate is 30 parts by weight or more, the adhesion resistance tends to be improved, and when the content of the silicate is 90 parts by weight or less, the dispersibility tends to be improved.

In addition to the above silicate, the inorganic component essentially contains at least one selected from iron oxide and iron sulfide. Further, the total weight ratio of iron oxide and iron sulfide to the total of silicate, iron oxide and iron sulfide is less than 2% by weight. The silicate may be present together with a trace amount of the iron compound, but since the iron compound has a higher specific gravity than the silicate, the weight ratio of the iron compound to the total of the silicate, iron oxide and iron sulfide is 2% by weight or more. If there is, it hinders uniform adhesion of the silicate to the rubber and causes dust scattering. The iron compound in the present invention is at least one selected from iron oxide and iron sulfide, and may contain both.
The total weight ratio of iron oxide and iron sulfide to the total of silicate, iron oxide and iron sulfide is preferably 1.8% by weight or less, more preferably 1.6% by weight or less, still more preferably 1.4% by weight. % Or less, particularly preferably 1.2% by weight or less. On the other hand, the lower limit of the total weight ratio of iron oxide and iron sulfide to the total of silicate, iron oxide and iron sulfide is preferably more than 0% by weight, more preferably 0.0001% by weight, still more preferably 0.001. By weight%, particularly preferably 0.01% by weight, most preferably 0.05% by weight.

As a method for adjusting the weight ratio of iron oxide and iron sulfide to the total of silicate, iron oxide and iron sulfide, for silicates in which the weight ratio of the iron compounds present together is less than 2% by weight, a commercially available product thereof is obtained. Although it is possible, the silicate containing the iron compound existing together may be treated by a centrifuge method, a centrifugation method, or the like, or the iron compound may be mixed.

[Analysis method of weight ratio of iron compound]
The weight ratio of the iron compound present with the silicate is measured by powder X-ray diffraction. When the measured value was below the detection limit, it was set to 0% by weight.

The inorganic component may contain an inorganic substance other than silicate, iron oxide and iron sulfide. The inorganic substances other than silicate, iron oxide and iron sulfide are not particularly limited, but for example, carbonates such as calcium carbonate, sodium carbonate and magnesium carbonate; sulfates such as calcium sulfate and barium sulfate; amorphous silica, Metal oxides such as alumina, magnesium oxide, antimony trioxide, titanium oxide, and white carbon; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and iron hydroxide; red iron oxide; carbon black; graphite and the like. Among the inorganic substances other than salts, iron oxide and iron sulfide, carbonate is preferable from the viewpoint of adhesion resistance of unsulfided rubber. Further, it is more preferable that it is at least one selected from calcium carbonate, sodium carbonate and magnesium carbonate.

The average particle size of the inorganic component is not particularly limited, but in consideration of adhesion to unvulcanized rubber and the like, it is preferably 0.1 to 200 μm, more preferably 0.1 to 100 μm, and even more preferably 0. It is 1 to 50 μm, particularly preferably 0.1 to 40 μm, and most preferably 0.1 to 30 μm.

[Surfactant]
The surfactant is an essential component in the present invention, a component that assists the dispersion of the adhesive composition, and a component that assists "wetting" of the unvulcanized rubber. Since the surfactant is contained in the adhesive composition for unvulcanized rubber of the present invention, the dispersibility of the inorganic component is improved and the detachment from the unvulcanized rubber can be suppressed. It can be uniformly coated on the surface of unvulcanized rubber.

The surfactant used in the present invention essentially contains an anionic surfactant and a nonionic surfactant. Anionic surfactants improve the dispersibility of the adhesive composition, and nonionic surfactants improve the adhesion of the adhesive composition to rubber. Therefore, both anionic and nonionic surfactants are essential.

The important points in the present invention are represented by the weight ratio of the iron compound to iron oxide and iron sulfide to the total of silicate, iron oxide and iron sulfide, and the anionic surfactant (A) and the nonionic surfactant (B). It is a correlation with the weight ratio (A / B).
In other words, it was found that the substance that inhibits the stability of the adhesive composition was an iron compound, and when the iron compound had a specific value, the anionic surfactant (A) and the nonionic surfactant (B) were found. ) And Is blended in a specific ratio, it has been found that the iron compound can be appropriately dispersed.

That is, in order to satisfy both the dispersibility and the shedding prevention performance, the weight ratio (A / B) represented by the anionic surfactant (A) and the nonionic surfactant (B) is 0.1 to 1. Must be range. If the A / B is less than 0.1, the dispersibility is lowered. On the other hand, when A / B exceeds 1, the dropout prevention property is lowered. A / B are (1) 0.12 to 0.98, (2) 0.14 to 0.96, (3) 0.15 to 0.95, (4) 0.16 to 0.94, ( 5) 0.25 to 0.90, (6) 0.25 to 0.85 are preferable in this order (the larger the number in parentheses, the more preferable).

The anionic surfactant and the nonionic surfactant are not particularly limited, and may contain one kind or two or more kinds.
Anionic surfactants include, for example, potassium caprate, sodium caprate, sodium laurate, potassium laurate, sodium palmitate, potassium plumitate, potassium stearate, sodium stearate, sodium palm kernel oil fatty acid, palm kernel oil. Fatty soaps such as potassium fatty acid, potassium palm stearate, sodium palm stearate, sodium coconut oil fatty acid, potassium coconut oil fatty acid, sodium beef fat fatty acid, potassium beef fat fatty acid; sodium lauryl sulfate, ammonium lauryl sulfate, sodium stearyl sulfate, sodium cetyl sulfate, etc. Alkyl sulfate ester salt; polyoxyalkylene alkyl ether acetate salt such as polyoxyethylene tridecyl ether sodium acetate; alkylbenzene sulfonate such as sodium dodecylbenzene sulfonate; polyoxyalkylene alkyl ether sulfate; sodium dioctyl sulfosuccinate, 2 -Long-chain sulfosuccinates such as Na ethylhexyl sulfosuccinate; N-acylsarcosine salts such as oleoyl sarcosin sodium and lauroyl sarcosin sodium; Higher fatty acids such as amide sulfonates; alkyl phosphates such as sodium monostearyl phosphate; polyoxyalkylene alkyl ether phosphates such as sodium polyoxyethylene oleyl ether phosphate, sodium polyoxyethylene stearyl ether phosphate; Examples thereof include long-chain N-acylglutamates such as sodium monosodium N-lauroyl glutamate and disodium N-stearoyl-L-glutamate, and one or more of them may be used in combination.

Examples of the nonionic surfactant include decyl ether with 3 mol of polyoxyethylene, decyl ether with 3 mol of polyoxyethylene and 1 mol of polyoxypropylene, decyl ether with 5 mol of polyoxyethylene, and polyoxyethylene 7. Molly added decyl ether, polyoxyethylene 3 mol added isodecyl ether, polyoxyethylene 3 mol added and polyoxypropylene 1 mol added isodecyl ether, polyoxyethylene 5 mol added isodecyl ether, polyoxyethylene 7 Isodecyl ether with molar addition, lauryl ether with 3 mol of polyoxyethylene, lauryl ether with 3 mol of polyoxyethylene and 1 mol of polyoxypropylene, lauryl ether with 5 mol of polyoxyethylene, 7 mol of polyoxyethylene Lauryl ether, tridecyl ether with 3 mol of polyoxyethylene, tridecyl ether with 3 mol of polyoxyethylene and 1 mol of polyoxypropylene, tridecyl ether with 5 mol of polyoxyethylene, 7 mol of polyoxyethylene Tridecyl ether, Isotridecyl ether with 3 mol of polyoxyethylene, Isotridecyl ether with 3 mol of polyoxyethylene and 1 mol of polyoxypropylene, Isotridecyl ether with 5 mol of polyoxyethylene, Polyoxy Isotridecyl ether with 7 mol of ethylene, myristyl ether with 3 mol of polyoxyethylene, myristyl ether with 3 mol of polyoxyethylene and 1 mol of polyoxypropylene, myristyl ether with 5 mol of polyoxyethylene, polyoxyethylene Myristyl ether with 7 mol, cetyl ether with 3 mol of polyoxyethylene, cetyl ether with 3 mol of polyoxyethylene and 1 mol of polyoxypropylene, cetyl ether with 5 mol of polyoxyethylene, 7 mol of polyoxyethylene Polyoxyalkylene alkyl ethers such as cetyl ethers; polyoxyalkylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ethers and polyoxyethylene octylphenyl ethers; polyoxys such as polyoxyethylene monolaurates and polyoxyethylene monooleates. Alkylene fatty acid ester; polyoxyethylene sorbitan monostearate, polyoki Polyoxyalkylene sorbitan fatty acid ester such as siethylene sorbitan monooleate; polyoxyalkylene alkylamine; fatty acid alkanolamide; polyoxyalkylene fatty acid amide; polyoxyalkylene cured castor oil; polyoxyalkylene sorbitol fatty acid ester; polyglycerin fatty acid ester; alkyl Examples thereof include glycerin ether; polyoxyalkylene cholesteryl ether; alkyl polyglucoside; sucrose fatty acid ester; oxyethylene-oxypropylene block polymer, and one or more of them may be used in combination.

The amount of the surfactant contained in the non-vulverized rubber adhesive composition of the present invention is not particularly limited, but is preferably 1 to 1 when the total amount of the inorganic component and the surfactant is 100 parts by weight. It is 40 parts by weight, more preferably 2 to 35 parts by weight, still more preferably 3 to 30 parts by weight, and particularly preferably 4 to 25 parts by weight. When the content of the surfactant is 1 part by weight or more, the dispersibility tends to be improved, and when it is 40 parts by weight or less, the adhesiveness tends to be improved.

The adhesive composition for unvulcanized rubber of the present invention may further contain the following components in addition to the components described above.

[Metal soap]
Metal soap is a component that adheres to the surface of unvulcanized rubber and can reduce friction between unvulcanized rubber. Examples of metal soaps include magnesium laurate, calcium laurate, zinc laurate, magnesium myristate, calcium myristate, zinc myristate, magnesium palmitate, calcium palmitate, zinc palmitate, magnesium stearate, calcium stearate, stearate. Examples thereof include zinc acid, aluminum trioctadecanoate, aluminum dioctadecanoate, aluminum monooctadecanoate, calcium octadecate, zinc octadecanoate, magnesium octadecanoate, barium octadecanoate, etc., and one or more of them may be used in combination. ..
As the metal soap, at least one selected from magnesium stearate, calcium stearate and zinc stearate is preferable because it has a high effect of reducing friction between unvulcanized rubbers.

Moreover, it is preferable that the adhesive composition for unvulcanized rubber of the present invention contains a carbonate and / or a metal soap in that the effect of the present invention can be obtained.
When the non-vulverized rubber adhesive composition of the present invention contains a carbonate and / or a metal soap, the total content of the carbonate and the metal soap is not particularly limited, but is the total of the inorganic component and the surfactant. When the amount is 100 parts by weight, it is preferably 1 to 40 parts by weight, more preferably 2 to 35 parts by weight, still more preferably 3 to 30 parts by weight, and particularly preferably 4 to 25 parts by weight. When the total content of the carbonate and / or metal soap is 1 part by weight or more, the dispersibility tends to be improved, and when it is 40 parts by weight or less, the adhesion resistance tends to be improved.

[Water-soluble polymer]
The water-soluble polymer is a component that can impart viscosity to the adhesive composition for unvulcanized rubber and improve the adhesion to the surface of unvulcanized rubber. In particular, when the composition for unvulcanized rubber is in the form of an aqueous dispersion described later, the effect can be further enhanced.
Examples of water-soluble polymers include oxidized starch, acetate starch, phosphoric acid starch, carboxymethyl starch, carboxyethyl starch, hydroxyethyl starch, positive starch, cyanoethylated starch, dialdehyde starch and other starches; mannan; alginic acid, alginic acid. Alginates such as sodium, propylene glycol alginate, triethanolamine alginate, ammonium alginate; cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, carboxymethyl cellulose; Natural gums such as taracant gum, arabic gum, guar gum, xanthan gum, British gum, glucomannan, gellan gum, tara gum, locust bean gum, carrageenan; sodium polyacrylic acid; polyvinyl alcohol; polyethylene glycol; polyethylene oxide; water-soluble acrylic resin; water-soluble Examples thereof include sex urethane resin; water-soluble melamine resin; water-soluble epoxy resin; water-soluble butadiene resin; water-soluble phenol resin and the like.

[Multivalent alcohol]
Polyhydric alcohol is a component that adheres to the surface of unvulcanized rubber, can impart lubricity between unvulcanized rubbers, and reduces friction between 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 thereof include ethane, trimethylolpropane, ditrimethylolpropane, xylitol, sorbitol, mannitol, martitol, maltotriose, glucose, sucrose, fructose, and maltose, and one or more of them may be used in combination.

[Defoamer]
Examples of the defoaming agent include silicone-based defoaming agents such as polymethylsiloxane and polyether-modified Sirico; oil-based defoaming agents such as castor oil, sesame oil, flaxseed oil, and animal and vegetable oils; stearic acid, oleic acid, and palmitic acid. Defoamers based on fatty acids such as isoamyl stearate, distearyl succinate, ethylene glycol distearate, butyl stearate and the like; polyoxyalkylene monohydric alcohol di-t-amylphenoxyethanol, 3 -Alcohol-based defoamers such as hepthanol and 2-ethylhexanol; ether-based defoamers such as di-t-amylphenoxyethanol 3-heptyl cellosolve nonyl cellosolve 3-heptyl carbitol; tributyl osphate, tris (butoxyethyl) fuosphate Phosphate defoamers such as; amine defoamers such as diamilamine; amide defoamers such as polyalkyleneamide and acylate polyamine; sulfate ester defoamers such as sodium lauryl sulfate; polyoxyalkylene Antifoaming agent; mineral oil and the like may be mentioned, and one kind or two or more kinds may be used in combination.

〔Preservative〕
Examples of preservatives include thiazoles such as thiazole and 2-mercaptothiazole; thiocyanates such as methylenebisthiocyanate and ammonium thiocyanate; sulfidides such as o-benzoixulfimide and phenylmercuric-o-benzoixulfimide. Alkyldialkylthiocarbamates such as methyldimethylthiocarbamate and ethyldiethyldithiocarbamate; Phenol sulfides such as tetramethylthiraum sulfide and tetraethyltiraum sulfide; Kind; Dithiocarbamates such as ferric diethyldithiocarbamate and lead dimethyldithiocarbamate; Sulfamides such as o-toluenesulfonamide and benzenesulphonanilide; 1-aminonaphthyl-4-sulfonic acid, 1-amino-2-naphthol-4 Aminosulfonic acids such as −sulfonic acid; Phenols such as pentachlorophenol and o-phenylphenol and alkali metal salts thereof ;; Chloride such as tetrachloro-p-benzoquinone and 2,3-dichloro-1,4-naphthoquinone. Kinones; nitro group-containing compounds such as dinitrocaprylphenylcrotonate and dinitro-o-cresol; 1,3,5-trihydroxyethylhexahydro-1,3,5-triazine, 1,3,5-triethylhexa Triazines such as hydro-1,3,5-triazine; organic mercury compounds such as phenylmerculic phthalate and o-hydroxyphenylmerculic 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 or more of them may be used in combination.

〔water〕
The adhesive composition for unvulcanized rubber of the present invention may contain water. It is preferable that the adhesive composition of the unvulcanized rubber contains water from the viewpoint of handleability.
The water may be tap water, ion-exchanged water, distilled water, or the like, and is not particularly limited, but ion-exchanged water or distilled water is preferable. Further, from the viewpoint of quality control, it is preferable that the water is soft water because its hardness can be adjusted.

When the form of the adhesive composition for unvulcanized rubber of the present invention is an aqueous dispersion, the weight ratio of water to the adhesive composition for unvulcanized rubber is not particularly limited, but is preferably 90. It is ~ 99.99% by weight, more preferably 92.5 to 99.95% by weight, still more preferably 95 to 99.5% by weight. When the weight ratio of water is 90% by weight or more, the drying property tends to be improved, and when it is 99.9% by weight or less, the adhesion property tends to be improved.

[Manufacturing method of adhesive for unvulcanized rubber]
In the non-vulcanized rubber adhesive composition of the present invention, the method for producing the same is as long as it includes a step of mixing an inorganic component with a surfactant, a metal soap, a fatty acid soap, and other components. There are no particular restrictions on the mixing order or the mixing equipment used. The unvulcanized rubber adhesive composition can be produced, for example, by sequentially adding and mixing each component to a mixer such as a ribbon type mixer or a vertical screw type mixer.

[Manufacturing method of anti-vulcanized rubber]
The method for producing an anti-vulcanized rubber of the present invention includes a treatment step of adhering the above-mentioned adhesive composition for unvulcanized rubber to the surface of the 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 the adhesive composition for unvulcanized rubber in the form of the above-mentioned aqueous dispersion is preferable.

When the treatment process is performed by the wet method, a method of spraying an adhesive composition for unvulcanized rubber in the form of an aqueous dispersion, a method of spraying on rubber with a trickle, a method of immersing in an aqueous dispersion, etc. Can be mentioned.
The method of immersing in an aqueous dispersion is preferable because the adhesive composition for unvulcanized rubber can be uniformly adhered. The unvulcanized rubber used in the production method of the present invention is usually in a state of being heated to 100 to 180 ° C., and the unvulcanized rubber can be cooled by a method of immersing it in an aqueous dispersion. 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 after adhering the aqueous dispersion may be carried out. The drying method is not particularly limited, but the cost may be low if the method is forcibly dried by sending hot air with a hot air blower or a blow heater.

In the treatment step, a dry method, that is, a method using an unvulcanized rubber adhesive composition containing no water may be used.
The unvulcanized rubber that has been subjected to the adhesion-proofing treatment produced in this manner can prevent the unvulcanized rubbers from adhering to each other when they are stacked and stored until the next step is performed.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to these examples. The evaluation of each physical property in Examples and Comparative Examples was carried out as follows.

[Adhesion resistance]
NR / BR test piece (natural rubber / butadiene rubber; thickness 0.) heated to 100 ° C. with respect to the aqueous dispersion of the adhesive composition for unvulcanized rubber (water weight ratio is 98.5% by weight). (5 cm x 5 cm x 3 cm) was immersed and immediately pulled up. Two soaked rubber test pieces were prepared, air-dried and then stacked, and ^{a load of 1000 kg / m 2} was applied and the rubber test pieces were left in a constant temperature bath at 40 ° C. for 24 hours. The test piece taken out from the constant temperature bath was air-cooled to room temperature, and the peeling drag (N / cm) was measured at a speed of 100 mm / min using a tensile tester. The smaller the peeling drag, the easier it is to peel off and the higher the adhesion resistance. The evaluation criteria are as follows, and the case where the peeling drag is less than 2 N / cm is regarded as acceptable.
Peeling drag is 1 N / cm or less: Very good adhesion (unvulcanized rubber can be easily peeled off, index is ◎)
Peeling drag is more than 1N / cm and less than 2N / cm: Good adhesion (unvulcanized rubber can be peeled off without load, index is ○)
Peeling drag is 2N / cm or more and 3N / cm or less: Poor adhesion (the load when peeling unvulcanized rubber is large, the adhesion is low, the index is △)
Peeling drag is over 3 N / cm: Very poor adhesion (rubbers stick to each other and peeling is difficult. Very low adhesion, index is x)

[Drop prevention]
An NR / BR rubber test piece (natural rubber / butadiene rubber; thickness 0.5 cm × length 10 cm × width 10 cm) was prepared, and an aqueous dispersion of an adhesive composition for unvulcanized rubber (weight ratio of water was 98. The rubber test piece heated to 100 ° C. was immersed twice in succession with respect to 5% by weight) and immediately pulled up. After the test piece was air-dried, each of the six sides of the test piece was rubbed by hand 10 times, and the shedding prevention property of the unvulcanized rubber adhesive composition was visually evaluated.
Ingredients do not adhere to hands: Especially high in prevention of falling off (index is ◎)
There is no scattering of ingredients in the surrounding area, but the ingredients adhere to the hands: Highly preventive from falling off (index is ○)
Ingredients adhere to the hands and scatter in the surrounding area: Low prevention of falling off (many foreign substances on rubber, index is x)

(Example 1)
80 g of bentonite 1, 10 g of calcium carbonate, 2 g of sodium dioctyl sulfosuccinate and 8 g of POE (3) tridecyl ether were uniformly mixed to obtain an adhesive composition for unvulcanized rubber.
Next, 4.5 g of the above-mentioned adhesive composition was added to 295.5 g of tap water and uniformly dispersed in water to obtain an aqueous dispersion of the unvulcanized rubber adhesive composition. Using the obtained aqueous dispersion, the adhesion resistance and the dropout prevention property were evaluated. The results of the evaluation are shown in Table 1, and they were excellent in adhesion resistance and dropout prevention.

(Examples 2 to 23)
In Examples 2 to 23, an unvulcanized rubber adhesive composition and an aqueous dispersion thereof were obtained and evaluated in the same manner as in Example 1 except that the compositions were changed as shown in Tables 1 to 3. .. The evaluation results are shown in Tables 1 to 3.

(Comparative Example 1)
80 g of bentonite 5, 10 g of calcium carbonate, 2 g of sodium dioctyl sulfosuccinate and 8 g of POE (3) tridecyl ether were uniformly mixed to obtain an adhesive composition for unvulcanized rubber.
Next, 4.5 g of the above-mentioned adhesive composition was added to 295.5 g of tap water and uniformly dispersed in water to obtain an aqueous dispersion of the unvulcanized rubber adhesive composition. Using the obtained aqueous dispersion, the adhesion resistance and the dropout prevention property were evaluated. The results of the evaluation are shown in Table 4, and the drop-off prevention property was poor.

(Comparative Examples 2 to 8)
In Comparative Examples 2 to 8, an unvulcanized rubber adhesive composition and an aqueous dispersion thereof were obtained and evaluated in the same manner as in Comparative Example 1 except that the composition was changed as shown in Table 4. The results are shown in Table 4, respectively.
In the above Examples and Comparative Examples, POE (n) means polyoxyethylene (number of repeating units of oxyethylene: n), and POP (n) means polyoxypropylene (repeating unit of polyoxypropylene: n). Means.
The types of iron compounds contained in the silicates used and the weight ratio of the iron compounds to the silicates are as follows.
Bentonite 1: 0.1% by weight of iron oxide, 99.9% by weight of silicate
Bentonite 2: 0.5% by weight of iron oxide, 99.5% by weight of silicate
Bentonite 3: 1% by weight of iron oxide and iron sulfide, 99% by weight of silicate
Bentonite 4: 2% by weight of iron oxide and iron sulfide, 98% by weight of silicate
Bentonite 5: 5% by weight of iron oxide and iron sulfide, 95% by weight of silicate
Bentonite 6: 10% by weight of iron oxide and iron sulfide, 90% by weight of silicate
Kaolin: 0.1% by weight of iron oxide, 99.9% by weight of silicate

As can be seen from Tables 1 to 3, the adhesive composition for unvulverized rubber of Examples 1 to 23 is an adhesive composition for unvulverized rubber containing an inorganic component and a surfactant. The inorganic component essentially contains a silicate and at least one selected from iron oxide and iron sulfide, and the total weight ratio of iron oxide and iron sulfide to the total of silicate, iron oxide and iron sulfide is 2% by weight. Less than, the surfactant comprises an anionic surfactant (A) and a nonionic surfactant (B), the surfactant comprises an anionic surfactant (A) and a nonionic surfactant (B), and ( Since the weight ratio (A / B) represented by the weight of A) / the weight of (B) is 0.1 to 1, it is possible to suppress the scattering of dust due to dropping, which is a subject of the present application.
On the other hand, as can be seen from Table 4, when the total weight ratio of iron oxide and iron sulfide to the total of silicate, iron oxide and iron sulfide is 2% by weight or more (Comparative Examples 1 and 2), anionic surface activity. When the weight ratio (A / B) of the agent (A) and the nonionic surfactant (B) is not in the range of 0.1 to 1 (Comparative Examples 3 to 5), when there is no nonionic surfactant (B) ( In Comparative Example 6), in the absence of silicate (Comparative Examples 7 and 8), at least one of the problems of the present application, that is, anti-shedding property and anti-adhesion property, cannot be solved.

The adhesive composition for unvulcanized rubber of the present invention is used in the production processing process of unvulcanized rubber products, and is stacked until the unvulcanized rubber is transferred to the next molding or vulcanization process. It is possible to prevent the rubber from adhering to the rubber when it is stored. At that time, the problem of dust generation due to falling off is greatly reduced, so that the productivity of rubber products can be improved.

Claims (4)

An adhesive composition for unvulcanized rubber containing an inorganic component and a surfactant.
The inorganic component essentially contains silicate and at least one selected from iron oxide and iron sulfide.
The total weight ratio of the iron oxide and the iron sulfide to the total of the silicate, the iron oxide and the iron sulfide is less than 2% by weight.
The surfactant contains an anionic surfactant (A) and a nonionic surfactant (B), and the weight ratio (A / B) represented by the weight of (A) / the weight of (B) is 0.1 to 1. 1. The adhesive composition for unvulcanized rubber. The adhesive composition for unvulcanized rubber according to claim 1, further containing a carbonate and / or a metal soap. The adhesive composition for unvulcanized rubber according to claim 1 or 2, wherein the anionic surfactant (A) contains a fatty acid soap. Anti-vulcanized unvulcanized rubber comprising a treatment step of adhering the adhesive composition for unvulcanized rubber according to any one of claims 1 to 3 to the surface of the molded unvulcanized rubber. Manufacturing method.