JP2022060625A - Adhesion preventive composition for unvulcanized rubber and use thereof - Google Patents

Abstract

To provide an adhesion preventive composition for unvulcanized rubber that excels in both of adhesion prevention and disintegration, and a method for producing unvulcanized rubber that undergoes adhesion preventive treatment with the adhesion preventive composition for unvulcanized rubber.SOLUTION: An adhesion preventive composition for unvulcanized rubber includes inorganic components, which essentially include silicate, a surfactant and a metallic soap or wax. When the adhesion preventive composition for unvulcanized rubber is 100 pts.wt., the silicate is 10-35 pts.wt. The silicate includes at least one selected from iron oxide and iron sulfide. The ratios of the weights of the iron oxide and the iron sulfide to the total of the silicate, the iron oxide and the iron sulfide are less than 2 wt.% in total. The surfactant essentially includes a nonionic surfactant with an HLB of 3-13 by Griffin method.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.

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 the inorganic powder, a water-swellable inorganic powder such as bentonite is generally used. Water-swellable inorganic powder swells in water and becomes fine particles, so it has excellent adhesion to rubber. However, since it becomes fine particles, the cohesive force between the particles at the time of drying is strong, and the hardness of the dried solidified product is remarkably increased.
As a countermeasure against this, an adhesive that has improved the disintegration property of the dried solidified product has been developed. not.

Patent Document 1 discloses a wear-proof composition comprising a water-soluble polymer having a film-forming property and an anionic active agent or a nonionic active agent. This anti-wearing composition is characterized by not using an inorganic powder, and can suppress the formation of a dry solidified product. but,
In order to exhibit sufficient adhesive performance, it is necessary to use it at a high concentration, in which case the water retention of the water-soluble polymer becomes significantly high, and the drying step after applying the adhesive composition. It takes time and reduces productivity.
Patent Document 2 discloses an adhesion preventive agent for rubber, which is mainly composed of a specific inorganic powder other than Bennite and has improved disintegration property of a dried solidified product. However, an adhesive that does not mainly contain a water-swellable inorganic powder such as bentonite is inferior in adhesiveness, and therefore needs to be used at a high concentration in order to obtain sufficient adhesiveness. At high concentrations, even if the disintegration property of the dried solidified product is improved, the risk of forming a lump of the adhesive that becomes a foreign substance on the rubber increases.
As described above, the adhesives having improved disintegration property are shown in Patent Documents 1 and 2, but at the same time, none of them satisfy sufficient adhesiveness.

Japanese Unexamined Patent Publication No. 62-32127 Japanese Unexamined Patent Publication No. 14-363532

An object of the present invention is an unvulcanized rubber protective agent composition having excellent adhesiveness and disintegration property at the same time, and an unvulcanized non-vulcanized rubber adhesive composition performed by using the unvulcanized rubber adhesive composition. The present invention is to provide a method for producing vulcanized rubber.

As a result of diligent studies to solve the above problems, the present inventor has made a surfactant containing a nonionic surfactant showing HLB by a specific Griffin method, an inorganic component containing a specific iron compound, a metal soap and / Alternatively, it has been found that a problem can be solved by using a non-vulcanized rubber adhesive composition containing wax.
That is, the adhesive composition for unvulcanized rubber of the present invention is an adhesive composition for unvulcanized rubber containing an inorganic component, a surfactant, a metal soap and / or a wax. ,
When the inorganic component indispensably contains a silicate and at least one selected from iron oxide and iron sulfide, and the amount of the unsulfurized rubber adhesive composition is 100 parts by weight, the silicate is used. It is 10 to 35 parts by weight, and 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 essentially contains a nonionic surfactant of HLB 3 to 13 according to the Griffin method.

When the unvulcanized rubber adhesive composition is 100 parts by weight, the total amount of the metal soap and / or wax is preferably 10 to 70 parts by weight.
It is preferable to further contain a carbonate.

The method for producing an unvulcanized unvulcanized 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.

Since the adhesive composition for unvulcanized rubber of the present invention is excellent in adhesiveness and disintegration at the same time, it is excellent in productivity in the unvulcanized rubber manufacturing process.

[Adhesive composition for unvulcanized rubber]
The adhesive composition for unvulcanized rubber of the present invention comprises an inorganic component that requires a silicate, a surfactant that requires a nonionic surfactant having an HLB of 3 to 13 by the Griffin method, and a metal soap. And / or a non-vulcanized rubber adhering agent composition containing wax.
Hereinafter, each component will be described in detail.

[Inorganic component]
The inorganic component is a component of a material that forms a film on the surface of unvulcanized rubber and exhibits adhesiveness.
In the non-vulcanized rubber adhesive of the present invention, the inorganic component contains silicate as an essential component.
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, innosilicates, phyllosilicates, tect silicates, etc. according to the silicate tetrahedron connection method, and the silicates for unsulfurized rubber of the present invention. In the dressing, 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 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 the like, and these may be used alone or in combination of two or more.

Solo silicates are classified as complex ligated 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 lenite such as zoisite and clinozoisite; melilite such as okelmite 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; auxite; beryl; iron tourmaline, magnesio-foit, lisia tourmaline and the like; osumilite and the like. Seeds or two or more may be used in combination.

Innosilicates 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 innosilicate is not particularly limited, and examples thereof include pyroxenes such as diopside, clinoenstatite, enstatite, acumite, and spodium; anthophyllite, tremolite, indigo flash, and amphibole such as roadnite. These may be used alone or in combination of two or more.

The phyllosilicate is classified as a layered connection type silicate, and has a structure represented by the chemical formula of SiO ₂ as a basic composition. The phyllosilicate is not particularly limited, but is, for example, smectite such as montmorillonite, byderite, nontronite, saponite, hectrite, soconite, and stibunsite; vermiculite such as divermiculite and trivermiculite; halloysite, kaolin, and ende. Kaolinite such as light, deckite, nacrite, 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-connected silicates and have a basic composition 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, anorthite, and neferin; zeolites such as leucite, scoles zeolite, and heulandite; scapolite, and the like. 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 exchangeable 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 in water and the film property is improved. Further, among smectites, montmorillonite is preferable because it has particularly remarkable water swelling property.

Montmorillonite is a mineral of a dihedron type hydrous layered silicate, and contains 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 exchanged 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 film of bentonite is excellent in adhesiveness and slipperiness, it is more preferable that the silicate in the adhesive for unvulcanized rubber of the present invention contains bentonite as an essential component. Further, when bentonite contains sodium bentonite in a high purity, the water swelling effect is remarkably most preferable.

Further, the inorganic component used in the present invention preferably has a small weight ratio of iron oxide and iron sulfide to the total of silicate, iron oxide and iron sulfide. Sirates often exist together with trace amounts of carbonates and iron compounds, but iron compounds have a higher specific gravity than silicates and are not excellent in water dispersibility. Therefore, if the weight ratio of the iron compound to the total of the silicate, iron oxide and iron sulfide is large, the uniform adhesion of the silicate to the rubber is hindered and the adhesion is deteriorated. Therefore, from the viewpoint of promoting uniform adhesion of the adhesive and enhancing the adhesive property, it is preferable that the weight ratio of the iron compound is as small as possible.

The weight ratio of iron oxide and iron sulfide to the total of silicate, iron oxide and iron sulfide is preferably less than 2%, more preferably less than 1.8%, still more preferably less than 1.6%, particularly preferably 1. Less than 0.4%, most preferably less than 1.2%.

The preferable lower limit of the weight ratio of iron oxide and iron sulfide to the total of silicate, iron oxide and iron sulfide is 0.1% by weight, more preferably 0.05% by weight, still more preferably 0.01% by weight, and more. It is more preferably 0.001% by weight, particularly preferably 0.0001% by weight, and most preferably more than 0% 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 compound present together is less than 2% by weight, a commercially available product thereof is obtained. However, the silicate containing the iron compound coexisting with the iron compound may be treated by a centrifuge method, a centrifugation method, or the like, or the iron compound may be mixed.
The iron compound in the present invention is at least one selected from iron oxide and iron sulfide, and may contain both.

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

Regarding the weight ratio of the silicate to the total weight of the unvulcanized rubber adhesive composition, preferably, the silicate is 10 to 10 parts by weight when the unvulcanized rubber adhesive composition is 100 parts by weight. 35 parts by weight is preferable. It is more preferably 12.5 to 32.5 parts by weight, and particularly preferably 15 to 30 parts by weight.

[Surfactant]
The surfactant is an essential component in the present invention, and is a component that assists the adhesion of the adhesive composition to the unvulcanized rubber. Since the surfactant is contained in the adhesive composition for unvulcanized rubber of the present invention, the adhesion to the unvulcanized rubber is improved, so that the surface of the unvulcanized rubber is more uniformly coated. Improves adhesion.

The surfactant used in the present invention essentially contains a nonionic surfactant having an HLB of 3 to 13 according to the Griffin method. Nonionic surfactants improve the adhesion of the adhesive composition to unvulcanized rubber.

Here, the HLB by the Griffin method is a numerical value that can be calculated by the following (I) based on the molecular structure. That is, the HLB by the Griffin method takes a numerical value from 0 to 20, and the smaller the value is, the more lipophilic it is, and the larger the value is, the more hydrophilic it is.
HLB = 20 × (total formula weight of hydrophilic part / molecular weight) (I)
The nonionic surfactant having an HLB of 3 to 13 according to the Griffin method is not particularly limited and may contain one kind or two or more kinds. The role of the nonionic surfactant having an HLB of 3 to 13 by the Griffin method is to generate scum in the circulation of the dispersion of the adhesive containing the silicate and the metal soap and / or the wax, thereby forming a scum on the rubber surface. The purpose is to form a wavy adhesive film.
If the HLB according to the Griffin method is less than 3, the wettability to the rubber is insufficient, and if it exceeds 13, the foam-suppressing property is insufficient.
The HLB by the Griffin method is preferably 4 to 12, more preferably 5 to 11, and particularly preferably 6 to 10 from the viewpoint of adhesion resistance and disintegration.

As the nonionic surfactant having an HLB of 3 to 13 by the Griffin method, for example, a nonionic surfactant represented by the following chemical formula (1) can be used.
RO- (AO) n-H (1)
In the chemical formula (1), R is an aliphatic hydrocarbon group. 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. AO represents 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 polymerization unit to which an alkylene oxide having 2 to 4 carbon atoms is added. When a plurality of types of oxyalkylene groups are contained, these groups may be arranged in a block shape or at random.
The weight ratio of the surfactant to the total weight of the unvulcanized rubber adhesive composition is not particularly limited, but is preferably 1 to 30% by weight from the viewpoint of adhesion and foaming of the aqueous dispersion. .. It is more preferably 1 to 28% by weight, particularly preferably 1 to 26% by weight, and most preferably 1 to 24% by weight.

[Metal soap]
Metal soap is a component that adheres to the surface of unvulcanized rubber and reduces friction between unvulcanized rubber. In addition, it is a component that weakens the aggregation of the dried solidified product of the adhesive and improves the disintegration property.
Metallic soaps 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, barium octadecanoate and the like.
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.
The weight ratio of the metal soap to the total weight of the unvulcanized rubber protective agent composition is preferably 100 parts by weight when the unvulcanized rubber adhesive composition is made up of 100 parts by weight from the viewpoint of achieving the effect of the present application. , The metal soap is preferably 10 to 70 parts by weight. It is more preferably 12.5 to 67.5 parts by weight, and particularly preferably 15 to 65 parts by weight.

The average particle size of the metal soap is not particularly limited, but is preferably 0.1 to 200 μm from the viewpoint of friction reducing effect, disintegration improving effect, and powder removal of the metal soap adhering to the surface of unvulcanized rubber. It is preferably 0.1 to 100 μm, more preferably 0.1 to 50 μm, particularly preferably 0.1 to 40 μm, and most preferably 0.1 to 30 μm.

[wax]
Like metal soap, wax is a component that adheres to the surface of unvulcanized rubber and reduces friction between unvulcanized rubber. In addition, it is a component that weakens the aggregation of the dried solidified product of the adhesive and improves the disintegration property.
The wax is not particularly limited, and includes, for example, plant-based wax, animal-based wax, mineral-based wax, petroleum wax, synthetic hydrocarbon-based wax, modified wax, hydride wax, fatty acid amide, anhydrous phthalic acid imide, and the like. Particles are mentioned, and one kind or two or more kinds may be used in combination.

The vegetable wax is not particularly limited, and examples thereof include candelilla wax, carnauba wax, rice wax, Japan wax, cheek oil, sugar wax, bayberry wax, ochery wax, and esparto wax.
The animal wax is not particularly limited, and examples thereof include beeswax, lanolin, spermaceti, insect wax, and shellac wax.
The mineral wax is not particularly limited, and examples thereof include montan wax, ozokerite, and selecin.
The petroleum wax is not particularly limited, and examples thereof include paraffin wax, microkristang wax, and petroleum lactam.
The synthetic hydrocarbon wax is not particularly limited, and examples thereof include Fischer-Tropsch wax and polyethylene wax.
The modified wax is not particularly limited, and examples thereof include a montan wax derivative, a paraffin wax derivative, and a microkristang wax derivative.

The hydride wax is not particularly limited, but is, for example, cured 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- Examples thereof include 12-hydroxystearate and ethylene glycol-mono-12-hydroxystearate.
The fatty acid amide is not particularly limited, but is, for example, lauric acid amide, stearic acid amide, oleic acid amide, erucic acid amide, N, N'-xylylenebis stearic acid amide, coconut oil fatty acid monoethanolamide, N. -Oleyl stearate amide, N, N'-diorail adipic acid amide and the like can be mentioned.
Among the waxes described above, at least one selected from vegetable waxes, petroleum waxes, synthetic hydrocarbon waxes, and hydrogenated waxes is preferable.
The weight ratio of the wax to the total weight of the unvulcanized rubber protective agent composition is preferably 100 parts by weight when the unvulcanized rubber adhesive composition is 100 parts by weight from the viewpoint of achieving the effect of the present application. The wax is preferably 10 to 70 parts by weight. It is more preferably 12.5 to 67.5 parts by weight, and particularly preferably 15 to 65 parts by weight.

The average particle size of the wax is not particularly limited, but is preferably 0.1 to 200 μm, more preferably 0.1 to 100 μm, still more preferably, from the viewpoint of friction reducing effect, disintegration improving effect, and wax powder falling off. Is 0.1 to 50 μm, particularly preferably 0.1 to 40 μm, and most preferably 0.1 to 30 μm.

The adhesive composition for unvulcanized rubber of the present invention may further contain the following components in addition to the components described above.
[Other inorganic components]
Other inorganic components are components that adhere to the surface of unvulcanized rubber, prevent adhesion between unvulcanized rubbers, and reduce friction between unvulcanized rubbers.
Examples of other inorganic powders include carbonates such as calcium carbonate, sodium carbonate and magnesium carbonate; sulfates such as calcium sulfate and barium sulfate; amorphous silica, alumina, magnesium oxide, antimony trioxide and titanium oxide. Metal oxides such as white carbon; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, iron hydroxide; Bengala; carbon black; graphite and the like. As the other inorganic component, carbonate is preferable and not yet used. It is further preferable that it is at least one selected from calcium carbonate, which has a high effect of reducing friction between vulture rubbers, sodium carbonate and magnesium carbonate, which promotes swelling of bentonite in water and further improves adhesion resistance.

[Anionic surfactant]
Examples of anionic surfactants include potassium capricate, sodium caprate, sodium laurate, potassium laurate, sodium palmitate, potassium plumitate, potassium stearate, sodium stearate, sodium palm kernel oil fatty acid, and palm kernel oil. Fatty soaps such as potassium fatty acid, potassium palm stearate, sodium palm stearate, sodium palm oil fatty acid, potassium palm 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 such as polyoxyethylene tridecyl ether sodium acetate; Alkylbenzene sulfonate such as dodecylbenzene sulfonate sodium; 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 acid amide sulfonates such as; alkyl phosphates such as sodium monostearyl phosphate; polyoxyalkylene alkyl ether phosphates such as polyoxyethylene oleyl ether sodium phosphate, polyoxyethylene stearyl ether sodium phosphate; Examples thereof include long-chain N-acylglutamates such as sodium monosodium N-lauroyl glutamate and disodium N-stearoyl-L-glutamate.

[Water-soluble polymer]
The water-soluble polymer is a component that imparts viscosity to the aqueous dispersion of the adhesive composition for unvulcanized rubber and improves the adhesion to the surface of the unvulcanized rubber.
The water-soluble polymer is not particularly limited, but for example, starches such as oxidized starch, acetate starch, phosphate starch, carboxymethyl starch, carboxyethyl starch, hydroxyethyl starch, positive starch, cyanoethylated starch, and dialdehyde starch. Mannan; Arginic acids such as alginic acid, sodium alginate, propylene glycol alginate, triethanolamine alginate, ammonium alginate; methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxyethylethylcellulose, carboxymethylcellulose Ethyl cellulose ethers such as; natural gums such as taracanth 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; Examples thereof include water-soluble acrylic resin; water-soluble urethane resin; water-soluble melamine resin; water-soluble epoxy resin; water-soluble butadiene resin; and water-soluble phenol resin.

[Multivalent alcohol]
The polyhydric alcohol is a component that adheres to the surface of the unvulcanized rubber, imparts lubricity between the unvulcanized rubbers, and reduces friction between the unvulcanized rubbers.
The polyhydric alcohol is not particularly limited, but for example, glycerin, 1,3-butanediol, propylene glycol, dipropylene glycol, pentylene glycol, neopentyl glycol, hexylene glycol, polyethylene glycol, erythritol, pentaerythritol, di Pentaerythritol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, xylitol, sorbitol, mannitol, multitoll, maltotriose, glucose, sucrose, glycolose, maltose, etc. may be mentioned, and one or more of them may be used in combination. May be good.

[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 oil; stearic acid, oleic acid, and palmitic acid. Defoamers based on fatty acids such as: Isoamyl stearate, distearyl succinate, ethylene glycol distearate, butyl stearate and other fatty acid ester defoamers; polyoxyalkylene monohydric alcohol di-t-amylphenoxyethanol, 3 -Alcohol-based defoaming agents such as hepthanol and 2-ethylhexanol; Phosphoric acid ester-based defoaming agent such as; Amin-based defoaming agent such as diamilamine; Amid-based defoaming agent such as polyalkylene amide and acylate polyamine; Sulfate-based defoaming agent such as lauryl sulfate ester sodium; Polyoxyalkylene Antifoaming agent; examples include mineral oil.

〔Preservative〕
Examples of the preservative include thiazoles such as thiazole and 2-mercaptothiazole; thiocyanates such as methylenebisthiocyanate and ammonium thiocyanate; sulfidides such as o-benzoixlufmid and phenylmercuric-o-benzoixulfidide. Alkyldialkylthiocarbamates such as methyldimethylthiocarbamate and ethyldiethyldithiocarbamate; Tyraum sulfides such as tetramethyltyraum sulfide and tetraethyltiraum sulfide; Classes; 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 -Amino sulfonic 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 dinitrocapril phenylcrotonate 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 phenylmercuric 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.

〔water〕
The water may be tap water, ion-exchanged water, distilled water or the like, and is not particularly limited, but ion-exchanged water, distilled water or the like is preferable. Further, from the viewpoint of water hardness, it is preferable that the water is soft water from the viewpoint of quality control.

[Manufacturing method of adhesive for unvulcanized rubber]
Regarding the method for producing the non-vulcanized rubber adhesive according to the present invention, if it includes a step of mixing an inorganic powder, a surfactant, a metal soap or wax, and other components, the mixing order and use are used. There are no particular restrictions on the mixing equipment, etc. The non-vulcanized rubber adhesive can be produced, for example, by sequentially adding and mixing each component to a powder mixer such as a ribbon type mixer.

[Manufacturing method of anti-vulcanized rubber]
The method for producing an unvulcanized unvulcanized 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 an aqueous dispersion containing water as the adhesive composition for unvulcanized rubber is preferable.
When the treatment step is performed by the wet method, a method of spraying an unvulcanized rubber adhesive composition (water dispersion), a method of spraying the rubber with a trickle, a method of immersing in the dispersion, and the like 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. Then, the step of drying the unvulcanized rubber after adhering the aqueous dispersion may be carried out. The drying method is not particularly limited, but a method of forcibly drying by sending hot air with a hot air blower or a blow heater may be low in cost.
The concentration of the aqueous dispersion is preferably 0.01 to 10%, more preferably 0.05 to 7.5%, and 0.1 to 5. 0% is more preferable. If it is less than 0.01%, the adhesiveness may be deteriorated, and if it is more than 10%, the drying property may be deteriorated.
In the treatment step, a dry method, that is, a method using an unvulcanized rubber adhesive composition containing no water may be used.
The non-vulcanized rubber produced in this manner and which has been subjected to the anti-adhesion treatment 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 performed as follows.

[Detability]
NR / BR test piece (natural rubber / butadiene rubber; thickness 0.5 cm × length 5 cm ×) heated to 100 ° C. with respect to the aqueous dispersion (2.0% concentration) of the non-vulcanized rubber adhesive composition. Immediately pull up by immersing (3 cm wide). Two soaked rubber test pieces are prepared, air-dried, stacked, and a load of 1000 kg / m ² is applied and 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 adhesiveness (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 2 N / cm or more and 3 N / cm or less: Poor adhesiveness (load when peeling unvulcanized rubber is large, low adhesiveness, index is △)
Peeling drag is over 3 N / cm: Very poor adhesiveness (rubbers are in close contact with each other and difficult to peel off. Very low adhesiveness, index is x)

[Collapse]
The aqueous dispersion of the unvulcanized rubber adhesive composition was concentrated and dried to prepare a 10 mm square dry solidified product. The hardness of each dried solidified product was measured with a durometer, and the case where the value was less than 70 was regarded as acceptable.
Numerical value less than 60: Very good disintegration (dry solidified easily disintegrates, index is ◎)
Numerical value is 60 or more and less than 70: Good disintegration (dry solidified product disintegrates, index is ○)
Numerical value is 70 or more and less than 80: Poor disintegration (dry solidified product is a little hard to disintegrate, index is △)
Numerical value is 80 or more or cannot be measured: Very poor disintegration (dry solidified material is difficult to disintegrate, index is ×)

(Example 1)
Bentonite 1 20 g, zinc stearate 60 g, and POE (3) tridecyl ether 20 g were uniformly mixed to obtain an adhesive for unvulcanized rubber.
Next, 6 g of the above-mentioned adhesive composition was added to 294 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 disintegration property.

(Examples 2 to 16)
In Examples 2 to 16, an aqueous dispersion of an unvulcanized rubber adhesive composition was obtained and evaluated in the same manner as in Example 1 except that the compositions were changed as shown in Tables 1 and 2. The evaluation results are shown in Tables 1 and 2.
(Comparative Example 1)
Bentonite 5 20 g, zinc stearate 60 g, and POE (3) tridecyl ether 20 g were uniformly mixed to obtain an adhesive for unvulcanized rubber.
Next, 6 g of the above-mentioned adhesive composition was added to 294 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 disintegration property were evaluated. The results of the evaluation are shown in Table 3, and the adhesion resistance was poor.

(Comparative Examples 2-9)
In Comparative Examples 2 to 9, an aqueous dispersion of an unvulcanized rubber adhesive composition was obtained and evaluated in the same manner as in Comparative Example 1 except that the composition was changed as shown in Table 3. The results are shown in Table 3.
In the above Examples and Comparative Examples, POE (m) means polyoxyethylene (number of repeating units of oxyethylene: m). POP (n) means polyoxypropylene (number of repeating units of oxypropylene: n).
The types of iron compounds contained in the silicate used and the weight ratio of the iron compounds to the silicate are as follows.
Bentonite 1: Iron oxide 0.1% by weight, silicate 99.9% by weight
Bentonite 2: Iron oxide 0.5% by weight, silicate 99.5% by weight
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
Kaolin: 0.1% by weight of iron oxide, 99.9% by weight of silicate

As can be seen from Tables 1 and 2, the non-sulfurized rubber protective agent compositions of Examples 1 to 16 contain an inorganic component, a surfactant, a metal soap and / or a wax. The agent composition essentially contains the silicate and at least one selected from iron oxide and iron sulfide as the inorganic component, and the unsulfurized rubber adhesive composition is 100 parts by weight. Sometimes, the silicate is 10 to 35 parts by weight, and 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. Since the surfactant contains a nonionic surfactant having HLB 3 to 13, it satisfies both the adhesive resistance and disintegration performance, which are the subjects of the present application.
On the other hand, as can be seen from Table 3, when the total weight ratio of iron oxide and iron sulfide to the total of the silicate, the iron oxide and the iron sulfide is 2% by weight or more (Comparative Examples 1 and 2), the silicate is used. When not (Comparative Examples 3 and 4), when there is no metal soap and wax (Comparative Example 5), when there is no nonionic surfactant (Comparative Examples 6 and 7), when the HLB of the nonionic surfactant is not 3 to 13. (Comparative Examples 8 and 9) do not satisfy any one of the subject matter of the present application, adhesiveness or disintegration.

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 dry solidified product of the adhesive has good disintegration property, and it is possible to reduce the defects of the rubber product.

Claims (4)

An adhesive composition for unvulcanized rubber containing an inorganic component, a surfactant, a metal soap and / or a wax.
The inorganic component essentially contains a silicate and at least one selected from iron oxide and iron sulfide.
When the unvulcanized rubber adhesive composition is 100 parts by weight, the silicate is 10 to 35 parts by weight.
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.
An adhesive composition for unvulcanized rubber, wherein the surfactant indispensably contains a nonionic surfactant of HLB3 to 13 by the Griffin method. The adhesive for unvulcanized rubber according to claim 1, wherein the total amount of the metal soap and / or wax is 10 to 70 parts by weight when the composition of the protective agent composition for unvulcanized rubber is 100 parts by weight. Agent composition. The adhesive composition for unvulcanized rubber according to any one of claims 1 and 2, further containing a carbonate. The unvulcanized unvulcanized rubber, which comprises 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.