JP2023075023A - Anti-adhesion composition for unvulcanized rubber, anti-adhesion composition moisture dispersant for unvulcanized rubber, and unvulcanized rubber - Google Patents

Abstract

To provide an anti-adhesion composition for unvulcanized rubber having viscosity not so high, and capable of combining, in addition to excellent anti-adhesion, both lubricity and dustability.SOLUTION: In order to achieve the above object, an anti-adhesive composition for unvulcanized rubber of the present invention comprises the following components (A) to (C) and water, and the following component (B) contains the following component (B1) and the following component (B2), and a mass ratio (B1)/(B2) of the following component (B1) to the following component (B2) is in the range of 1 to 20. (A) a water-soluble polymer (B) a metal soap (C) a surfactant (B1) at least one metal soap selected from the group consisting of fatty acid calcium and fatty acid lithium (B2), at least one metal soap selected from the group consisting of fatty acid zinc, fatty acid magnesium, and fatty acid aluminum.SELECTED DRAWING: None

Description

The present invention relates to an anti-adhesion agent composition for unvulcanized rubber, an aqueous dispersion of an anti-adhesion agent composition for unvulcanized rubber, and an unvulcanized rubber.

In rubber production and processing sites, an anti-adhesion agent is applied to the surface of rubber (for example, unvulcanized rubber) for the purpose of preventing adhesion of the rubber.

Anti-adhesion agents for rubber containing inorganic powder as a main component are widely used as anti-adhesion agents for rubber. These can generally be used by making them into the form of an aqueous dispersion and then adhering them to the rubber surface (Patent Documents 1 and 2). In addition, various anti-adhesion agents using water-soluble polymers and the like have been proposed in order to reduce dust derived from inorganic powder. For example, in Patent Documents 3 and 4, water-soluble polymers (sodium alginate, CMC, sodium polyacrylate, PVA, etc.), water-soluble polysaccharides (xanthan gum), etc. are blended to increase the viscosity of the anti-adhesive aqueous dispersion. and improve the adhesion of the anti-adhesion agent to the rubber surface.

JP-A-50-149770 JP 2013-001720 A JP-A-62-032127 JP 2009-161667 A

In the anti-adhesive composition for unvulcanized rubber, if the lubricity is poor, the unvulcanized rubber coated with the anti-adhesive composition for unvulcanized rubber becomes less slippery when in contact with other rubbers, metals, etc. There is a risk. Further, if the anti-adhesive composition for unvulcanized rubber has poor scattering properties, the anti-adhesive composition for unvulcanized rubber may scatter and pollute the surrounding environment.

Further, if the viscosity of the anti-adhesive composition for unvulcanized rubber is too high, the adhesion to the rubber surface is improved as described above, but the fluidity of the anti-adhesive composition for unvulcanized rubber is reduced, etc. Because of the reason, there is a possibility that the handleability (ease of handling) may deteriorate.

Therefore, the present invention provides an anti-adhesion agent composition for unvulcanized rubber that is not too high in viscosity and is capable of achieving both excellent anti-adhesion properties and lubricity and scattering properties, for unvulcanized rubber An object of the present invention is to provide an anti-adhesive composition aqueous dispersion and an unvulcanized rubber.

In order to achieve the above object, the anti-adhesive composition for unvulcanized rubber of the present invention is
including the following components (A) to (C) and water,
The following component (B) includes the following component (B1) and the following component (B2),
The mass ratio (B1)/(B2) of the following component (B1) and the following component (B2) is in the range of 1-20.

(A) water-soluble polymer (B) metal soap (C) surfactant (B1) at least one metal soap selected from the group consisting of fatty acid calcium and fatty acid lithium (B2) fatty acid zinc, fatty acid magnesium, and fatty acid at least one metal soap selected from the group consisting of aluminum

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

The unvulcanized rubber of the present invention is characterized in that the components (A) to (C) in the antiadhesive composition for unvulcanized rubber of the present invention adhere to the surface.

According to the present invention, the viscosity is not too high, and in addition to excellent anti-adhesion properties, an anti-adhesive composition for unvulcanized rubber capable of achieving both lubricity and scattering properties, for unvulcanized rubber An anti-adhesive composition aqueous dispersion and an unvulcanized rubber can be provided.

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

According to the anti-adhesive composition for unvulcanized rubber of the present invention, as described above, in addition to excellent anti-adhesion properties, it is possible to achieve both lubricity and scattering properties. Here, in the present invention, the term "lubricity" means that when the unvulcanized rubber coated with the unvulcanized rubber anti-adhesive composition comes into contact with other members (e.g., other rubbers, metals, etc.) , is defined as the property of reducing the frictional resistance generated on the contact surface. In addition, in the present invention, the term "scatterability" is defined as the property of the anti-adhesive composition for unvulcanized rubber and the dried product thereof to scatter. It can be said that the anti-adhesive composition for unvulcanized rubber has excellent scattering property as the scattering property is low (difficult to scatter). The anti-adhesive composition for unvulcanized rubber of the present invention is excellent in handleability (ease of handling) due to, for example, low scattering properties (difficult to scatter).

In the present invention, methods for measuring anti-adhesiveness, lubricity, scattering property and viscosity are not particularly limited.

The anti-adhesive composition for unvulcanized rubber of the present invention is, for example, 25 to 70% by mass of the component (A) with respect to 100% by mass of the total mass of components other than water, and 20 to 70% by mass of the component (B). 60% by mass, and 10 to 20% by mass of the component (C). As a result, for example, an anti-adhesion agent for unvulcanized rubber having even better anti-adhesion properties and lubricity can be obtained.

The anti-adhesive composition for unvulcanized rubber of the present invention, for example, the mass ratio (A) / (B) of the component (A) and the component (B) is in the range of 0.5 to 3 good too. As a result, for example, an anti-adhesion agent for unvulcanized rubber having a better balance between lubricity and scattering properties can be obtained.

The anti-adhesion treatment method for unvulcanized rubber of the present invention includes, for example, the components (A) to (C) in the anti-adhesion agent composition for unvulcanized rubber of the present invention. It may be a method for anti-adhesion treatment of unvulcanized rubber, characterized by including an anti-adhesion treatment step of performing adhesion treatment. In the anti-adhesion treatment step, for example, the anti-adhesion agent composition for unvulcanized rubber of the present invention or the aqueous dispersion of the anti-adhesion agent composition for unvulcanized rubber of the present invention is attached to the surface of the unvulcanized rubber. Further, by volatilizing water, it may be a step of attaching the components (A) to (C) in the anti-adhesive composition for unvulcanized rubber of the present invention to the surface of the unvulcanized rubber. More specifically, the anti-adhesion treatment step is, for example, the unvulcanized rubber anti-adhesion agent composition adhesion step of attaching the unvulcanized rubber anti-adhesion agent composition of the present invention to the surface of the unvulcanized rubber and a drying step of drying the anti-adhesive composition for unvulcanized rubber on the surface of the unvulcanized rubber to form a coating on the surface of the unvulcanized rubber.

Specific examples of the present invention will be described in more detail below.

[1. Anti-adhesive composition for unvulcanized rubber]
The anti-adhesive composition for unvulcanized rubber of the present invention is, as described above,
including the following components (A) to (C) and water,
The following component (B) includes the following component (B1) and the following component (B2),
The mass ratio (B1)/(B2) of the following component (B1) and the following component (B2) is in the range of 1-20.

(A) water-soluble polymer (B) metal soap (C) surfactant (B1) at least one metal soap selected from the group consisting of fatty acid calcium and fatty acid lithium (B2) fatty acid zinc, fatty acid magnesium, and fatty acid at least one metal soap selected from the group consisting of aluminum

The anti-adhesive composition for unvulcanized rubber of the present invention has the above composition, so that the viscosity is not too high, and in addition to excellent anti-adhesion properties, it is possible to achieve both lubricity and scattering properties. be.

Each component of the anti-adhesive composition for unvulcanized rubber of the present invention is described below.

[1-1. Component (A): water-soluble polymer]
The component (A) is, as described above, a water-soluble polymer. In the anti-adhesive composition for unvulcanized rubber of the present invention, the component (A), that is, the water-soluble polymer (hereinafter sometimes referred to as "water-soluble polymer (A)") is placed in water, or It is a polymer compound that can be dispersed or dissolved in the anti-adhesive composition for unvulcanized rubber of the present invention by putting it in water and then heating it. As a result, for example, an effect of covering the unvulcanized rubber can be obtained, and an anti-adhesion effect can be obtained. Thus, said component (A) acts, for example, as a film-forming agent. Further, for example, by using the component (A) and the component (B) in combination, anti-adhesion properties are exhibited.

In the anti-adhesive composition for unvulcanized rubber of the present invention, the content of the water-soluble polymer (A) is not particularly limited, but for example, the lower limit is It may be 25% by mass or more, for example, 30% by mass or more, 40% by mass or more, or 50% by mass or more, and, for example, 70% by mass or less, 60% by mass or less, 40% by mass or less, or 35% by mass % or less. When the content of the water-soluble polymer (A) is 25% by mass or more with respect to the total mass of components other than water, for example, an effect of covering unvulcanized rubber can be obtained. Further, the anti-adhesive composition for unvulcanized rubber of the present invention has a water-soluble polymer (A) content of 70% by mass or less with respect to the total mass of components other than water, for example, It has excellent drying properties and can be dried quickly.

The water-soluble polymer (A) may be, for example, a water-soluble polymer such that a 2% by mass aqueous solution of the water-soluble polymer (A) has a viscosity of 3 to 6000 mPa·s at 25°C. The water-soluble polymer having a viscosity of 3 mPa·s or more at 25° C. in the 2% by mass aqueous solution provides, for example, an effect of increasing the adhesion amount to unvulcanized rubber. By being a water-soluble polymer having a viscosity of 6000 mPa·s or less in the 2% by mass aqueous solution, for example, an effect of excellent drying property can be obtained. The viscosity of the 2% by mass aqueous solution may be, for example, 10 mPa s or more, 40 mPa s or more, 80 mPa s or more, or 100 mPa s or more, or 5500 mPa s or less, 5000 mPa s or less, or 4500 mPa s. Below, it may be 4000 mPa·s or less, 300 mPa·s or less, 200 mPa·s or less, or 100 mPa·s or less.

The water-soluble polymer (A) is not particularly limited, but may be, for example, a polymer having a lower limit of solubility in 100 g of water at 25° C. of 1 g or more, 10 g or more, or 50 g or more. In the present invention, the "polymer" is not particularly limited, but the lower limit of the weight average molecular weight may be, for example, 1000 or more, 5000 or more, or 10,000 or more, and the upper limit of the weight average molecular weight is particularly limited. However, it may be, for example, 500,000 or less.

The type of water-soluble polymer (A) is not particularly limited, and only one type may be used, or multiple types may be used in combination. The water-soluble polymer (A) may be, for example, a synthetic water-soluble polymer or a natural water-soluble polymer. The “synthetic water-soluble polymer” may be, for example, an artificially synthesized polymer with a chemical structure that does not exist in nature, or an artificially synthesized polymer with a naturally occurring chemical structure. Also, the “natural water-soluble polymer” may be, for example, a polymer having a chemical structure that exists in nature, extracted from nature, produced, or the like. Examples of synthetic water-soluble polymers include, but are not limited to, carboxymethylcellulose (CMC), alkylcellulose, hydroxyalkylcellulose, hydroxyalkylalkylcellulose, polyacrylic acid, sodium polyacrylate, polyacrylamide, and polyvinyl alcohol (PVA). , polyvinylpyrrolidone, polyethylene glycol, polyethylene oxide, water-soluble urethane resin, water-soluble melamine resin, water-soluble epoxy resin, water-soluble butadiene resin, water-soluble phenol resin, and the like. Examples of natural water-soluble polymers include, but are not limited to, proteins, xanthan gum, guar gum, welan gum, locust bean gum, daiutan gum, tamarind gum, tamarind seed gum, tragacanth gum, arabic gum, carrageenan, rhamzan gum, and succinoglycan. , tara gum, gellan gum, karaya gum, pectin, alginic acid derivatives, cellulose ethers and the like.

Component (A) is preferably polyvinyl alcohol, carboxymethylcellulose (CMC), alkylcellulose, hydroxyalkylcellulose, hydroxyalkylalkylcellulose, polyacrylic acid, sodium polyacrylate, starches, mannan, alginic acids, and natural gums. proteins, polyvinylpyrrolidone, polyethylene glycol, polyethylene oxide, polyacrylamide resins, water-soluble urethane resins, water-soluble melamine resins, water-soluble epoxy resins, water-soluble butadiene resins, water-soluble phenolic resins, etc., more preferably At least one selected from the group consisting of polyvinyl alcohol (PVA), CMC, polyacrylic acid, sodium polyacrylate, methylcellulose, hydroxyethylcellulose and hydroxypropylmethylcellulose, more preferably PVA, hydroxypropylmethylcellulose and methylcellulose At least one selected from the group consisting of The viscosity of CMC is preferably 10 to 100,000 mPa·s, more preferably 100 to 100,000 mPa·s, still more preferably 200 to 90,000 mPa·s as a 2% by mass aqueous solution. The viscosity of PVA is preferably 2 to 500 mPa·s, more preferably 5 to 400 mPa·s, and still more preferably 10 to 200 mPa·s as a 4% by mass aqueous solution. From the viewpoint of improving the adhesion amount of the anti-adhesive composition for unvulcanized rubber of the present invention to the unvulcanized rubber, it is preferable that the viscosity of the component (A) is not too low. From the viewpoint of improving the drying property of the anti-adhesive composition for unvulcanized rubber of the present invention, it is preferable that the viscosity of the component (A) is not too high. In the present invention, the "adhesion amount" of the unvulcanized rubber anti-adhesion agent composition refers to the adhesion amount of all components other than water in the unvulcanized rubber anti-adhesion agent composition to the surface of the unvulcanized rubber. say.

The content (amount) of the component (A) in the anti-adhesion agent composition for unvulcanized rubber of the present invention is not particularly limited, for example, the anti-adhesion agent composition for unvulcanized rubber of the present invention It may be 1-20% by weight, 2-20% by weight, 3-20% by weight, 4-18% by weight, or 5-16% by weight of the total weight. In order to prevent deterioration of handling due to excessive increase in viscosity of the anti-adhesive composition for unvulcanized rubber of the present invention, the content of the component (A) is It is preferred not to exceed 20% by mass relative to the total mass of the anti-adhesive composition. Further, from the viewpoint of the ease of forming a film after applying the anti-adhesive composition for unvulcanized rubber, the content of the component (A) is 100% by mass of the total mass of the components (solid content) other than water. is preferably 25% by mass or more. The content of component (A) is more preferably 25 to 75% by mass, still more preferably 28 to 70% by mass, still more preferably 30 to 65% by mass, relative to 100% by mass of the total mass of components other than water. be.

In addition, the component (A) may contain, for example, a nonionic cellulose ether (hereinafter sometimes referred to as "component (A2)"). The component (A2) functions, for example, to improve anti-adhesiveness and removability of deposits on equipment by a thermal gel effect or toughening of the film itself of the anti-adhesive composition for unvulcanized rubber. Specifically, for example, the component (A2) increases the viscosity of the anti-adhesive composition for unvulcanized rubber of the present invention on hot unvulcanized rubber immediately after kneading, so that the unvulcanized rubber of the present invention It is believed that the adhesion of the anti-adhesion agent composition for rubber is improved and the anti-adhesion property is improved. Further, for example, as the component (A), by using together the component (A2) and a component other than the component (A2) (hereinafter sometimes referred to as “component (A1)”), a low cost and high prevention It becomes an anti-adhesive composition for unvulcanized rubber that exhibits adhesion.

The type of component (A2) is not particularly limited, and one type may be used alone, or multiple types may be used in combination. The component (A2) is preferably at least one selected from the group consisting of alkylcellulose, hydroxyalkylcellulose, and hydroxyalkylalkylcellulose. In these, the alkyl group is not particularly limited, but is, for example, a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms. . More preferably, the component (A2) is hydroxyalkylmethylcellulose such as hydroxyethylmethylcellulose, hydroxypropylmethylcellulose and hydroxybutylmethylcellulose, alkylcellulose such as methylcellulose, ethylcellulose and ethylmethylcellulose, hydroxyalkylcellulose such as hydroxyethylcellulose, and the like. More preferably, at least one selected from the group consisting of hydroxypropylmethylcellulose, methylcellulose, ethylcellulose, ethylmethylcellulose, and hydroxyethylmethylcellulose, and particularly preferably selected from the group consisting of methylcellulose, ethylcellulose, and ethylmethylcellulose. at least one type of

When the component (A1) and the component (A2) are used in combination, the component (A1) is selected from the group consisting of PVA, and the component (A2) is selected from the group consisting of methyl cellulose, ethyl cellulose, ethyl methyl cellulose, hydroxypropyl methyl cellulose, and the like. It is preferable to use together with at least one of the above from the viewpoint of exhibiting the effect of the present invention at low cost and high anti-adhesion property.

The content (amount) of the component (A2) in the anti-adhesion agent composition for unvulcanized rubber of the present invention is not particularly limited, for example, the anti-adhesion agent composition for unvulcanized rubber of the present invention 0.05 to 20% by mass, 0.1 to 15% by mass, 0.2 to 10% by mass, or 0.5 to 6% by mass with respect to the total mass, for example, components other than water (solid content) It is 0.1 to 60% by mass with respect to the total mass of 100% by mass. From the viewpoint of the ease of forming a film after applying the anti-adhesive composition for unvulcanized rubber, the content of the component (A2) is 0.5% with respect to 100% by mass of the total mass of components other than water. It is preferably from 1 to 50% by mass, more preferably from 1 to 40% by mass. In order to prevent the viscosity of the anti-adhesive composition for unvulcanized rubber of the present invention from excessively increasing and the handling from deteriorating, the content of the component (A2) is It is preferred not to exceed 20% by mass relative to the total mass of the anti-adhesive composition.

The molar substitution degree (MS) of component (A2) is not particularly limited, but is preferably 0.1 to 0.5, more preferably 0.1 to 0.45, still more preferably 0.1 to 0.45. 4. The molar degree of substitution (MS) is defined as the average number of moles of hydroxypropoxy groups and hydroxyethoxy groups bonded per glucose ring unit of cellulose in the molecule of component (A2). For example, in the case of methylcellulose, the number of bonded hydroxypropoxy and hydroxyethoxy groups is 0, so the molar degree of substitution (MS) is '0'.

The degree of substitution (DS) per glucose of the component (A2) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.5, still more preferably 1.0. ~3.0. The degree of substitution (DS) is defined as the average number of hydroxyl groups substituted with methoxy groups per glucose ring unit of cellulose in the molecule of component (A2).

The viscosity of the component (A2) is not particularly limited, but is preferably 10 to 30,000 mPa s for a 2% by mass aqueous solution, more preferably 100 to 20,000 mPa s for a 2% by mass aqueous solution, and still more preferably 200 for a 2% by mass aqueous solution. ~15000 mPa·s.

The mass ratio (A1)/(A2) of the component (A1) and the component (A2) is not particularly limited, but from the viewpoint of achieving both adhesion prevention and low cost, the range is preferably from 1 to 30. The lower limit is more preferably 1.5 or more, 2 or more, or 3 or more, and the upper limit is more preferably 25 or less, 20 or less, or 15 or less.

[1-2. Component (B): Metal Soap]
In the anti-adhesive composition for unvulcanized rubber of the present invention, component (B) is a metal soap as described above. The metal soap (B) is, for example, a metal salt of a higher fatty acid or a derivative thereof other than a sodium salt and a potassium salt, and is, for example, a salt other than an alkali metal salt among the above metal salts.

In the anti-adhesive composition for unvulcanized rubber of the present invention, component (B) contains both component (B1) and component (B2) below, as described above.

(B1) at least one metal soap selected from the group consisting of fatty acid calcium and fatty acid lithium (B2) at least one metal soap selected from the group consisting of fatty acid zinc, fatty acid magnesium, and fatty acid aluminum

The type of component (B) (metal soap (B)) is not particularly limited except that it contains both component (B1) and component (B2). Each of the component (B1) and the component (B2) may be used singly or in combination. In addition, the component (B) (metallic soap (B)) may or may not contain components other than the component (B1) and the component (B2). As described above, the metal soap (B) is, for example, a metal salt of a higher fatty acid or a derivative thereof other than the sodium salt and the potassium salt, and is, for example, the metal salt other than the alkali metal salt. . A higher fatty acid is, for example, a fatty acid having 8 or more carbon atoms, 10 or more carbon atoms, 12 or more carbon atoms, 14 or more carbon atoms, or 16 or more carbon atoms. hereinafter, 22 or less, 20 or less, or 18 or less carbon atoms. A higher fatty acid derivative may be, for example, a higher fatty acid substituted with one or more substituents. Specific examples of the metal soap (B) include calcium caprylate, lithium caprylate, zinc caprylate, magnesium caprylate, calcium caprate, lithium caprate, zinc caprate, magnesium caprate, calcium laurate, and lithium laurate. , Zinc Laurate, Magnesium Laurate, Calcium Myristate, Lithium Myristate, Zinc Myristate, Magnesium Myristate, Calcium Palmitate, Lithium Palmitate, Zinc Palmitate, Magnesium Palmitate, Calcium Stearate, Lithium Stearate, Stearic Acid Zinc, magnesium stearate, aluminum stearate, aluminum trioctadecanoate, aluminum dioctadecanoate, aluminum monooctadecanoate, calcium octadecanoate, lithium octadecanoate, zinc octadecanoate, magnesium octadecanoate, calcium oleate, lithium oleate, olein zinc acid, magnesium oleate, calcium behenate, lithium behenate, zinc behenate, magnesium behenate, calcium 12-hydroxystearate, lithium 12-hydroxystearate, zinc 12-hydroxystearate, magnesium 12-hydroxystearate, Calcium 14-octadecanoate, Lithium 14-octadecanoate, Zinc 14-octadecanoate, Magnesium 14-octadecanoate, Calcium 8-octadecanoate, Lithium 8-octadecanoate, Zinc 8-octadecanoate, Magnesium 8-octadecanoate, 6- Calcium octadecanoate, lithium 6-octadecanoate, zinc 6-octadecanoate, magnesium 6-octadecanoate, calcium cocoate, lithium cocoate, zinc cocoate, magnesium cocoate, calcium palmate, lithium palmate, palm oil Fatty acid zinc, palm oil fatty acid magnesium, palm kernel oil fatty acid calcium, palm kernel oil fatty acid lithium, palm kernel oil fatty acid zinc, palm kernel oil fatty acid magnesium, beef tallow fatty acid calcium, beef tallow fatty acid lithium, beef tallow fatty acid zinc, tallow fatty acid magnesium, castor oil fatty acid Examples include calcium, lithium castor oil, zinc castor oil, and magnesium castor oil.

The metal soap (B) is preferably a divalent metal salt of a fatty acid having an average carbon chain length of 12 to 22, more preferably a divalent metal of a higher fatty acid having 14 to 20 or 16 to 18 carbon atoms. is salt. Also, the metal soap (B) is preferably a calcium salt, a magnesium salt, or a zinc salt. Among them, Ca stearate, Zn stearate, and Mg stearate are preferable from the viewpoint of high distribution volume and low cost.

The content (blending amount) of the metal soap (B) is not particularly limited, but is, for example, 1 to 25% by mass, 2 to 20% by mass, based on the total mass of the antiadhesive composition for unvulcanized rubber of the present invention. %, or 3 to 18% by mass, for example, 20 to 60% by mass with respect to the total mass of all components (solid content) other than water. It is preferable that the mass of the metal soap (B) is 20% by mass or more based on the total mass of all components other than water from the viewpoint of the lubricity of the adhesion-preventing film, and if it is 60% by mass or less, the unvulcanized rubber It is preferable from the viewpoint of suppressing powder scattering of the anti-adhesive composition for anti-adhesion and suppressing deterioration of handling properties due to high viscosity. The content (blending amount) of the metal soap (B) may be, for example, 25% by mass or more or 30% by mass or more, for example, 50% by mass or less, relative to the total mass of all components (solid content) other than water. It may be 45% by mass or less or 40% by mass or less.

The mass ratio (A)/(B) between the component (A) and the metal soap (B) is not particularly limited, but is preferably in the range of 0.5 to 3, as described above. If it is 0.5 or more, it is easy to suppress powder scattering of the anti-adhesive composition for unvulcanized rubber, and if it is 3 or less, it is prevention by mixing and dispersing the component (A) and the metal soap (B). It is easy to obtain the effect of improving the sex. The lower limit of the mass ratio (A)/(B) between component (A) and metallic soap (B) is more preferably 0.6 or more, 0.7 or more, or 0.8 or more, and the upper limit is The value is more preferably 2.5 or less, 2.0 or less, or 1.5 or less.

In the anti-adhesion agent composition for unvulcanized rubber of the present invention, the component (B1) functions, for example, as a lubricant, and enhances the dispersibility of the component (A) to improve anti-adhesion properties.

Although the component (B1) is not particularly limited, examples of the metal soaps exemplified as the component (B) include fatty acid calcium or fatty acid lithium metal soaps. As described above, the component (B1) may be used singly or in combination. Calcium stearate and lithium stearate are particularly preferable as the component (B1) from the viewpoint that they can contribute to cost reduction because they are widely available at low prices.

In the anti-adhesion agent composition for unvulcanized rubber of the present invention, the content of the component (B1) is not particularly limited, but relative to the total mass of the anti-adhesion agent composition for unvulcanized rubber, for example 0.5 to 20% by mass, preferably the lower limit is 0.8% by mass or more, 1% by mass or more, or 2% by mass or more, and preferably the upper limit is 15% by mass or less, 12% by mass or less, or 10% by mass % or less, relative to 100% by mass of the total mass of components (solid content) other than water, for example 15 to 70% by mass, or 20 to 60% by mass, preferably the lower limit is 20% by mass or more, 25% by mass % or more, or 30 mass % or more, and preferably the upper limit is 55 mass % or less, 52 mass % or less, or 50 mass % or less. From the viewpoint of suppressing or preventing insufficient lubricity of the anti-adhesion film, it is preferable that the content of the component (B1) is not too low. Preferably. From the viewpoint of suppressing or preventing powder scattering and viscosity increase of liquid products (anti-adhesive composition for unvulcanized rubber or aqueous dispersion of anti-adhesive composition for unvulcanized rubber) and not deteriorating handleability, It is preferable that the content of the component (B1) is not too high, and particularly preferably 60% by mass or less with respect to 100% by mass of the total solid content.

In the unvulcanized rubber anti-adhesive composition of the present invention, the component (B2), for example, acts as a lubricant, and the unvulcanized rubber anti-adhesive composition or unvulcanized rubber by the component (B1) It works to suppress the thickening of the anti-adhesive composition aqueous dispersion.

Although the component (B2) is not particularly limited, examples of the metal soaps exemplified as the component (B) include fatty acid zinc, fatty acid magnesium, and fatty acid aluminum. As described above, the component (B2) may be used singly or in combination. As the component (B2), zinc stearate and magnesium stearate are particularly preferred from the viewpoint that they are widely distributed and readily available at low prices and thus can contribute to cost reduction.

In the anti-adhesive composition for unvulcanized rubber of the present invention, the content of the component (B2) is not particularly limited. 2 to 8% by mass, or 0.5 to 5% by mass, preferably the lower limit is 0.3% by mass or more, 0.5% by mass or more, or 0.8% by mass or more, preferably the upper limit is 7% by mass or less, 6% by mass or less, or 5% by mass or less, relative to 100% by mass of the total mass of components other than water (solid content), for example, 2 to 30% by mass, 2 to 25% by mass, Or 2.5 to 25% by mass, preferably the lower limit is 3% by mass or more, or 5% by mass or more, preferably the upper limit is 25% by mass or less, 20% by mass or less, or 15% by mass or less be. From the viewpoint of suppressing or preventing insufficient lubricity of the anti-adhesion film, it is preferable that the content of the component (B2) is not too low. It is preferable that it is above. From the viewpoint of suppressing or preventing powder scattering and viscosity increase of liquid products (anti-adhesive composition for unvulcanized rubber or aqueous dispersion of anti-adhesive composition for unvulcanized rubber) and not deteriorating handleability, It is preferable that the content of the component (B2) is not too high, and particularly preferably 25% by mass or less with respect to 100% by mass of the total solid content.

Further, in the anti-adhesive composition for unvulcanized rubber of the present invention, the mass ratio (B1) / (B2) of the component (B1) and the component (B2) (the mass of the component (B1) is the component The numerical value divided by the mass of (B2)) is, as described above, in the range of 1 to 20, preferably with a lower limit of 1.5 or more, 2 or more, 2.5 or more, or 3 or more, preferably The upper limit is 19 or less, 15 or less, 12 or less, or 10 or less. If the mass ratio (B1)/(B2) is less than 1, the anti-adhesion property tends to be insufficient, and if it exceeds 20, the viscosity suppressing effect tends to be insufficient.

[1-3. Component (C): Surfactant]
In the anti-adhesive composition for unvulcanized rubber of the present invention, the content of the component (C), that is, the surfactant (hereinafter sometimes referred to as "surfactant (C)") is not particularly limited, With respect to the total mass of the anti-adhesive composition for unvulcanized rubber of the present invention, for example, 0.5 to 12% by mass, 1 to 10% by mass, or 2 to 8% by mass, all components other than water ( For example, it is 10 to 20% by mass with respect to the total mass of solid content). When the content of the surfactant (C) is 10% by mass or more with respect to the total mass of the components other than water, for example, the metal soap (B) has an improved dispersing effect and becomes difficult to separate. % or less, for example, the dispersibility is moderately suppressed, the adhesion becomes good, and the anti-adhesion property also becomes good. The content of the surfactant (C) may be, for example, 10% by mass or more or 12% by mass or more, for example, 18% by mass or less or 16% by mass or less, relative to the total mass of the components other than water. good. The method for measuring adhesion to unvulcanized rubber is not particularly limited, but for example, it can be measured by the measuring method described in Examples below.

Surfactant (C), for example, imparts dispersibility in water to the anti-adhesive composition for unvulcanized rubber of the present invention, and improves adhesion to unvulcanized rubber by improving wettability. Improve. Surfactant (C) is not particularly limited, and may be used alone or in combination of multiple types. For example, at least one of an anionic surfactant and a nonionic surfactant may be used. Although the anionic surfactant is not particularly limited, examples thereof include the following (i) to (iv). The nonionic surfactant is not particularly limited, and examples thereof include the following (v).

(i) Carboxylic acid-type anionic surfactants such as higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, acylamino carboxylates, etc. (ii) higher Sulfuric acid ester type anionic surfactants such as alcohol sulfates, polyoxyalkylene higher alcohol sulfates, alkylphenyl ether sulfates, polyoxyalkylene alkylphenyl ether sulfates, and glycerin fatty acid ester monosulfate salts (iii) Sulfonic acid-type anionic surfactants such as alkanesulfonates, α-olefinsulfonates, linear alkylbenzenesulfonates, α-sulfofatty acid ester salts, and dialkylsulfosuccinates (iv) alkyl phosphate salts, polyoxy Phosphate ester type anionic surfactants such as alkylene alkyl phosphate salts, polyoxyalkylene alkylphenyl phosphate salts, glycerin fatty acid ester monophosphate ester salts (v) Polyoxyalkylene alkyl ether type nonionic surfactants

The counter ion of the anionic surfactant is not particularly limited, but alkali metals such as sodium and potassium, and alkanolamines such as monoethanolamine and diethanolamine are preferable. These may be used alone or in combination of multiple types.

As the anionic surfactant, a dialkylsulfosuccinate is preferable, and a dioctylsulfosuccinate Na salt is more preferable, since an anti-adhesive composition having excellent wettability with the surface of the unvulcanized rubber can be obtained.

Nonionic surfactants are not particularly limited, but in the present invention, for example, nonionic surfactants represented by the following formula (1) can be used. The nonionic surfactant of the following formula (1), together with the anionic surfactant, in addition to reducing the surface tension of the anti-adhesive composition against the surface of the unvulcanized rubber, the unvulcanized anti-adhesive composition It is presumed that this has the effect of effectively increasing the adhesion to the rubber surface. However, this guess does not limit the present invention.

RO-(AO) _n -H (1)

In the above formula (1), R represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms. The aliphatic hydrocarbon group may be linear or branched. Also, it may be either saturated or unsaturated. The number of carbon atoms in R is preferably 12 to 16, more preferably 12 to 13, from the viewpoint of excellent dispersibility of component (A).
AO represents an oxyalkylene group having 2 to 4 carbon atoms, and n is the average number of added moles of AO.
n is, for example, 1-30, 1-25 or 2-15. Specifically, n is 1 or more (that is, not 0) from the viewpoint of preventing deterioration in surfactant ability and deterioration in dispersibility of component (A). Also, from the viewpoint of preventing deterioration in adhesion due to excessively high hydrophilicity, n is 30 or less, 25 or less, or 20 or less. When n is in the range of 1 to 30, 1 to 25, or 1 to 20, the dispersibility of component (A) is further improved and the unvulcanized rubber surface is highly hydrophobic. Also, it is presumed that the adhesion is improved by imparting sufficient viscoelasticity to the dry coating of the anti-adhesive composition for unvulcanized rubber. However, this guess does not limit the present invention.

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

Specific examples of nonionic surfactants are not particularly limited, but for example, lauryl ether EO, cetyl ether EO, stearyl ether EO, oleyl ether EO, decyl ether EO, isodecyl ether EO, tridecyl ether EO, secondary alcohol ether EO, synthetic alcohol ether EOPO, lauryl ether EOPO, decyl ether EOPO, isodecyl ether EOPO, tridecyl ether EOPO, stearyl ether EOPO and the like.

[1-4. water]
In the anti-adhesion agent composition for unvulcanized rubber of the present invention, the water content is not particularly limited, relative to the total mass of the anti-adhesion agent composition for unvulcanized rubber, for example, 50% by mass or more, 60 It may be 90% by mass or more, or 70% by mass or more, or 90% by mass or less, 85% by mass or less, or 80% by mass or less.

Water, for example, functions to impart fluidity to the anti-adhesive composition for unvulcanized rubber of the present invention, making it easier to handle. Water is not particularly limited, and may be, for example, tap water, distilled water, ion-exchanged water, or the like.

[1-5. Optional components, etc.]
The anti-adhesive composition for unvulcanized rubber of the present invention may or may not contain optional components other than the components (A) to (C) and water. For example, the anti-adhesion agent composition for unvulcanized rubber of the present invention optionally contains additives such as antifoaming agents, preservatives, wettability aids, viscosity aids, and foreign matter reduction aids. may be included as

Antifoaming agents include, but are not limited to, oil-based antifoaming agents such as castor oil, sesame oil, linseed oil, and animal and vegetable oils; isoamyl stearate, distearyl succinate, ethylene glycol distearate, butyl stearate, and the like. fatty acid ester antifoaming agents; alcohol antifoaming agents such as polyoxyalkylene monohydric alcohol, di-t-amylphenoxyethanol, 3-heptanol, 2-ethylhexanol; di-t-aminophenoxyethanol, 3-heptyl cellosolve , nonyl cellosolve, 3-heptyl carbitol and other ether antifoaming agents; tributyl phosphate, tris (butoxyethyl) phosphate and other phosphate ester antifoaming agents; diamylamine and other amine antifoaming agents; polyalkyleneamides , amide antifoaming agents such as acylate polyamines; mineral oils; silicone oils; Only one type of the antifoaming agent may be used, or a plurality of types may be used in combination.

The preservative is not particularly limited, but examples thereof include derivatives of isothiazolinone. The isothiazolinone derivatives are not particularly limited. ), dichlorooctylisothiazolinone (DCOIT, DCOI) and their derivatives. Only one kind of the antiseptic may be used, or a plurality of kinds may be used in combination.

Examples of wettability aids include, but are not limited to, alcohols. More specific examples include methanol, ethanol, hexanol, glycerin, 1,3-butanediol, propylene glycol, dipropylene glycol, Examples include pentylene glycol, hexylene glycol, polyethylene glycol, sorbitol, maltitol, sucrose, erythritol, xylitol, polyethylene glycol, polypropylene glycol, adducts of ethylene oxide and propylene oxide of polyhydric alcohols, and the like. Only one type of the wettability aid may be used, or a plurality of types may be used in combination.

The viscosity of the anti-adhesive composition for unvulcanized rubber of the present invention is not particularly limited, for example, because it is difficult to separate and has good handleability (handling), the anti-adhesive composition for unvulcanized rubber Viscosity measured after 10 rotations at 25°C with a BH viscometer at 20 rpm after 3 days from the manufacture of the product is preferably 25,000 mPa s or less, more preferably 1,000 to 25,000 mPa s, and still more preferably 2,000 to 2,000 mPa s. 25,000 mPa·s, particularly preferably 3,000 to 24,000 mPa·s, preferably with a lower limit of 4,000 mPa·s or more, 5,000 mPa·s or more, or 6,000 mPa·s or more, preferably with an upper limit of 20,000 mPa·s or less. , 15000 mPa·s or less, or 10000 mPa·s or less. From the viewpoint of suppressing or preventing the separation of the unvulcanized rubber anti-adhesive composition, it is preferable that the viscosity of the unvulcanized rubber anti-adhesive composition is not too low, and deterioration of handling such as being difficult to come out of the container From the viewpoint of suppressing or preventing, it is preferable that the viscosity of the anti-adhesive composition for unvulcanized rubber is not too high.

[2. Method for producing anti-adhesive composition for unvulcanized rubber]
The method for producing the anti-adhesive composition for unvulcanized rubber of the present invention is not particularly limited, for example, all components of the anti-adhesive composition for unvulcanized rubber (the components (A) to (C) and It can be produced by mixing water and optional ingredients that are blended as necessary. There are no particular restrictions on the order of mixing and the devices and equipment used for mixing. For example, after mixing water, a water-soluble polymer (above-mentioned component (A)), and a surfactant (above-mentioned component (C)), metal soap (above-mentioned component (B)) and other optional components are mixed. methods and the like. As described above, the device used for mixing is not particularly limited, but for example, a device having a configuration in which a stirring blade is provided in a container can be used. Specifically, liquid mixers such as general liquid mixers, vortex mixers, static mixers, homogenizers and line homomixers can be used.

[3. How to use the anti-adhesive composition for unvulcanized rubber]
The method of using the anti-adhesive composition for unvulcanized rubber of the present invention is not particularly limited, and may be, for example, the same as or similar to the method of using a general anti-adhesive composition for unvulcanized rubber. The method of using the anti-adhesive composition for unvulcanized rubber of the present invention is specifically, for example, as follows, but is not limited thereto.

The anti-adhesion treatment method for unvulcanized rubber using the anti-adhesion agent composition for unvulcanized rubber of the present invention is, for example, as described above, the component ( A) to (C) may be adhered to the surface of the unvulcanized rubber to prevent adhesion. Adhesion to the unvulcanized rubber surface can be carried out, for example, by a wet method described later. Even if the anti-adhesion treated unvulcanized rubber treated in this way is stacked or folded and stored, the unvulcanized rubbers do not adhere to each other. Further, such a method for anti-adhesion treatment of unvulcanized rubber can also be said to be, for example, a method for producing anti-adhesion treated unvulcanized rubber.

The anti-adhesive composition for unvulcanized rubber of the present invention may be used as it is, or may be further diluted with water and used in the form of a water-diluted solution (aqueous dispersion). In the anti-adhesive composition for unvulcanized rubber of the present invention, the concentration when attached to the surface of the unvulcanized rubber is not particularly limited, but with respect to the total mass of the anti-adhesive composition for unvulcanized rubber, other than water may be, for example, 0.5% by mass or more, 1% by mass or more, or 2% by mass or more, and may be, for example, 15% by mass or less, 10% by mass or less, or 5% by mass or less. good too. If the concentration is not too high, for example, the effects of low scattering and fast drying can be obtained. If the concentration is not too low, for example, effects such as high adhesion prevention and high lubricity can be obtained. The anti-adhesion agent composition for unvulcanized rubber of the present invention, for example, can exhibit high anti-adhesion even at a low concentration when attached to the surface of unvulcanized rubber, so that a small amount of adhesion exhibits high anti-adhesion. I can do it. In addition, the viscosity when attached to the unvulcanized rubber surface is not particularly limited, but may be, for example, 1 mPa s or more, 5 mPa s or more, or 10 mPa s or more, for example, 30 mPa s or less, 20 mPa s or less. or less, or 15 mPa·s or less. If the viscosity is not too high, for example, the effects of low scattering and fast drying can be obtained. If the viscosity is not too low, for example, effects such as high adhesion prevention and high lubricity can be obtained.

In the anti-adhesion treatment step, for example, as described above, the anti-adhesion agent composition for unvulcanized rubber of the present invention or the anti-adhesion agent composition for unvulcanized rubber of the present invention. It is a step of attaching the components (A) to (C) in the anti-adhesive composition for unvulcanized rubber of the present invention to the surface of the unvulcanized rubber by attaching it to the surface and further volatilizing water. may More specifically, the anti-adhesion treatment step is, for example, the unvulcanized rubber anti-adhesion agent composition adhesion step of attaching the unvulcanized rubber anti-adhesion agent composition of the present invention to the surface of the unvulcanized rubber and a drying step of drying the anti-adhesive composition for unvulcanized rubber on the surface of the unvulcanized rubber to form a coating on the surface of the unvulcanized rubber. Such an anti-adhesion treatment process is called a wet method, for example. The wet method is not particularly limited, and for example, it can be carried out in the same manner as the wet method for general anti-adhesive compositions for unvulcanized rubber.

In the step of attaching the anti-adhesion composition for unvulcanized rubber, for example, the unvulcanized rubber which is in a high temperature state (for example, about 80 to 150 ° C.) due to heat when formed into a sheet or the like, is unvulcanized. It is preferable to adhere the anti-adhesive composition for sulfur rubber.

As a specific method of the adhesion preventive composition for unvulcanized rubber step, for example, a method of spraying an antiadhesive composition for unvulcanized rubber on unvulcanized rubber with a shower device, for unvulcanized rubber A dipping method in which unvulcanized rubber is immersed for a short period of time in a tank containing an anti-adhesive composition can be used. Further, a method of applying an anti-adhesive composition for unvulcanized rubber to unvulcanized rubber using a coating device may be employed, or these methods may be used in combination as appropriate.

According to the anti-adhesion agent composition for unvulcanized rubber of the present invention, as described above, dust can be reduced, high anti-adhesion properties can be exhibited even with a small adhesion amount, and high lubricity can be obtained.

The type of rubber to which the anti-adhesive composition for unvulcanized rubber of the present invention can be applied is not particularly limited as long as it is unvulcanized rubber. Examples of the rubber species include rubbers such as natural rubber (NR), butadiene rubber (BR), styrene-butadiene rubber (SBR), IIR (butyl rubber), and EPDM (ethylene propylene rubber), and a plurality of these rubbers. Mixed rubbers are mentioned.

As described above, the anti-adhesion agent composition for unvulcanized rubber and the aqueous dispersion of the anti-adhesion agent composition for unvulcanized rubber of the present invention are compatible with lubricity and scattering property in addition to excellent anti-adhesion properties. is possible. Further, according to the anti-adhesive composition for unvulcanized rubber and the aqueous dispersion of the anti-adhesive composition for unvulcanized rubber of the present invention, for example, the following effects can be obtained. For example, low cost can be achieved by not using organic particles. Further, for example, by using the component (A1) and the component (A2) in combination, it is possible to exhibit excellent anti-adhesiveness even to natural rubber (NR). Further, for example, by using the component (A1) and the component (A2) in combination, even if the metal soap (B) is used in high-temperature rubber and the dispersibility of the metal soap (B) is lowered, excellent anti-adhesion properties can be exhibited.

Next, examples of the present invention will be described. However, the present invention is not limited to the following examples.

[Example 1]
An anti-adhesive composition for unvulcanized rubber of Example 1 was produced as follows.

893 g of water was placed in a reactor and heated to 80° C. or higher. After that, in the reaction vessel, hydroxypropyl methylcellulose (trade name “Metolose 60SH-4000”, degree of methoxy group substitution 1.9, hydroxypropoxy group substitution molar number 0.25, 2% viscosity 4000 mPa s, Shin-Etsu Chemical Co., Ltd. company) was added and mixed for 2 hours. The hydroxypropylmethylcellulose is a water-soluble polymer and corresponds to the component (A) in the anti-adhesive composition for unvulcanized rubber of the present invention. After cooling the mixture obtained by mixing for 2 hours in this way to 20 ° C. or less, 50 g of calcium laurate (manufactured by Taihei Kagaku Sangyo Co., Ltd.), 10 g of zinc laurate (Nitto Kasei Kogyo Co., Ltd.), coconut alcohol EO 5 g of adduct (Rheox (registered trademark) CC-150, manufactured by Lion Specialty Chemicals), 10 g of sodium alpha olefin sulfonate (Liporan (registered trademark) LB-840, manufactured by Lion Specialty Chemicals), and preservative (trade name “Topside 609”, manufactured by Permachem Asia Co., Ltd.) was added and stirred to obtain a liquid anti-adhesive composition for unvulcanized rubber. The calcium laurate is fatty acid calcium, and corresponds to the component (B1) in the antiadhesive composition for unvulcanized rubber of the present invention. The zinc laurate is fatty acid zinc and corresponds to the component (B2) in the antiadhesive composition for unvulcanized rubber of the present invention. Both the coconut alcohol EO adduct and the sodium alpha-olefin sulfonate are surfactants and correspond to the component (C) in the antiadhesive composition for unvulcanized rubber of the present invention. The antiseptic agent corresponds to an optional component other than the components (A) to (C).

[Examples 2 to 44, Comparative Examples 1 to 5]
In the same manner as in Example 1, except that the type and composition of the raw materials were changed as shown in Tables 2 to 5 below, antiadhesive compositions for unvulcanized rubber of Examples 2 to 44 and Comparative Examples 1 to 5 manufactured things. In addition, the product name (product name), manufacturer and characteristics (composition) of each raw material used in the production of the anti-adhesive compositions for unvulcanized rubber of Examples 1 to 44 and Comparative Examples 1 to 5 are shown in Table 1 below. show.

[Production and performance evaluation of anti-adhesive composition aqueous dispersion for unvulcanized rubber]
The anti-adhesion agent composition for unvulcanized rubber of each of the examples and comparative examples was diluted with water 20 times (mass ratio), and the anti-adhesion agent composition for unvulcanized rubber aqueous dispersion (anti-adhesion agent suspension liquid) was produced. An anti-adhesion treatment was performed on unvulcanized rubber using this anti-adhesion agent composition aqueous dispersion for unvulcanized rubber, and each performance of anti-adhesion, lubricity, scattering and removability of deposits on equipment was evaluated. The anti-adhesion treatment method and evaluation method for each of the above performances are shown below.

(1) Evaluation rubber <evaluation>
For various evaluations, the following unvulcanized SBR rubber and unvulcanized NR rubber were used as evaluation rubbers.
(Unvulcanized SBR rubber)
For 100 parts by mass of SBR (manufactured by Asahi Kasei Corporation, trade name "Tafden 4850"), 30 parts by mass of SAF carbon (manufactured by Mitsubishi Chemical Corporation, trade name "Dia Black A") and JSRAROMA (process oil ) (manufactured by Nippon Sun Oil Co., Ltd., product name “Aroma 790”) 15 parts by mass, zinc white (manufactured by Hakusui Tech Co., Ltd., zinc white 2 types) 3 parts by mass, stearic acid (manufactured by NOF Corporation , Camellia) 1 part by mass, 6PPD (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., trade name “Nocrac 6C”) 1 part by mass, CBS (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., trade name “Noccellar CZ-G”) ”) and 1.5 parts by mass of sulfur (manufactured by Tsurumi Chemical Co., Ltd.) (total 151.5 parts by mass) of unvulcanized SBR rubber was used.

(Unvulcanized NR rubber)
For 100 parts by mass of NR (RSS#3), 10 parts by mass of white carbon (manufactured by Tosoh Silica Co., Ltd., trade name "Nip Seal VN-3") and ISAF (Intermediate Super Abrasion Furnace) black (Tokai Carbon ( Co., Ltd., trade name “SEAST 6”) 30 parts by mass, JSRAROMA (process oil) (manufactured by Nippon Sun Oil Co., Ltd., trade name “Aroma 790”) 15 parts by mass, and zinc oxide (Hakusui Tech Co., Ltd.) , zinc white 2) 3 parts by mass, stearic acid (manufactured by NOF Corporation, camellia) 1 part by mass, and 6PPD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., trade name "Nocrac 6C") 1 part by mass , CBS (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., trade name “Noccellar CZ-G”) 1 part by mass, sulfur (manufactured by Tsurumi Chemical Co., Ltd.) 1.5 parts by mass (total 162.5 parts by mass ) Unvulcanized NR rubber was used.

(2) Evaluation of anti-adhesion property The above unvulcanized rubber is kneaded with an open roll at a temperature of 80 to 120 ° C. to form a rubber sheet (thickness: 5 to 8 mm, 60 cm × 15 cm), and the rubber immediately after being unwound The sheet is obtained by diluting the anti-adhesive composition for unvulcanized rubber obtained in each example of Examples 1 to 44 and Comparative Examples 1 to 5 with water 20 times Anti-adhesion for unvulcanized rubber It was immersed for about 1 second in 1 L of an aqueous dispersion of the agent composition (antiadhesive suspension, temperature 40°C). After that, the rubber sheet was quickly lifted vertically, left to stand vertically at room temperature, and dried naturally. In this manner, the rubber sheet (unvulcanized rubber) was subjected to anti-adhesion treatment.

The rubber sheet after the anti-adhesion treatment was cut into 6 cm × 15 cm and two sheets were superimposed to form a laminated test piece. ² was applied and left at 60° C. for 12 hours.

After that, the test piece was returned to room temperature and subjected to a 180° peel test using a tensile tester [AGS-500D type, SHIMADZU] to measure the peel resistance (N/cm) at a tensile speed of 300 mm/min. The smaller the peel resistance (N/cm), the better the anti-adhesion property.

(3) Evaluation of lubricity The rubber sheet (unvulcanized rubber) was subjected to anti-adhesion treatment in the same manner as in (2) Anti-adhesion evaluation. Next, the dried unvulcanized rubber sheet after the anti-adhesion treatment was cut into a rectangle of 5×15 cm. This rubber was placed on a stainless steel plate, the plate was gradually inclined, and the angle of inclination during sliding down was measured. The lower the starting angle, the better the lubricity.

(4) Evaluation of Scattering Resistance The rubber sheet (unvulcanized rubber) was subjected to anti-adhesion treatment in the same manner as in (2) Anti-adhesion evaluation. Next, the dried unvulcanized rubber sheet after the anti-adhesion treatment was cut into a rectangle of 6×15 cm, and the weight was measured. The front and back surfaces of this rubber were swept with a brush 10 times, and then the weight was measured again to calculate the scattering amount. It shows that the smaller the amount of scattering, the more excellent the scattering property.

(5) Evaluation of Viscosity The viscosity of the adhesion preventive composition for unvulcanized rubber before being diluted 20 times (mass ratio) with water was measured after 3 days from production. A BH type viscometer (Tokimec Co., Ltd., trade name "Viscometer BII") was used to measure the viscosity, and the viscosity was measured after 10 rotations at 25°C and 20 rpm.

The type and composition of the raw materials in the anti-adhesive compositions for unvulcanized rubber of Examples 1 to 44 and Comparative Examples 1 to 5, and the anti-adhesion, lubricity, scattering and viscosity performances evaluated as described above. The evaluation results are summarized in Tables 2 to 5 below. In Tables 2 to 5 below, the numerical value indicating the amount of each raw material (including water) is the content (mass%) with respect to the total mass (including water) of the anti-adhesive composition for unvulcanized rubber. . Further, "A ratio", "B ratio" and "C ratio" are respectively component (A), component (B) and It is a numerical value showing the content (% by mass) of the component (C). "A/B" is the ratio of the weight of component (A) divided by the weight of component (B). "B1/B2" is the ratio of the weight of component (B1) divided by the weight of component (B2).

As shown in Tables 2 to 5, the anti-adhesive compositions for unvulcanized rubber of Examples 1 to 44 had good anti-adhesion properties, lubricity, and scattering properties. On the other hand, the anti-adhesion agent composition for unvulcanized rubber of Comparative Example 1, which did not use the component (A), had good lubricity and scattering properties, but the anti-adhesion property was lower than that of the examples. was significantly inferior. The anti-adhesion agent composition for unvulcanized rubber of Comparative Example 2, which did not use the component (B), had good anti-adhesion properties, but was significantly inferior in lubricity and scattering properties as compared with the examples. was The anti-adhesive composition for unvulcanized rubber of Comparative Example 3, which did not use the component (C), had good lubricity and scattering properties, but the anti-adhesion properties were significantly inferior to those of Examples. was Moreover, the anti-adhesive composition for unvulcanized rubber of Comparative Example 3 had a viscosity as high as 22000 mPa·s, and was slightly inferior in handleability as compared with Examples. The anti-adhesion agent composition for unvulcanized rubber of Comparative Example 4, in which the component (B1) was used as the component (B) but the component (B2) was not used, had both anti-adhesion, lubricity and scattering properties. It was good, but due to its high viscosity of 22,000 mPa·s, its handleability was slightly inferior to that of the examples. The anti-adhesive composition for unvulcanized rubber of Comparative Example 5 in which the component (B2) was used as the component (B) but the component (B1) was not used had good anti-adhesion properties and scattering properties, but Lubricity was significantly inferior to that of Examples.

Claims (5)

including the following components (A) to (C) and water,
The following component (B) includes the following component (B1) and the following component (B2),
An antiadhesive composition for unvulcanized rubber, wherein the mass ratio (B1)/(B2) of the following component (B1) and the following component (B2) is in the range of 1 to 20.

(A) water-soluble polymer (B) metal soap (C) surfactant (B1) at least one metal soap selected from the group consisting of fatty acid calcium and fatty acid lithium (B2) fatty acid zinc, fatty acid magnesium, and fatty acid at least one metal soap selected from the group consisting of aluminum With respect to 100% by mass of the total mass of components other than water,
25 to 70% by mass of the component (A), 20 to 60% by mass of the component (B), and 10 to 20% by mass of the component (C) for unvulcanized rubber according to claim 1 Anti-adhesive composition. The mass ratio (A) / (B) of the component (A) and the component (B) is in the range of 0.5 to 3, antiadhesive composition for unvulcanized rubber according to claim 1 or 2 . An anti-adhesive composition for unvulcanized rubber, comprising the anti-adhesion composition for unvulcanized rubber according to any one of claims 1 to 3 and water. Unvulcanized rubber characterized in that the components (A) to (C) in the antiadhesive composition for unvulcanized rubber according to any one of claims 1 to 3 are attached to the surface.