JP7713614B2 - Liquid anti-adhesive composition for unvulcanized rubber, water-diluted liquid anti-adhesive composition for unvulcanized rubber, and unvulcanized rubber - Google Patents

Description

The present disclosure relates to a liquid anti-adhesive composition for unvulcanized rubber, a water-diluted liquid anti-adhesive composition for unvulcanized rubber, and unvulcanized rubber.

At rubber production and processing sites, anti-adhesion agents are applied to the surface of rubber (e.g., unvulcanized rubber) to prevent the rubber from sticking together.

Anti-adhesives for rubber that are primarily composed of inorganic powders are widely used. These are generally used in the form of an aqueous dispersion and then adhered to the rubber surface (Patent Documents 1-2). Also, in order to reduce dust resulting from inorganic powders, anti-adhesives for unvulcanized rubber that are primarily composed of fatty acid soaps and metal soaps have been proposed (Patent Documents 3-4).

Japanese Unexamined Patent Publication No. 50-149770 JP 2013-001720 A JP 2017-088686 A Japanese Patent Application Publication No. 56-047476

On the other hand, anti-adhesive agents containing metal soaps tend to produce scum foam that is difficult to eliminate. Scum foam can cause overflows from work tanks, contaminate the work environment, and become foreign matter when mixed into products.

Therefore, the present disclosure aims to provide a liquid anti-adhesive composition for unvulcanized rubber, a water-diluted liquid anti-adhesive composition for unvulcanized rubber, and unvulcanized rubber, which have excellent anti-adhesive and anti-foaming effects.

In order to achieve the above object, the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure comprises:
It is characterized by containing the following components (A) to (E) and water.

(A) a water-soluble polymer other than the following component (D); (B) a metal soap containing the following components (B1) and (B2); (B1) at least one compound selected from the group consisting of fatty acid calcium, and fatty acid lithium; (B2) at least one compound selected from the group consisting of fatty acid zinc, fatty acid magnesium, and fatty acid aluminum; (C) a surfactant other than the component (B) and the following component (E); (D) at least one compound selected from the group consisting of water-soluble polymers having a thixotropy index (2 rpm/20 rpm) of 4.0 or more in a 2% by mass aqueous solution at 20°C; (E) at least one compound represented by the following chemical formula (I) and a salt thereof:

R ¹ -XY (I)

In the above chemical formula (I),
R ¹ is a hydrocarbon group having 7 to 25 carbon atoms;
X is NH or CONH,
Y is H or (CH ₂ ) _m NR ² R ³ , provided that when X is NH, then Y is not H;
m is an integer from 2 to 4,
^R2 and ^R3 are each H, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms;
^R2 and ^R3 may be the same or different.

The water-diluted liquid anti-adhesive composition for unvulcanized rubber disclosed herein is characterized by containing the liquid anti-adhesive composition for unvulcanized rubber disclosed herein and water.

The unvulcanized rubber disclosed herein is characterized in that the components (A) to (E) in the liquid anti-adhesive composition for unvulcanized rubber disclosed herein are adhered to the surface.

According to the present disclosure, it is possible to provide a liquid anti-adhesive composition for unvulcanized rubber, a water-diluted liquid anti-adhesive composition for unvulcanized rubber, and unvulcanized rubber, which have excellent anti-adhesive effects and anti-foaming properties.

The present disclosure will be described in more detail below with reference to examples. However, the present disclosure is not limited to the following description.

In the present disclosure, "alkyl" includes, for example, linear or branched alkyl. In the present disclosure, the alkyl group is not particularly limited, but examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups.

In this disclosure, "alkylene" includes, for example, linear alkylene (methylene or polymethylene) or branched alkylene. In this disclosure, the alkylene group is not particularly limited, but examples include a methylene group, a dimethylene group (ethylene group), an ethylidene group, a trimethylene group, a 1-methylethylene group (propylene group), a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, a 1,1-dimethylethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decamethylene group.

The following describes the embodiments of the present disclosure in more detail. However, the present disclosure is not limited to the following embodiments.

[1. Liquid anti-adhesive composition for unvulcanized rubber]
As described above, the liquid anti-adhesive composition for unvulcanized rubber according to the present disclosure is characterized in that it contains the following components (A) to (E) and water.

(A) a water-soluble polymer other than the following component (D); (B) a metal soap containing the following components (B1) and (B2); (B1) at least one compound selected from the group consisting of fatty acid calcium, and fatty acid lithium; (B2) at least one compound selected from the group consisting of fatty acid zinc, fatty acid magnesium, and fatty acid aluminum; (C) a surfactant other than the component (B) and the following component (E); (D) at least one compound selected from the group consisting of water-soluble polymers having a thixotropy index (2 rpm/20 rpm) of a 2% by mass aqueous solution at 20°C of 4.0 or more; (E) at least one compound represented by the following chemical formula (I) and a salt thereof:

R ¹ -XY (I)

In the above chemical formula (I),
R ¹ is a hydrocarbon group having 7 to 25 carbon atoms;
X is NH or CONH,
Y is H or (CH ₂ ) _m NR ² R ³ , provided that when X is NH, then Y is not H;
m is an integer from 2 to 4,
^R2 and ^R3 are each H, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms;
^R2 and ^R3 may be the same or different.

[1-1. Component (A): Water-soluble polymer other than component (D)]
As described above, the component (A) is a water-soluble polymer other than the component (D). In the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure, the component (A), i.e., the water-soluble polymer other than the component (D) (hereinafter sometimes referred to as "water-soluble polymer (A)"), is a polymer compound that can be dispersed or dissolved in the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure by placing it in water or by heating it after placing it in water. This provides, for example, a coating effect on the unvulcanized rubber, and provides an anti-adhesive effect. In this way, the component (A) acts, for example, as a film-forming agent. In addition, for example, the component (A) and the component (B) are used in combination to exhibit anti-adhesive properties.

In the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure, the content of the water-soluble polymer (A) is not particularly limited, but may be, for example, 20% by mass or more, 25% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more, for example, 70% by mass or less, 60% by mass or less, 40% by mass or less, or 35% by mass or less, based on 100% by mass of the total mass of the components other than water (solid content). When the content of the water-soluble polymer (A) is 20% by mass or more based on 100% by mass of the total mass of the components other than water, for example, the film-forming effect on the unvulcanized rubber is excellent. In addition, when the content of the water-soluble polymer (A) is 30% by mass or more based on 100% by mass of the total mass of the components other than water, for example, the adhesion prevention effect is excellent. Furthermore, when the content of the water-soluble polymer (A) is 70% by mass or less based on the total mass of the components other than water, the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure is excellent in drying properties and can be dried quickly.

The content (mixture amount) of the water-soluble polymer (A) in the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure is not particularly limited, but may be, for example, 3 to 20 mass%, 4 to 18 mass%, or 5 to 16 mass% relative to the total mass of the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure. In order to prevent the viscosity of the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure from increasing too much and causing deterioration in handling, it is preferable that the content of the water-soluble polymer (A) is 20 mass% or less relative to the total mass of the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure.

The water-soluble polymer (A) may be, for example, a water-soluble polymer having a viscosity of 3 to 300 mPa·s in a 2% by mass aqueous solution of the water-soluble polymer (A) at 25°C. The water-soluble polymer having a viscosity of 3 mPa·s or more in a 2% by mass aqueous solution at 25°C can provide, for example, an effect of improving the amount of adhesion to unvulcanized rubber. The water-soluble polymer having a viscosity of 300 mPa·s or less in a 2% by mass aqueous solution can provide, for example, an effect of excellent drying properties. The viscosity of the 2% by mass aqueous solution may be, for example, 10 mPa·s or more or 100 mPa·s or more, or 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 disclosure, the "polymer" is not particularly limited, but may have a lower limit of mass average molecular weight of, for example, 1,000 or more, 5,000 or more, or 10,000 or more, and the upper limit of mass average molecular weight is not particularly limited, but may be, for example, 500,000 or less.

The type of water-soluble polymer (A) is not particularly limited, and one type may be used alone 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 having a chemical structure that does not exist in nature, or an artificially synthesized polymer having a chemical structure that exists in nature. The "natural water-soluble polymer" may be, for example, a polymer having a chemical structure that exists in nature that is extracted or generated from nature. The synthetic water-soluble polymer is not particularly limited, but examples thereof include carboxymethylcellulose (CMC), polyacrylic acid, sodium polyacrylate, polyacrylamide, polyvinyl alcohol (PVA), polyvinylpyrrolidone, polyethylene glycol, polyethylene oxide, methylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, water-soluble acrylic resin, water-soluble urethane resin, water-soluble melamine resin, water-soluble epoxy resin, water-soluble butadiene resin, water-soluble phenol resin, etc. Examples of natural water-soluble polymers include, but are not limited to, proteins, welan gum, tamarind gum, tamarind seed gum, tragacanth gum, gum arabic, carrageenan, rhamsan gum, succinoglycan, tara gum, karaya gum, pectin, alginic acid derivatives, and cellulose ethers.

The water-soluble polymer (A) is preferably at least one selected from the group consisting of polyvinyl alcohol, CMC, polyacrylic acid, sodium polyacrylate, methyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, and water-soluble acrylic resin, and more preferably at least one of methyl cellulose and hydroxypropyl methyl cellulose. From the viewpoint of improving the adhesion amount of the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure to the unvulcanized rubber, it is preferable that the viscosity of the water-soluble polymer (A) is not too low. From the viewpoint of improving the drying property of the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure, it is preferable that the viscosity of the water-soluble polymer (A) is not too high. In this disclosure, the "adhesion amount" of the liquid anti-adhesive composition for unvulcanized rubber refers to the adhesion amount of all components other than water in the liquid anti-adhesive composition for unvulcanized rubber to the unvulcanized rubber surface.

[1-2. Component (B): Metal soap containing component (B1) and component (B2)]
In the liquid anti-adhesive composition for unvulcanized rubber according to the present disclosure, component (B) is, as described above, a metal soap containing components (B1) and (B2) (hereinafter, may be referred to as "metal soap (B)").

As described above, the component (B1) is at least one compound selected from the group consisting of fatty acid calcium and fatty acid lithium. The fatty acid may be, for example, a derivative thereof. The fatty acid derivative is, for example, a fatty acid substituted with one or more substituents. The component (B1) may be, for example, at least one compound selected from the group consisting of calcium salts and lithium salts of the fatty acid derivatives. The fatty acid may be, for example, a higher fatty acid. The higher fatty acid is, for example, a fatty acid having 8 or more, 12 or more, or 14 or more carbon atoms, and the upper limit of the carbon number is not particularly limited, but is, for example, 22 or less, 20 or less, or 18 or less carbon atoms. Specific examples of the component (B1) include calcium caprylate, lithium caprylate, calcium caprate, lithium caprate, calcium laurate, lithium laurate, calcium myristate, lithium myristate, calcium palmitate, lithium palmitate, calcium stearate, lithium stearate, calcium octadecanoate, lithium octadecanoate, calcium 12-hydroxystearate, lithium 12-hydroxystearate, calcium 14-octadecanoate, lithium 14-octadecanoate, calcium 8-octadecanoate, lithium 8-octadecanoate, calcium 6-octadecanoate, lithium 6-octadecanoate, calcium coconut fatty acid, lithium coconut fatty acid, calcium palm oil fatty acid, lithium palm oil fatty acid, calcium palm kernel fatty acid, and lithium palm kernel fatty acid. Among these, calcium stearate is preferred from the viewpoint of being widely distributed and easily available at low cost.

In the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure, the content of the component (B1) is not particularly limited, but may be, for example, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, or 35% by mass or more, relative to 100% by mass of the total mass of the components other than water (solid content), and may be, for example, 60% by mass or less, 50% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less. When the content of the component (B1) is 5% by mass or more relative to 100% by mass of the total mass of the components other than water, for example, the anti-adhesive coating has excellent slip properties. In addition, when the content of the component (B1) is 60% by mass or less relative to 100% by mass of the total mass of the components other than water, for example, the powder scattering suppression effect is excellent, and the viscosity increase of the liquid product can be suppressed, resulting in excellent handleability.

The content (amount) of the component (B1) in the liquid anti-adhesive composition for unvulcanized rubber disclosed herein is not particularly limited, but may be, for example, 0.5 to 5 mass%, 0.7 to 3 mass%, 1.0 to 3 mass%, or 1.5 to 3 mass% relative to the total mass of the liquid anti-adhesive composition for unvulcanized rubber disclosed herein.

As described above, the component (B2) is at least one compound selected from the group consisting of fatty acid zinc, fatty acid magnesium, and fatty acid aluminum. The fatty acid may be, for example, a derivative thereof. The fatty acid derivative is, for example, a fatty acid substituted with one or more substituents. The component (B2) may be, for example, at least one compound selected from the group consisting of a zinc salt, a magnesium salt, and an aluminum salt of the fatty acid derivative. The fatty acid may be, for example, a higher fatty acid. The higher fatty acid is, for example, a fatty acid having 8 or more, 12 or more, or 14 or more carbon atoms, and the upper limit of the carbon number is not particularly limited, but is, for example, 22 or less, 20 or less, or 18 or less carbon atoms. Specific examples of the component (B2) include zinc caprylate, magnesium caprylate, zinc caprate, magnesium caprate, zinc laurate, magnesium laurate, aluminum laurate, zinc myristate, magnesium myristate, zinc palmitate, magnesium palmitate, zinc stearate, magnesium stearate, aluminum stearate, aluminum trioctadecanoate, aluminum dioctadecanoate, aluminum monooctadecanoate, zinc octadecanoate, magnesium octadecanoate, zinc oleate, and magnesium oleate. , zinc behenate, magnesium behenate, zinc 12-hydroxystearate, magnesium 12-hydroxystearate, zinc 14-octadecanoate, magnesium 14-octadecanoate, zinc 8-octadecanoate, magnesium 8-octadecanoate, zinc 6-octadecanoate, magnesium 6-octadecanoate, zinc coconut fatty acid, magnesium coconut fatty acid, zinc palm oil fatty acid, magnesium palm oil fatty acid, zinc palm kernel oil fatty acid, magnesium palm kernel oil fatty acid, zinc beef tallow fatty acid, magnesium beef tallow fatty acid, zinc castor oil fatty acid, and magnesium castor oil fatty acid. Among these, zinc stearate and magnesium stearate are preferred from the viewpoints of being widely distributed and easily available at low cost.

In the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure, the content of the component (B2) is not particularly limited, but may be, for example, 2.5% by mass or more, 5% by mass or more, 10% by mass or more, or 15% by mass or more, for example, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, or 15% by mass or less, based on 100% by mass of the total mass of the components other than water (solid content). When the content of the component (B2) is 2.5% by mass or more based on 100% by mass of the total mass of the components other than water, for example, the anti-adhesive coating has excellent slip properties. In addition, when the content of the component (B2) is 40% by mass or less based on 100% by mass of the total mass of the components other than water, for example, the foaming inhibitory effect and the powder scattering inhibitory effect are excellent, and the viscosity increase of the liquid product can be suppressed, resulting in excellent handleability.

The content (amount) of the component (B2) in the liquid anti-adhesive composition for unvulcanized rubber disclosed herein is not particularly limited, but may be, for example, 0.5 to 5 mass%, 0.8 to 4 mass%, 1.0 to 3.5 mass%, or 1.5 to 3.5 mass% relative to the total mass of the liquid anti-adhesive composition for unvulcanized rubber disclosed herein.

In the liquid anti-adhesive composition for unvulcanized rubber disclosed herein, the content of metal soap (B) may be, for example, 20% by mass or more, 30% by mass or more, or 35% by mass or more relative to 100% by mass of the total mass of components other than water (solids), and may be, for example, 60% by mass or less, 50% by mass or less, or 40% by mass or less.

The mass ratio (B1)/(B2) of the component (B1) to the component (B2) may be, for example, 0.1 or more, 0.2 or more, or 0.3 or more, and may be, for example, 1.0 or less, 0.9 or less, or 0.8 or less. If it is 0.1 or more, it has an excellent anti-adhesion effect, and if it is 1.0 or less, it has an excellent foaming suppression effect and can suppress the increase in viscosity of the liquid product, resulting in excellent handleability.

[1-3. Component (C): Surfactant other than component (B) and component (E)]
In the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure, the content of the component (C), i.e., a surfactant other than the components (B) and (E) (hereinafter sometimes referred to as "surfactant (C)") is not particularly limited, but is, for example, 1 to 10 mass% or 2 to 8 mass% relative to the total mass 100 mass% of the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure, and is, for example, 10 to 25 mass% relative to the total mass 100 mass% of the components other than water (solid content). When the content of the surfactant (C) is 10 mass% or more relative to the total mass 100 mass% of the components other than water, for example, the dispersing effect of the metal soap (B) is improved and separation becomes difficult, and when it is 25 mass% or less, for example, dispersibility is moderately suppressed, adhesion becomes good, and anti-adhesiveness is also good. The content of the surfactant (C) may be, for example, 12% by mass or more, 14% by mass or more, or 15% by mass or more, and may be, for example, 20% by mass or less, 18% by mass or less, or 16% by mass or less, relative to 100% by mass of the total mass of components other than water. The method for measuring the adhesion to unvulcanized rubber is not particularly limited, and can be measured, for example, by the measurement method described in the Examples below.

The surfactant (C) imparts dispersibility in water to the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure, and improves wettability, thereby improving adhesion to unvulcanized rubber. The 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. The anionic surfactant is not particularly limited, but examples thereof include the following (i) to (iv). The nonionic surfactant is not particularly limited, but 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, and acylamino carboxylates. (ii) Sulfate type anionic surfactants such as higher alcohol sulfates, polyoxyalkylene higher alcohol sulfates, alkyl phenyl ether sulfates, polyoxyalkylene alkyl phenyl ether sulfates, and glycerin fatty acid ester monosulfate. (iii) Sulfonic acid type anionic surfactants such as alkanesulfonates, α-olefin sulfonates, linear alkylbenzene sulfonates, α-sulfofatty acid ester salts, and dialkyl sulfosuccinates. (iv) Phosphate type anionic surfactants such as alkyl phosphate salts, polyoxyalkylene alkyl phosphate salts, polyoxyalkylene alkyl phenyl phosphate salts, and glycerin fatty acid ester monophosphate salts. (v) Polyoxyalkylene alkyl ether type nonionic surfactants.

The counter ion of the anionic surfactant is not particularly limited, but is preferably an alkali metal such as sodium or potassium, or an alkanolamine such as monoethanolamine or diethanolamine. These may be used alone or in combination.

As an anionic surfactant, dialkyl sulfosuccinate is preferred, and dioctyl sulfosuccinate Na salt is more preferred, as it provides an anti-adhesive composition that has excellent wettability with the surface of unvulcanized rubber.

The nonionic surfactant is not particularly limited, but in the present disclosure, for example, a nonionic surfactant represented by the following formula (1) can be used. It is presumed that the nonionic surfactant of the following formula (1), together with the anionic surfactant, not only reduces the surface tension of the adhesion-preventive composition with respect to the surface of the unvulcanized rubber, but also effectively increases the adhesion of the adhesion-preventive composition to the surface of the unvulcanized rubber. However, this presumption does not limit the present disclosure in any way.

RO-(AO) _n -H (1)

In the formula (1), R represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms. The aliphatic hydrocarbon group may be linear or branched. In addition, it may be either saturated or unsaturated. The number of carbon atoms in R is preferably 12 to 16, and 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 represents the average number of moles of AO added.
n is, for example, 1 to 30, 1 to 25, or 2 to 15. Specifically, from the viewpoint of preventing the decrease in surface activity and the decrease in dispersibility of component (A), n is 1 or more (i.e., not 0). In addition, from the viewpoint of preventing the decrease in adhesion due to excessively high hydrophilicity, n is 30 or less, or 25 or less. It is presumed that if n is in the range of 1 to 30 or 1 to 25, the dispersibility of component (A) is further improved, and even when the hydrophobicity of the unvulcanized rubber surface is high, sufficient viscoelasticity is imparted to the dried coating of the liquid adhesion preventive agent composition for unvulcanized rubber, thereby improving adhesion. However, this presumption does not limit the present disclosure in any way.

The oxyalkylene group having 2 to 4 carbon atoms is, for example, a polymerized unit formed by the 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) formed by the addition of ethylene oxide, an oxypropylene group (PO) formed by the addition of propylene oxide, and an oxybutylene group (BO) formed by the addition of butylene oxide. (AO) _n contains at least an oxyethylene group in its structure. When (AO) _n contains a plurality of types of oxyethylene groups (EO), oxypropylene groups (PO), and oxybutylene groups (BO), these groups may be arranged in a block form or randomly. A preferable (AO) _n is composed of only an oxyethylene group (EO) from the viewpoint of excellent balance between hydrophilicity and hydrophobicity.

Specific examples of nonionic surfactants include, but are not limited to, 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, etc.

[1-4. Component (D): water-soluble polymer]
As described above, the component (D) is at least one compound selected from the group consisting of water-soluble polymers having a thixotropy index (2 rpm/20 rpm) (hereinafter simply referred to as "TI value") of a 2% by mass aqueous solution at 20°C of 4.0 or more (hereinafter sometimes referred to as "water-soluble polymer (D)"). The TI value can be measured, for example, as follows. 2 g of the water-soluble polymer is added to 98 g of water, mixed at 80°C for 30 minutes to completely dissolve, and then cooled to the temperature to be measured. Thereafter, the viscosity of the prepared aqueous solution is measured using a BH viscometer with the rotation speed set to 2 rpm and 20 rpm. The viscosity values obtained are calculated using the following formula (viscosity value obtained at 2 rpm/viscosity value obtained at 20 rpm). The TI value is not particularly limited, but may be, for example, 4.0 or more, or 6.0 or more, and may be, for example, 15.0 or less, 12.0 or less, 10.0 or less, or 8.0 or less. This provides, for example, a stabilizing effect for the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure. In this manner, the component (D) functions, for example, as a stabilizer.

The content of the water-soluble polymer (D) is not particularly limited, but may be, for example, 0.01 to 0.6% by mass, 0.03 to 0.6% by mass, or 0.05 to 0.5% by mass relative to the total mass of the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure, and may be, for example, 0.01 to 10% by mass relative to 100% by mass of the total mass of the components other than water (solids). When the content of the water-soluble polymer (D) is 0.01% by mass or more relative to the total mass of the components other than water, for example, the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure is less likely to separate, and when it is 10% by mass or less, for example, the viscosity of the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure increases too much, which can prevent deterioration of handling. The content of the water-soluble polymer (D) may be, for example, 0.1% by mass or more, or 0.5% by mass or more, and may be, for example, 8.0% by mass or less, or 4.0% by mass or less, relative to the total mass of the components other than water.

The water-soluble polymer (D) may be, for example, a water-soluble polymer having a viscosity of 3 to 300 mPa·s at 25°C when the water-soluble polymer (D) is in a 2% by mass aqueous solution. The water-soluble polymer having a viscosity of 3 mPa·s or more at 25°C when the water-soluble polymer is in a 2% by mass aqueous solution, for example, can improve the amount of adhesion to unvulcanized rubber. The water-soluble polymer having a viscosity of 300 mPa·s or less at 2% by mass can have an excellent drying property. The viscosity of the 2% by mass aqueous solution may be, for example, 10 mPa·s or more, or 100 mPa·s or more, or 200 mPa·s or less, or 100 mPa·s or less.

The water-soluble polymer (D) is not particularly limited, but may be, for example, a polymer whose lower limit of solubility in 100 g of water at 25°C is 1 g or more, 10 g or more, or 50 g or more.

The type of water-soluble polymer (D) is not particularly limited, and one type may be used alone or multiple types may be used in combination. The water-soluble polymer (D) may be, for example, a synthetic water-soluble polymer or a natural water-soluble polymer. Preferred examples of the water-soluble polymer (D) include diutan gum, xanthan gum, guar gum, locust bean gum, gellan gum, etc., which have a TI value of 4.0 or more.

[1-5. Component (E): Defoamer]
In the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure, the anti-foaming agent (E) is at least one of the compound represented by the chemical formula (I) and a salt thereof, as described above (hereinafter, may be referred to as "anti-foaming agent (E)"). The content of the anti-foaming agent (E) is not particularly limited, but is, for example, 0.01 to 5 mass%, 0.03 to 5 mass%, or 0.03 to 2 mass% relative to the total mass 100 mass% of the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure, and is, for example, 0.2 to 20 mass% relative to the total mass 100 mass% of the components other than water (solid content). The content of the anti-foaming agent (E) may be, for example, 0.3 mass% or more, 0.4 mass% or more, or 0.5 mass% or more relative to the total mass 100 mass% of the components other than water, and may be, for example, 19.5 mass% or less, 19 mass% or less, 15 mass% or less, or 10 mass% or less.

The defoaming agent (E) is, for example, a compound having a melting point of 80° C. or less. Examples of the compound having a melting point of 80° C. or less include at least one compound selected from the group consisting of the following components (E-1) to (E-3). If the melting point is 80° C. or less, the defoaming property is excellent.

(E-1) Fatty acid amides (also called fatty acid amides)
(E-2) Amidoamine (E-3) At least one of N-alkyl alkylenediamine and its fatty acid salt

The component (E-1) is, for example, a compound represented by the chemical formula (I) in which ^R1 is a hydrocarbon group having 7 to 25 carbon atoms, X is CONH, and Y is H. The component (E-1) is, for example, preferably a fatty acid amide having an unsaturated bond in the hydrocarbon group, more preferably oleic acid amide or erucic acid amide, and even more preferably oleic acid amide.

The component (E-2) is, for example, ^a compound represented by the chemical formula (I) in which ^R1 is a hydrocarbon group having 7 to 25 carbon atoms, X is CONH ^, Y is ( _CH2 ) _mNR2R3 , m is an integer of 2 to 4, and ^R2 and ^R3 are each H, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and ^R2 and ^R3 may be the same or different. Preferred examples of the component (E-2) include palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, and behenic acid dimethylaminopropylamide (also known as behenamidopropyldimethylamine), and one type may be used alone or multiple types may be used in combination.

The component (E-3) is, for example, ^a compound represented by the chemical formula (I) in which ^R1 is a hydrocarbon group having 7 to 25 carbon atoms, X is NH, Y is ( _CH2 ) _mNR2R3 ^, m is an integer of 2 to 4, and ^R2 and ^R3 are each H, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and ^R2 and ^R3 may be the same or different. The component (E-2) is preferably, for example, an N-alkyl (C14 to C18) trimethylenediamine oleate.

[1-6. Mass ratio of each component]
The mass ratio (A)/(B) of the component (A) to the component (B) is not particularly limited, but may be, for example, in the range of 0.2 to 4.0, and the lower limit is more preferably 0.4 or more, 0.6 or more, 0.8 or more, or 0.9 or more, and the upper limit is more preferably 3.0 or less, 2.0 or less, 1.0 or less, or 0.9 or less. If it is in the above range, the adhesion prevention property will be more excellent.

The mass ratio (A)/(D) of the component (A) to the component (D) is not particularly limited, but may be, for example, in the range of 3 to 500, and the lower limit is more preferably 4 or more, 5 or more, 10 or more, 15 or more, 25 or more, 50 or more, or 70 or more, and the upper limit is more preferably 400 or less, 200 or less, 100 or less, 90 or less, 80 or less, or 75 or less. Within the above ranges, the product stability and handleability will be better.

The mass ratio (C)/(E) of the component (C) to the component (E) is not particularly limited, but may be, for example, in the range of 0.5 to 100, and the lower limit is more preferably 1 or more, 3 or more, 5 or more, 7 or more, or 8 or more, and the upper limit is more preferably 80 or less, 70 or less, 60 or less, 50 or less, 25 or less, 10 or less, or 9 or less. Within the above ranges, the product stability and handleability will be better.

The mass ratio (D)/(E) of the component (D) to the component (E) is not particularly limited, but may be, for example, in the range of 0.005 to 50, and the lower limit is more preferably 0.01 or more, 0.05 or more, 0.1 or more, 0.2 or more, or 0.3 or more, and the upper limit is more preferably 20 or less, 10 or less, 5 or less, 2 or less, 1 or less, or 0.5 or less. Within the above ranges, the antifoaming properties and product stability will be more excellent.

[1-7. water]
In the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure, the water content is not particularly limited, and may be, for example, 50 mass % or more, 60 mass % or more, or 70 mass % or more, and may be, for example, 95 mass % or less, 90 mass % or less, 85 mass % or less, or 80 mass % or less, relative to the total mass of the liquid anti-adhesive composition for unvulcanized rubber.

Water, for example, serves to impart fluidity to the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure, making it easy to handle. The water is not particularly limited, and may be, for example, tap water, distilled water, ion-exchanged water, etc.
[1-8. Optional ingredients, etc.]
The liquid anti-adhesive composition for unvulcanized rubber of the present disclosure may or may not contain optional components other than the components (A) to (E) and water. For example, the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure may contain additives such as defoamers, preservatives, wettability aids, viscosity aids, and foreign matter reduction aids as optional components, as necessary.

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

The preservatives are not particularly limited, but examples thereof include isothiazolinone, pyridine, and iodine derivatives. The isothiazolinone derivatives are not particularly limited, but examples thereof include benzisothiazolinone (BIT), methylisothiazolinone (MIT, MI), chloromethylisothiazolinone (CMIT, CMI), octylisothiazolinone (OIT, OI), dichlorooctylisothiazolinone (DCOIT, DCOI), and derivatives thereof. The pyridine derivatives are not particularly limited, but examples thereof include pyridinethiol and derivatives thereof. The iodine derivatives are not particularly limited, but examples thereof include iodo-2-propargylbutylcarbamic acid and derivatives thereof. For example, the preservatives may be used alone or in combination.

The wettability aid is not particularly limited, but examples thereof include alcohols, and more specifically, examples thereof include methanol, ethanol, hexanol, glycerin, 1,3-butanediol, propylene glycol, dipropylene glycol, pentylene glycol, hexylene glycol, polyethylene glycol, sorbitol, maltitol, sucrose, erythritol, xylitol, polyethylene glycol, polypropylene glycol, ethylene oxide or propylene oxide adducts of polyhydric alcohols, etc. Only one type of the wettability aid may be used, or multiple types may be used in combination.

The viscosity of the liquid anti-adhesive composition for unvulcanized rubber disclosed herein is not particularly limited, but for example, because it is difficult to separate and has good handleability, the viscosity measured after 10 rotations at 20 rpm at 25°C using a BH type viscometer three days after the production of the liquid anti-adhesive composition for unvulcanized rubber is preferably 25,000 mPa·s or less, more preferably 3,000 to 25,000 mPa·s, even more preferably 6,000 to 25,000 mPa·s, and particularly preferably 6,000 to 24,000 mPa·s. From the viewpoint of suppressing or preventing separation of the liquid anti-adhesive composition for unvulcanized rubber, it is preferable that the viscosity of the liquid anti-adhesive composition for unvulcanized rubber is 3,000 mPa·s or more, and from the viewpoint of suppressing or preventing deterioration of handling, such as difficulty in removing the composition from a container, it is preferable that the viscosity of the liquid anti-adhesive composition for unvulcanized rubber is 25,000 mPa·s or less.

[2. Method for producing liquid anti-adhesive composition for unvulcanized rubber]
The method for producing the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure is not particularly limited, but can be produced, for example, by mixing all the components of the liquid anti-adhesive composition for unvulcanized rubber (components (A) to (E) and water, and optional components blended as necessary). The order of mixing and the equipment and facilities used for mixing are not particularly limited. For example, a method of mixing water and a water-soluble polymer (component (A) and component (D)), a surfactant (component (C)), and an antifoaming agent (component (E)) and then mixing a metal soap (component (B)) and other optional components can be exemplified. As described above, the equipment used for mixing is not particularly limited, but for example, an equipment having a configuration in which a stirring blade is provided in a container can be used. Specifically, for example, liquid mixers such as a general liquid mixer, a vortex mixer, a static mixer, a homogenizer, and a line homomixer can be exemplified.

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

The method for preventing adhesion of unvulcanized rubber using the liquid anti-adhesive composition for unvulcanized rubber disclosed herein may, for example, have an adhesion prevention treatment step in which the components (A) to (E) in the liquid anti-adhesive composition for unvulcanized rubber disclosed herein are adhered to the surface of the unvulcanized rubber to perform adhesion prevention treatment, as described above. The adhesion to the surface of the unvulcanized rubber can be performed, for example, by a wet method described later. The unvulcanized rubber that has been treated for adhesion prevention in this way does not adhere to each other even if it is stored, for example, stacked or folded. In addition, such an adhesion prevention treatment method for unvulcanized rubber can also be said to be, for example, a method for producing anti-adhesive treated unvulcanized rubber.

The liquid anti-adhesive composition for unvulcanized rubber of the present disclosure may be used as is, or may be further diluted with water and used in the form of a water-diluted liquid (aqueous dispersion). In the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure, the concentration when attached to the unvulcanized rubber surface is not particularly limited, but the total mass of components 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, relative to the total mass of the liquid anti-adhesive composition for unvulcanized rubber. If the concentration is not too high, for example, effects such as 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 slipperiness can be obtained. The liquid anti-adhesive composition for unvulcanized rubber of the present disclosure can exhibit high adhesion prevention even when the concentration is low when attached to the unvulcanized rubber surface, so that high adhesion prevention can be exhibited with a small amount of adhesion. The viscosity when applied to the surface of unvulcanized rubber is not particularly limited, and may be, for example, 1 mPa·s or more, 5 mPa·s or more, or 10 mPa·s or more, and may be, for example, 30 mPa·s or less, 20 mPa·s or less, or 15 mPa·s or less. If the viscosity is not too high, for example, effects such as low scattering and fast drying can be obtained. If the viscosity is not too low, for example, effects such as high adhesion resistance and high slipperiness can be obtained.

The adhesion prevention treatment step may be, for example, as described above, a step of adhering the liquid adhesion preventive composition for unvulcanized rubber of the present disclosure or a water-diluted liquid adhesion preventive composition for unvulcanized rubber of the present disclosure to the surface of the unvulcanized rubber, and further volatilizing the water, thereby adhering the components (A) to (E) in the liquid adhesion preventive composition for unvulcanized rubber of the present disclosure to the surface of the unvulcanized rubber. More specifically, the adhesion prevention treatment step may include, for example, a liquid adhesion preventive composition for unvulcanized rubber adhering step of adhering the liquid adhesion preventive composition for unvulcanized rubber of the present disclosure to the surface of the unvulcanized rubber, and a drying step of drying the liquid adhesion preventive composition for unvulcanized rubber on the surface of the unvulcanized rubber to form a coating on the surface of the unvulcanized rubber. Such an adhesion prevention treatment step is called, for example, a wet method. The wet method is not particularly limited, and for example, it can be performed in the same manner as a general wet method for a liquid adhesion preventive composition for unvulcanized rubber.

In the process of applying the liquid anti-adhesive composition for unvulcanized rubber, it is preferable to apply the liquid anti-adhesive composition for unvulcanized rubber to unvulcanized rubber that is in a high-temperature state (e.g., about 80 to 150°C) due to the heat generated when it is molded into a sheet or the like.

Specific methods for the step of applying the liquid anti-adhesive composition for unvulcanized rubber include, for example, a method of spraying the liquid anti-adhesive composition for unvulcanized rubber onto the unvulcanized rubber using a shower device, and a dip method of immersing the unvulcanized rubber for a short period of time into a tank containing the liquid anti-adhesive composition for unvulcanized rubber. In addition, a method of applying the liquid anti-adhesive composition for unvulcanized rubber onto the unvulcanized rubber using an applicator may also be employed, and these methods may be used in combination as appropriate.

As described above, the liquid anti-adhesive composition for unvulcanized rubber disclosed herein has excellent anti-adhesive effect and defoaming properties.

There are no particular limitations on the type of rubber to which the liquid anti-adhesive composition for unvulcanized rubber disclosed herein can be applied, as long as it is unvulcanized rubber. Examples of the rubber type include natural rubber (NR), butadiene rubber (BR), styrene butadiene rubber (SBR), IIR (butyl rubber), EPDM (ethylene propylene rubber), and the like, as well as rubbers in which multiple types of these are mixed.

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

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

820 g of water was placed in a reaction vessel and heated to 80°C or higher. Then, 40 g of hydroxypropyl methylcellulose (Metolose 60SH-4000, degree of methoxy group substitution 1.9, molar number of hydroxypropoxy group substitution 0.25, 2% viscosity 4000 mPa·s, manufactured by Shin-Etsu Chemical Co., Ltd.) was placed in the reaction vessel and mixed for 2 hours. The hydroxypropyl methylcellulose is a water-soluble polymer and corresponds to the component (A) in the liquid anti-adhesive composition for unvulcanized rubber disclosed herein. The mixture thus obtained after mixing for 2 hours was cooled to 30°C or less, and then 15g of calcium laurate (manufactured by Taihei Chemical Industry Co., Ltd.), 15g of magnesium myristate (manufactured by Taihei Chemical Industry Co., Ltd.), 0.5g of gellan gum (Kelcogel, manufactured by Sumitomo Pharma Food & Chemical Co., Ltd.), 0.3g of oleic acid amide (manufactured by Kanto Chemical Co., Ltd.), 10g of coconut alcohol EO adduct (Leox (registered trademark) CC-150, manufactured by Lion Specialty Chemicals Co., Ltd.), 5g of sodium alpha olefin sulfonate (Liporan (registered trademark) LB-840, manufactured by Lion Specialty Chemicals Co., Ltd.), and 1g of preservative (Slaoff EX, manufactured by Osaka Gas Chemicals Co., Ltd.) were added and stirred to obtain a liquid anti-adhesive composition for unvulcanized rubber. The calcium laurate is a metal soap and corresponds to the component (B-1) in the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure. The magnesium myristate is a metal soap, and corresponds to the component (B-2) in the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure. The gellan gum corresponds to the component (D) in the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure. The oleic acid amide is a defoaming agent, and corresponds to the component (E) in the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure. The coconut alcohol EO adduct and the sodium alpha-olefin sulfonate are both surfactants, and correspond to the component (C) in the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure. The preservative corresponds to an optional component other than the components (A) to (E).

[Examples 2 to 35, Comparative Examples 1 to 5]
Except for changing the types and compositions of the raw materials as shown in Tables 2 to 5 below, the liquid anti-adhesive compositions for unvulcanized rubber of Examples 2 to 35 and Comparative Examples 1 to 5 were produced in the same manner as in Example 1. The product name (product name), manufacturer, and characteristics (composition) of each raw material used in the production of the liquid anti-adhesive compositions for unvulcanized rubber of Examples 2 to 35 and Comparative Examples 1 to 5 are shown in Table 1 below.

[Production and performance evaluation of aqueous dilution of liquid anti-adhesive composition for unvulcanized rubber]
The liquid anti-adhesive composition for unvulcanized rubber of each of the Examples and Comparative Examples was diluted 20 times (by mass) with water to produce a water-diluted liquid anti-adhesive composition for unvulcanized rubber (anti-adhesive suspension). This water-diluted liquid anti-adhesive composition for unvulcanized rubber was used to perform an anti-adhesive treatment on unvulcanized rubber, and the performances of anti-adhesiveness, foaming property (anti-foaming property), lubricity, scattering property, stability, and viscosity were evaluated. The anti-adhesive treatment method and the evaluation method for each of the performances are shown below.

<Evaluation>
(1) Rubber for Evaluation In various evaluations, the following unvulcanized SBR rubber and unvulcanized NR rubber were used as rubber for evaluation.
(Unvulcanized SBR rubber)
Unvulcanized SBR rubber was used in which 100 parts by mass of SBR (manufactured by Asahi Kasei Corporation, product name "Tufden 4850") was blended with 30 parts by mass of SAF carbon (manufactured by Mitsubishi Chemical Corporation, product name "Diablack A"), 15 parts by mass of JSRAROMA (process oil) (manufactured by Japan Sun Oil Co., Ltd., product name "Aroma 790"), 3 parts by mass of zinc oxide (manufactured by Hakusui Tech Co., Ltd., zinc oxide type 2), 1 part by mass of stearic acid (manufactured by NOF Corporation, camellia), 1 part by mass of 6PPD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., product name "Nocrac 6C"), 1 part by mass of CBS (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., product name "Noccela CZ-G"), and 1.5 parts by mass of sulfur (manufactured by Tsurumi Chemical Co., Ltd.) (total 152.5 parts by mass).

(Unvulcanized NR rubber)
For 100 parts by mass of NR (RSS#3), 10 parts by mass of white carbon (manufactured by Tosoh Silica Corporation, trade name "Nipsil VN-3"), 30 parts by mass of ISAF black (manufactured by Tokai Carbon Co., Ltd., trade name "Seat 6"), 15 parts by mass of JSRAROMA (process oil) (manufactured by Nippon San Oil Co., Ltd., trade name "Aroma 790"), 3 parts by mass of zinc oxide (manufactured by Hakusui Tech Co., Ltd., zinc oxide type 2), 1 part by mass of stearic acid (manufactured by NOF Corp., camellia), 1 part by mass of 6PPD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., trade name "Nocrac 6C"), 1 part by mass of CBS (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., trade name "Noccela CZ-G"), and 1.5 parts by mass of sulfur (manufactured by Tsurumi Chemical Co., Ltd.) were blended (total 162.5 parts by mass) of unvulcanized NR rubber.

(2) Evaluation of adhesion prevention The unvulcanized rubber was 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 x 15 cm), and the rubber sheet immediately after being unwound was immersed for about 1 second in 1 L of a water-diluted liquid anti-adhesive composition for unvulcanized rubber (anti-adhesive suspension, temperature 40 ° C.) obtained by diluting the liquid anti-adhesive composition for unvulcanized rubber obtained in each of Examples 1 to 35 and Comparative Examples 1 to 5 20 times with water. Thereafter, the rubber sheet was quickly pulled up vertically, left standing in a vertical state at room temperature, and naturally dried. In this way, the anti-adhesive treatment of the rubber sheet (unvulcanized rubber) was performed.

The rubber sheet after the adhesion prevention treatment was cut into a size of 6 cm x 15 cm, and two pieces were stacked together to form a laminated test piece. A load of 1 t/ ^m2 was applied vertically from one side to the laminated test piece, and the test piece was left at 60°C for 12 hours.

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

(3) Evaluation of foaming property (defoaming property) The liquid anti-adhesive composition for unvulcanized rubber was diluted 20 times with water to prepare 1 L of an anti-adhesive suspension (temperature 40°C), which was circulated for 5 minutes from a height of 40 cm above the liquid surface using a circulation pump, and the foam height (mL) was measured. A lower foam height indicates better foaming property (i.e., better defoaming property).

(4) Evaluation of Slipperiness A rubber sheet (unvulcanized rubber) was subjected to anti-adhesive treatment in the same manner as in (2) Evaluation of Anti-adhesiveness. Next, the unvulcanized rubber sheet that had been dried after the anti-adhesive treatment was cut into a rectangle of 5 x 15 cm. This rubber was placed on a stainless steel plate, and the plate was gradually tilted to measure the tilt angle at which it slid down. The lower the start of sliding angle, the better the slipperiness.

(5) Evaluation of scattering properties A rubber sheet (unvulcanized rubber) was subjected to anti-sticking treatment in the same manner as in the evaluation of adhesion resistance in (2) above. Next, the dried unvulcanized rubber sheet after the anti-sticking treatment was cut into a rectangle of 6 x 15 cm and weighed. The front and back surfaces of the rubber were brushed 10 times, and the weight was measured again to calculate the amount of scattering. The smaller the amount of scattering, the better the scattering properties.

(6) Evaluation of Stability 100 mL of the liquid anti-adhesive composition for unvulcanized rubber before diluting 20 times (mass ratio) with water was placed in a sealed container and left to stand in a thermostatic chamber at 20° C. After standing for one week, the appearance was visually inspected to see if there was any separation. If no separation of the anti-adhesive composition for rubber was visually observed, it indicates good stability.

(7) Viscosity Evaluation The viscosity of the liquid anti-adhesive composition for unvulcanized rubber before dilution with water 20 times (mass ratio) was measured 3 days after production. The viscosity was measured using a BH type viscometer (Tokimec Co., Ltd., product name "Viscometer BII type") at 25°C and after 10 revolutions at 20 rpm.

The types and compositions of raw materials in the liquid anti-adhesive compositions for unvulcanized rubber of Examples 1 to 35 and Comparative Examples 1 to 5, and the evaluation results of each performance of anti-adhesiveness and foamability evaluated as described above, are summarized in Tables 2 to 5 below. In Tables 2 to 5 below, the numerical values showing the amount of each raw material (including water) used are the content (mass %) relative to the total mass (including water) of the liquid anti-adhesive composition for unvulcanized rubber.

As shown in Tables 2 to 5, the liquid anti-adhesive compositions for unvulcanized rubber of Examples 1 to 35 had good adhesion prevention and foaming properties. Although not shown in Tables 2 to 5, the lubricity (75 degrees or less), scattering (0.5 or less), stability (stable for one week or more), and liquid delivery (viscosity) (3000 to 25000 mPa·s) were also good. In contrast, the liquid anti-adhesive composition for unvulcanized rubber of Comparative Example 1, which did not use component (A), had significantly poorer adhesion prevention properties than the Examples. The liquid anti-adhesive composition for unvulcanized rubber of Comparative Example 2, which did not use component (B), had significantly poorer adhesion prevention properties than the Examples. In addition, the lubricity was 90 degrees, which was inferior to the Examples. The liquid anti-adhesive composition for unvulcanized rubber of Comparative Example 3, which did not use component (D), had poorer foaming properties than the Examples. In addition, the stability was not stable for one week or more, which was inferior to the Examples. The liquid anti-adhesive composition for unvulcanized rubber of Comparative Example 4, which did not use component (E), had poor foaming properties compared to the Examples. The liquid anti-adhesive composition for unvulcanized rubber of Comparative Example 5, which did not use component (C), had significantly poorer anti-adhesive properties compared to the Examples. In addition, the slipperiness was 90 degrees, which was poor compared to the Examples. The stability was also poor for more than one week, which was poor compared to the Examples.

<Additional Notes>
A part or all of the above-described embodiments and examples may be described as follows, but is not limited to the following.
(Appendix 1)
A liquid anti-adhesive composition for unvulcanized rubber, comprising the following components (A) to (E) and water:

(A) a water-soluble polymer other than the following component (D); (B) a metal soap containing the following components (B1) and (B2); (B1) at least one compound selected from the group consisting of fatty acid calcium, and fatty acid lithium; (B2) at least one compound selected from the group consisting of fatty acid zinc, fatty acid magnesium, and fatty acid aluminum; (C) a surfactant other than the component (B) and the following component (E); (D) at least one compound selected from the group consisting of water-soluble polymers having a thixotropy index (2 rpm/20 rpm) of a 2% by mass aqueous solution at 20°C of 4.0 or more; (E) at least one compound represented by the following chemical formula (I) and a salt thereof:

R ¹ -XY (I)

In the above chemical formula (I),
R ¹ is a hydrocarbon group having 7 to 25 carbon atoms;
X is NH or CONH,
Y is H or (CH ₂ ) _m NR ² R ³ , provided that when X is NH, then Y is not H;
m is an integer from 2 to 4,
^R2 and ^R3 are each H, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms;
^R2 and ^R3 may be the same or different.
(Appendix 2)
The liquid anti-adhesive composition for unvulcanized rubber according to claim 1, wherein the mass ratio (B1)/(B2) of the component (B1) to the component (B2) is in the range of 0.1 to 1.0.
(Appendix 3)
The liquid anti-adhesive composition for unvulcanized rubber according to claim 1 or 2, wherein the component (E) is a compound having a melting point of 80° C. or lower.
(Appendix 4)
The liquid anti-adhesive composition for unvulcanized rubber according to any one of Appendices 1 to 3, wherein the component (E) is at least one compound selected from the group consisting of the following components (E-1) to (E-3):

(E-1) Fatty acid amide (E-2) Amidoamine (E-3) At least one of N-alkyl alkylenediamine and its fatty acid salt (Appendix 5)
Based on 100% by weight of the total weight of ingredients other than water,
The component (A) is 20% by mass or more,
20 to 60% by mass of the component (B),
10 to 25% by weight of the component (C),
0.01 to 10% by mass of the component (D),
0.2 to 20% by mass of the component (E),
The liquid anti-adhesive composition for unvulcanized rubber according to any one of claims 1 to 4, comprising:
(Appendix 6)
Based on 100% by weight of the total weight of ingredients other than water,
The component (A) is 30% by mass or more,
The liquid anti-adhesive composition for unvulcanized rubber according to claim 5, comprising:
(Appendix 7)
7. A water-diluted liquid anti-adhesive composition for unvulcanized rubber, comprising the liquid anti-adhesive composition for unvulcanized rubber according to any one of claims 1 to 6 and water.
(Appendix 8)
An unvulcanized rubber having the components (A) to (E) in the liquid anti-adhesive composition for unvulcanized rubber according to any one of Appendix 1 to 6 adhered to the surface thereof.

This application claims priority based on Japanese Patent Application No. 2023-064947, filed on April 12, 2023, the disclosure of which is incorporated herein in its entirety.

Claims (7)

A liquid anti-adhesive composition for unvulcanized rubber, comprising the following components (A) to (E) and water:

(A) a water-soluble polymer other than the following component (D); (B) a metal soap containing the following components (B1) and (B2); (B1) at least one compound selected from the group consisting of fatty acid calcium, and fatty acid lithium; (B2) at least one compound selected from the group consisting of fatty acid zinc, fatty acid magnesium, and fatty acid aluminum; (C) a surfactant other than the component (B) and the following component (E); (D) at least one compound selected from the group consisting of water-soluble polymers having a thixotropy index (2 rpm/20 rpm) of a 2% by mass aqueous solution at 20°C of 4.0 or more; (E) at least one compound represented by the following chemical formula (I) and a salt thereof:

R ¹ -XY (I)

In the above chemical formula (I),
R ¹ is a hydrocarbon group having 7 to 25 carbon atoms;
X is NH or CONH,
Y is H or (CH ₂ ) _m NR ² R ³ , provided that when X is NH, then Y is not H;
m is an integer from 2 to 4,
^R2 and ^R3 are each H, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms;
^R2 and ^R3 may be the same or different. The liquid anti-adhesive composition for unvulcanized rubber according to claim 1, wherein the mass ratio (B1)/(B2) of the component (B1) to the component (B2) is in the range of 0.1 to 1.0. 2. The liquid anti-adhesive composition for unvulcanized rubber according to claim 1 , wherein the component (E) is a compound having a melting point of 80° C. or lower. The liquid anti-adhesive composition for unvulcanized rubber according to claim 1 , wherein the component (E) is at least one compound selected from the group consisting of the following components (E-1) to (E-3):

(E-1) fatty acid amide; (E-2) amidoamine; (E-3) at least one of N-alkyl alkylenediamine and its fatty acid salt; Based on 100% by weight of the total weight of ingredients other than water,
The component (A) is 20% by mass or more,
20 to 60% by mass of the component (B),
10 to 25% by weight of the component (C),
0.01 to 10% by mass of the component (D),
0.2 to 20% by mass of the component (E),
The liquid anti-adhesive composition for unvulcanized rubber according to claim 1, comprising: A water-diluted liquid anti-adhesive composition for unvulcanized rubber, comprising the liquid anti-adhesive composition for unvulcanized rubber according to any one of claims 1 to 5 and water. An unvulcanized rubber having the components (A) to (E) of the liquid anti-adhesive composition for unvulcanized rubber according to any one of claims 1 to 5 adhered to its surface.