Liquid anti-adhesive agent composition for unvulcanized rubber, aqueous dilution of liquid anti-adhesive agent composition for unvulcanized rubber, and unvulcanized rubber

Abstract

Provided is a liquid anti-adhesion agent composition for unvulcanized rubber, which exhibits an excellent adhesion-preventing effect and an excellent anti-foaming property.　The liquid anti-adhesion agent composition for unvulcanized rubber contains the following components (A) to (E) and water: (A): a water-soluble polymer other than component (D); (B): a metal soap containing component (B1) and component (B2) where (B1) is at least one of a calcium fatty acid salt and a lithium fatty acid salt and (B2) is at least one of a zinc fatty acid salt, magnesium fatty acid salt, and aluminum fatty acid salt; (C): a surfactant other than component (B) and component (E); (D): a water-soluble polymer having a thixotropy index, for its 2 mass% aqueous solution at 20°C, of at least 4.0; and (E): a compound with formula (I): R1-X-Y and / or a salt thereof, where R1 is a hydrocarbon group having 7-25 carbons, X is NH or CONH, Y is H or (CH2)mNR2R3, Y is not H when X is NH, m is an integer from 2-4, and R2 and R3 are each H, an alkyl group having 1-3 carbons, or a hydroxyalkyl group having 1-3 carbons.

Description

Technical Field

[0001] The present disclosure relates to a liquid anti-sticking agent composition for unvulcanized rubber, an aqueous dilution of the liquid anti-sticking agent composition for unvulcanized rubber, and unvulcanized rubber.

Background Art

[0002] In the production and processing site of rubber, for the purpose of preventing adhesion of rubber (for example, unvulcanized rubber), an anti-sticking agent is attached to the surface of the rubber.

[0003] As an anti-sticking agent for rubber, an anti-sticking agent for rubber mainly composed of inorganic powder is widely used. These can generally be used by attaching them to the rubber surface after being in the form of an aqueous dispersion (Patent Documents 1 to 2). In addition, in order to reduce dust derived from inorganic powder, an anti-sticking agent for unvulcanized rubber mainly composed of fatty acid soap and metal soap has been proposed (Patent Documents 3 to 4).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0005] On the other hand, an anti-sticking agent containing metal soap is likely to generate bubbles (scum bubbles) that are difficult to defoam. Scum bubbles can cause problems such as overflow from the working tank, contamination of the working environment, and foreign matter formation due to mixing into the product.

[0006] Therefore, an object of the present disclosure is to provide a liquid anti-sticking agent composition for unvulcanized rubber, a water-diluted liquid of the liquid anti-sticking agent composition for unvulcanized rubber, and unvulcanized rubber, which are excellent in anti-sticking effect and defoaming property.

Means for Solving the Problems

[0007] In order to achieve the above object, the liquid anti-sticking agent composition for unvulcanized rubber of the present disclosure 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 component (B1) and the following component (B2) (B1) At least one compound selected from the group consisting of calcium fatty acid and lithium fatty acid (B2) At least one compound selected from the group consisting of zinc fatty acid, magnesium fatty acid, and aluminum fatty acid (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 of a compound represented by the following chemical formula (I) and its salt R 1 -X-Y (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 (CH2) m NR 2 R 3 wherein when X is NH, Y is not H, m is an integer of 2 to 4, R 2 and R 3 are each H, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, R 2 and R 3 may be the same or different.

[0008] The aqueous dilution of the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure is characterized by containing the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure and water.

[0009] The unvulcanized rubber of the present disclosure is characterized in that the components (A) to (E) in the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure are adhered to the surface.

Advantages of the Invention

[0010] According to the present disclosure, it is possible to provide a liquid anti-adhesive agent composition for unvulcanized rubber, an aqueous dilution of the liquid anti-adhesive agent composition for unvulcanized rubber, and unvulcanized rubber, which are excellent in anti-adhesive effect and defoaming property.

Modes for Carrying Out the Invention

[0011] Hereinafter, the present disclosure will be described more specifically with examples. However, the present disclosure is not limited by the following description.

[0012] In the present disclosure, "alkyl" includes, for example, linear or branched alkyl. In the present disclosure, the alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, and the like.

[0013] In the present disclosure, "alkylene" includes, for example, linear alkylene (methylene or polymethylene) or branched alkylene. In the present disclosure, the alkylene group is not particularly limited, and examples thereof 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, a decamethylene group, and the like.

[0014] Hereinafter, embodiments of the present disclosure will be described more specifically. However, the present disclosure is not limited to the following embodiments.

[0015] [1. Liquid anti-adhesive agent composition for unvulcanized rubber] As described above, the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure 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 component (B1) and the following component (B2) (B1) At least one compound selected from the group consisting of calcium fatty acid and lithium fatty acid (B2) At least one compound selected from the group consisting of zinc fatty acid, magnesium fatty acid, and aluminum fatty acid (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 mass% aqueous solution at 20 °C (E) At least one of a compound represented by the following chemical formula (I) and a salt thereof R 1 -X-Y (I) In the chemical formula (I), R 1 is a hydrocarbon group having 7 to 25 carbon atoms, X is NH or CONH, Y is H, or (CH2) m NR 2 R 3 provided that when X is NH, Y is not H, m is an integer from 2 to 4, R 2 and R 3 are each H, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, R 2 and R 3 may be the same or different.

[0016] [1-1. Component (A): Water-soluble polymer other than component (D)] The component (A) is, as described above, a water-soluble polymer other than the component (D). In the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure, the water-soluble polymer other than the component (A), that is, 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 agent composition for unvulcanized rubber of the present disclosure by being put into water or heating after being put into water. Thereby, for example, a coating effect on the unvulcanized rubber can be obtained, and an anti-adhesive effect can be obtained. Thus, the component (A) functions as, for example, a film-forming agent. Further, for example, the component (A) and the component (B) are used in combination to exhibit anti-adhesive properties.

[0017] In the liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure, the content of the water-soluble polymer (A) is not particularly limited, but for example, it may be 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 with respect to 100% by mass of the total mass of components other than water (solid content), and for example, it may be 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 20% by mass or more with respect to 100% by mass of the total mass of components other than water, for example, the film-forming effect on the unvulcanized rubber is excellent. Further, when the content of the water-soluble polymer (A) is 30% by mass or more with respect to 100% by mass of the total mass of components other than water, for example, the anti-adhesion effect is excellent. Furthermore, in the liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure, when the content of the water-soluble polymer (A) is 70% by mass or less with respect to the total mass of components other than water, for example, it is excellent in drying property and can be dried quickly.

[0018] The content (blending amount) of the water-soluble polymer (A) in the liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure is not particularly limited, but for example, it may be 3 to 20% by mass, 4 to 18% by mass, or 5 to 16% by mass with respect to the total mass of the liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure. In order to prevent the viscosity of the liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure from rising too much and deteriorating the handling, it is preferable that the content of the water-soluble polymer (A) is 20% by mass or less with respect to the total mass of the liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure.

[0019] The water-soluble polymer (A) may be, for example, a water-soluble polymer having a viscosity of 3 to 300 mPa·s at 25°C in a 2% by mass aqueous solution of the water-soluble polymer (A). By being a water-soluble polymer having a viscosity of 3 mPa·s or more at 25°C in the 2% by mass aqueous solution, for example, an effect of improving the adhesion amount to the unvulcanized rubber can be obtained. By being a water-soluble polymer having a viscosity of 300 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 or 100 mPa·s or more, or 200 mPa·s or less or 100 mPa·s or less.

[0020] The water-soluble polymer (A) is not particularly limited. For example, it may be a polymer having a solubility lower limit of 1 g or more, 10 g or more, or 50 g or more in 100 g of water at 25°C. In the present disclosure, the "polymer" is not particularly limited, but the lower limit of the mass average molecular weight may be, for example, 1000 or more, 5000 or more, or 10,000 or more, and the upper limit of the mass average molecular weight is not particularly limited, but may be, for example, 500,000 or less.

[0021] The type of the water-soluble polymer (A) is not particularly limited, and it may be used alone or in combination of a plurality of types. 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, a polymer having a chemical structure not existing in nature artificially synthesized, or a polymer having a chemical structure existing in nature artificially synthesized. The "natural water-soluble polymer" may be, for example, a polymer having a chemical structure existing in nature extracted or produced from nature. Examples of the synthetic water-soluble polymer include, but are not limited to, carboxymethyl cellulose (CMC), polyacrylic acid, sodium polyacrylate, polyacrylamide, polyvinyl alcohol (PVA), polyvinylpyrrolidone, polyethylene glycol, polyethylene oxide, methyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, 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 the natural water-soluble polymer include, but are not limited to, protein, welan gum, tamarind gum, tamarind seed gum, tragacanth gum, gum arabic, carrageenan, ramzan gum, succinoglycan, tara gum, karaya gum, pectin, alginic acid derivative, cellulose ethers, etc.

[0022] The water-soluble polymer (A) is preferably at least one selected from the group consisting of polyvinyl alcohol, CMC, polyacrylic acid, sodium polyacrylate, methylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, and water-soluble acrylic resin, and more preferably at least one of methylcellulose and hydroxypropylmethylcellulose. From the viewpoint of improving the adhesion amount of the liquid anti-adhesion agent 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-adhesion agent 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 the present disclosure, the "adhesion amount" of the liquid anti-adhesion agent composition for unvulcanized rubber refers to the adhesion amount of all components other than water in the liquid anti-adhesion agent composition for unvulcanized rubber to the surface of the unvulcanized rubber.

[0023] [1-2. Component (B): Metal soap containing component (B1) and component (B2)] In the liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure, the component (B) is a metal soap containing the component (B1) and the component (B2) as described above (hereinafter may be referred to as "metal soap (B)").

[0024] As described above, the component (B1) is at least one compound selected from the group consisting of calcium fatty acid salts and lithium fatty acid salts. The fatty acid may be, for example, a derivative thereof. The derivative of the fatty acid 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 derivatives of the fatty acid. 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, 14 or more carbon atoms, and the upper limit of the number of carbon atoms is not particularly limited, but is, for example, 22 or less, 20 or less, 18 or less. Specific examples of the component (B1) include, for example, calcium caprylate, lithium caprylate, calcium capric acid, lithium capric acid, 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 oil fatty acid, lithium palm kernel oil fatty acid. Among them, calcium stearate is preferred from the viewpoint of high throughput and easy availability at low cost.

[0025] In the liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure, the content of the component (B1) is not particularly limited. However, for example, it may be 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, and for example, it may be 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, based on 100% by mass of the total mass of the components other than water (solid content). When the content of the component (B1) is 5% by mass or more based on 100% by mass of the total mass of the components other than water, for example, the anti-adhesion film has excellent lubricity. Further, when the content of the component (B1) is 60% by mass or less based on 100% by mass of the total mass of the components other than water, for example, it has an excellent effect of suppressing powder scattering and can suppress an increase in the viscosity of the liquid product, so it has excellent handleability.

[0026] The content (blending amount) of the component (B1) in the liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure is not particularly limited. However, for example, it may be 0.5 to 5% by mass, 0.7 to 3% by mass, 1.0 to 3% by mass, or 1.5 to 3% by mass based on the total mass of the liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure.

[0027] As described above, the component (B2) is at least one compound selected from the group consisting of zinc fatty acid, magnesium fatty acid, and aluminum fatty acid. The fatty acid may be, for example, its derivative. The derivative of the fatty acid 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 zinc salts, magnesium salts, and aluminum salts of the derivatives of the fatty acid. 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, 14 or more carbon atoms, and the upper limit of the number of carbon atoms is not particularly limited, but is, for example, 22 or less, 20 or less, 18 or less. Specific examples of the component (B2) include, for example, zinc caprylate, magnesium caprylate, zinc capric acid, magnesium capric acid, 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 mono - octadecanoate, zinc octadecanoate, magnesium octadecanoate, zinc oleate, 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, magnesium castor oil fatty acid. Among them, from the viewpoint of high throughput and easy availability at low cost, zinc stearate and magnesium stearate are preferred.

[0028] In the liquid anti-sticking agent composition for unvulcanized rubber of the present disclosure, the content of the component (B2) is not particularly limited. However, for example, it may be 2.5% by mass or more, 5% by mass or more, 10% by mass or more, or 15% by mass or more, and for example, it may be 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 with respect to 100% by mass of the total mass of components other than water (solid content). When the content of the component (B2) is 2.5% by mass or more with respect to 100% by mass of the total mass of components other than water, for example, the anti-sticking film has excellent lubricity. Further, when the content of the component (B2) is 40% by mass or less with respect to 100% by mass of the total mass of components other than water, for example, it has excellent foaming suppression effect and powder scattering suppression effect, and can suppress the increase in viscosity of the liquid product, so it has excellent handleability.

[0029] The content (blending amount) of the component (B2) in the liquid anti-sticking agent composition for unvulcanized rubber of the present disclosure is not particularly limited. However, for example, it may be 0.5 to 5% by mass, 0.8 to 4% by mass, 1.0 to 3.5% by mass, or 1.5 to 3.5% by mass with respect to the total mass of the liquid anti-sticking agent composition for unvulcanized rubber of the present disclosure.

[0030] In the liquid anti-sticking agent composition for unvulcanized rubber of the present disclosure, the content of the metal soap (B) may be, for example, 20% by mass or more, 30% by mass or more, or 35% by mass or more, and for example, it may be 60% by mass or less, 50% by mass or less, or 40% by mass or less with respect to 100% by mass of the total mass of components other than water (solid content).

[0031] 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 for example, it may be 1.0 or less, 0.9 or less, or 0.8 or less. If it is 0.1 or more, the anti-sticking effect is excellent, and if it is 1.0 or less, the foaming suppression effect is excellent, and the increase in viscosity of the liquid product can be suppressed, so the handleability is excellent.

[0032] [1-3. Component (C): Surfactant other than component (B) and component (E)] In the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure, the content of the component (C), that is, the surfactant other than the component (B) and the component (E) (hereinafter sometimes referred to as "surfactant (C)") is not particularly limited. However, based on 100% by mass of the total mass of the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure, for example, it is 1 to 10% by mass, or 2 to 8% by mass, and based on 100% by mass of the total mass of the components other than water (solid content), for example, it is 10 to 25% by mass. When the content of the surfactant (C) is 10% by mass or more based on 100% by mass of the total mass of the components other than water, for example, the dispersion effect of the metal soap (B) is improved and it becomes difficult to separate. When it is 25% by mass or less, for example, the dispersibility is moderately suppressed, the adhesiveness becomes good, and the 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 based on 100% by mass of the total mass of the components other than water, and may be, for example, 20% by mass or less, 18% by mass or less, or 16% by mass or less. The method for measuring the adhesiveness to the unvulcanized rubber is not particularly limited, but it can be measured, for example, by the measurement method described in the examples below.

[0033] The surfactant (C) improves the adhesiveness to the unvulcanized rubber, for example, by imparting dispersibility in water and improving wettability to the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure. The surfactant (C) is not particularly limited, and only one type may be used or a plurality of types may be used in combination. For example, at least one of an anionic surfactant and a nonionic surfactant may be used. The anionic surfactant is not particularly limited, and 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, and acylaminocarboxylates (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 monosulfates (iii) Sulfonate-type anionic surfactants such as alkane sulfonates, α-olefin sulfonates, linear alkylbenzene sulfonates, α-sulfo fatty acid esters, and dialkyl sulfosuccinates (iv) Phosphate ester-type anionic surfactants such as alkyl phosphate esters, polyoxyalkylene alkyl phosphate esters, polyoxyalkylene alkyl phenyl phosphate esters, and glycerin fatty acid ester monophosphates (v) Polyoxyalkylene alkyl ether-type nonionic surfactants

[0034] The counterions of the anionic surfactant are not particularly limited, but alkali metals such as sodium and potassium, and alkanolamines such as monoethanolamine and diethanolamine are preferred. These may be used alone or in combination of multiple types.

[0035] As the anionic surfactant, a dialkyl sulfosuccinate is preferred, and the Na salt of dioctyl sulfosuccinate is more preferred because an anti-adhesion agent composition with excellent wettability to the surface of the unvulcanized rubber can be obtained.

[0036] 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. The nonionic surfactant of the following formula (1) is presumed to have an effect of effectively enhancing the adhesion to the surface of the unvulcanized rubber of the anti-adhesion agent composition in addition to reducing the surface tension of the anti-adhesion agent composition with respect to the surface of the unvulcanized rubber when used together with the anionic surfactant. However, this presumption does not limit the present disclosure in any way. RO-(AO) n -H (1)

[0037] 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. Further, it may be either saturated or unsaturated. From the viewpoint of excellent dispersibility of the component (A), the number of carbon atoms of R is preferably 12 to 16, and more preferably 12 to 13. AO represents an oxyalkylene group having 2 to 4 carbon atoms, and n is the average number of moles of addition of AO. n is, for example, 1 to 30, 1 to 25, or 2 to 15. Specifically, from the viewpoint of preventing a decrease in surfactant performance and a decrease in the dispersibility of the component (A), n is 1 or more (that is, not 0). Further, from the viewpoint of preventing a decrease in adhesion due to excessive hydrophilicity, n is 30 or less, or 25 or less. If n is in the range of 1 to 30 or 1 to 25, the dispersibility of the component (A) is further improved, and even when the surface of the unvulcanized rubber is highly hydrophobic, it is presumed that the adhesion is improved by imparting sufficient viscoelasticity to the dry coating of the liquid anti-adhesive agent composition for unvulcanized rubber. However, this presumption does not limit the present disclosure in any way.

[0038] The oxyalkylene group having 2 to 4 carbon atoms is, for example, a polymerization unit formed 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) formed by addition of ethylene oxide, an oxypropylene group (PO) formed by addition of propylene oxide, and an oxybutylene group (BO) formed by addition of butylene oxide. (AO) n contains at least an oxyethylene group in its structure. (AO) n When (AO) contains a plurality of types among an oxyethylene group (EO), an oxypropylene group (PO), and an oxybutylene group (BO), these groups may be arranged in a block form or randomly. Preferred (AO) n consists only of an oxyethylene group (EO) from the viewpoint of excellent balance between hydrophilicity and hydrophobicity.

[0039] Specific examples of the nonionic surfactant are not particularly limited, and examples thereof include 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.

[0040] [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) of 4.0 or more in a 2% by mass aqueous solution at 20°C (hereinafter, may be simply referred to as "TI value"). (Hereinafter, may be referred to as "water-soluble polymer (D)"). The TI value can be measured, for example, as follows. Add 2 g of the water-soluble polymer to 98 g of water, mix at 80°C for 30 minutes to completely dissolve it, and then cool to the temperature at which measurement is planned. Then, set the rotation speed of the prepared aqueous solution to 2 rpm and 20 rpm with a BH viscometer and measure the viscosity. The obtained viscosity values are obtained by the following formula (viscosity value obtained at 2 rpm / viscosity value obtained at 20 rpm). The TI value is not particularly limited, and 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. Thereby, for example, the stabilizing effect of the liquid anti-adhesive composition for unvulcanized rubber of the present disclosure can be obtained. Thus, the component (D) acts as a stabilizer, for example.

[0041] The content rate of the water-soluble polymer (D) is not particularly limited, but is, for example, 0.01 to 0.6 mass%, 0.03 to 0.6 mass%, or 0.05 to 0.5 mass% with respect to the total mass of the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure, and may be, for example, 0.01 to 10 mass% with respect to 100 mass% of the total mass of components other than water (solid content). When the content rate of the water-soluble polymer (D) is 0.01 mass% or more with respect to the total mass of components other than water, for example, the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure is less likely to separate, and when it is 10 mass% or less, for example, it is possible to prevent the viscosity of the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure from rising too much and the handling from deteriorating. The content rate of the water-soluble polymer (D) may be, for example, 0.1 mass% or more, or 0.5 mass% or more with respect to the total mass of components other than water, and may be, for example, 8.0 mass% or less, or 4.0 mass% or less.

[0042] 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 of a 2 mass% aqueous solution of the water-soluble polymer (D). By being a water-soluble polymer having a viscosity of 3 mPa·s or more at 25°C of the 2 mass% aqueous solution, for example, an effect of improving the adhesion amount to unvulcanized rubber can be obtained. By being a water-soluble polymer having a viscosity of 300 mPa·s or less of the 2 mass% aqueous solution, for example, an effect of excellent drying property can be obtained. The viscosity of the 2 mass% aqueous solution may be, for example, 10 mPa·s or more, or 100 mPa·s or more, and may be 200 mPa·s or less, or 100 mPa·s or less.

[0043] The water-soluble polymer (D) is not particularly limited, but may be, for example, a polymer having a solubility lower limit of 1 g or more, 10 g or more, or 50 g or more in 100 g of water at 25°C.

[0044] The type of the water-soluble polymer (D) is not particularly limited, and only one type may be used or a plurality of 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. The water-soluble polymer (D) is preferably diutan gum, xanthan gum, guar gum, locust bean gum, gellan gum, etc. having a TI value of 4.0 or more.

[0045] [1-5. Component (E): Defoaming agent] In the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure, the defoaming agent (E) is, as described above, at least one of the compound represented by the above chemical formula (I) and its salt (hereinafter, may be referred to as "defoaming agent (E)"). The content of the defoaming agent (E) is not particularly limited, but is, for example, 0.01 to 5% by mass, 0.03 to 5% by mass, or 0.03 to 2% by mass with respect to 100% by mass of the total mass of the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure, and is, for example, 0.2 to 20% by mass with respect to 100% by mass of the total mass of the components other than water (solid content). The content of the defoaming agent (E) may be, for example, 0.3% by mass or more, 0.4% by mass or more, or 0.5% by mass or more with respect to 100% by mass of the total mass of the components other than water, and may be, for example, 19.5% by mass or less, 19% by mass or less, 15% by mass or less, or 10% by mass or less.

[0046] The defoaming agent (E) is, for example, a compound having a melting point of 80°C or lower. Examples of the compound having a melting point of 80°C or lower 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 lower, the defoaming property is excellent. (E-1) Fatty acid amide (also referred to as fatty acid amide) (E-2) Amidoamine (E-3) At least one of N-alkylalkylene diamine and its fatty acid salt

[0047] The component (E-1) is, for example, in the above chemical formula (I), R 1It is a compound in which the hydrocarbon group has 7 to 25 carbon atoms, X is CONH, and Y is H. The component (E-1) is preferably, for example, 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.

[0048] The component (E-2) is, for example, in the above chemical formula (I), R 1 is a hydrocarbon group having 7 to 25 carbon atoms, X is CONH, and Y is (CH2) m NR 2 R 3 , m is an integer of 2 to 4, R 2 and R 3 are each H, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and R 2 and R 3 may be the same or different. The component (E-2) is preferably, for example, dimethylaminopropylamide palmitate, dimethylaminopropylamide stearate, dimethylaminopropylamide behenate (also referred to as behenamidopropyl dimethylamine), and may be used alone or in combination of two or more.

[0049] The component (E-3) is, for example, in the above chemical formula (I), R 1 is a hydrocarbon group having 7 to 25 carbon atoms, X is NH, and Y is (CH2) m NR 2 R 3 , m is an integer of 2 to 4, R 2 and R 3 are each H, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and R 2 and R 3 may be the same or different. The component (E-2) is preferably, for example, N-alkyl (C14-C18) trimethylenediamine oleate.

[0050] [1-6. Mass ratio of each component] The mass ratio (A) / (B) of the component (A) and the component (B) is not particularly limited, but for example, it is preferably in the range of 0.2 to 4.0. The lower limit value is more preferably 0.4 or more, 0.6 or more, 0.8 or more, or 0.9 or more, and the upper limit value is more preferably 3.0 or less, 2.0 or less, 1.0 or less, or 0.9 or less. If it is within the above range, the anti-adhesion property will be more excellent.

[0051] The mass ratio (A) / (D) of the component (A) and the component (D) is not particularly limited, but for example, it is preferably in the range of 3 to 500. The lower limit value 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 value is more preferably 400 or less, 200 or less, 100 or less, 90 or less, 80 or less, or 75 or less. If it is within the above range, the product stability and handling property will be more excellent.

[0052] The mass ratio (C) / (E) of the component (C) and the component (E) is not particularly limited, but for example, it is preferably in the range of 0.5 to 100. The lower limit value is more preferably 1 or more, 3 or more, 5 or more, 7 or more, or 8 or more, and the upper limit value 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. If it is within the above range, the product stability and handling property will be more excellent.

[0053] The mass ratio (D) / (E) of the component (D) and the component (E) is not particularly limited, but for example, it is preferably in the range of 0.005 to 50. The lower limit value 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 value is more preferably 20 or less, 10 or less, 5 or less, 2 or less, 1 or less, or 0.5 or less. If it is within the above range, the defoaming property and product stability will be more excellent.

[0054] [1-7. Water] In the liquid anti-sticking agent composition for unvulcanized rubber of the present disclosure, the water content is not particularly limited, but may be, for example, 50% by mass or more, 60% by mass or more, or 70% by mass or more, and may be, for example, 95% by mass or less, 90% by mass or less, 85% by mass or less, or 80% by mass or less, based on the total mass of the liquid anti-sticking agent composition for unvulcanized rubber.

[0055] Water, for example, imparts fluidity to the liquid anti-sticking agent composition for unvulcanized rubber of the present disclosure and facilitates handling. Also, water is not particularly limited, and may be, for example, tap water, distilled water, ion-exchanged water, or the like. [1-8. Optional components, etc.] The liquid anti-sticking agent 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-sticking agent composition for unvulcanized rubber of the present disclosure may contain additives such as defoamers, preservatives, wetting aids, viscosity aids, and foreign matter reduction aids as optional components, if necessary.

[0056] The defoamer is not particularly limited, and examples include oil-based defoamers such as castor oil, sesame oil, linseed oil, and animal and vegetable oils; fatty acid ester-based defoamers such as isoamyl stearate, distearyl succinate, ethylene glycol distearate, and butyl stearate; alcohol-based defoamers such as polyoxyalkylene monohydric alcohol, di-t-amylphenoxyethanol, 3-heptanol, and 2-ethylhexanol; ether-based defoamers such as di-t-aminophenoxyethanol, 3-heptyl cellosolve, nonyl cellosolve, and 3-heptyl carbitol; phosphate ester-based defoamers such as tributyl phosphate and tris(butoxyethyl) phosphate; amine-based defoamers such as diamylamine; amide-based defoamers such as polyalkylene amide and acrylate polyamine; mineral oil; silicone oil; and the like. The defoamer may be used alone or in combination of two or more.

[0057] The preservatives are not particularly limited, and examples thereof include derivatives of isothiazolinone, pyridine, and iodine. The derivatives of the isothiazolinone are not particularly limited, and examples thereof include benzisothiazolinone (BIT), methylisothiazolinone (MIT, MI), chloromethylisothiazolinone (CMIT, CMI), octylisothiazolinone (OIT, OI), dichlorooctylisothiazolinone (DCOIT, DCOI), and their derivatives. The derivatives of the pyridine are not particularly limited, and examples thereof include pyridinethiol and their derivatives. The derivatives of the iodine are not particularly limited, and examples thereof include iodo-2-propynyl butylcarbamate and their derivatives. For example, only one type of the preservative may be used, or a plurality of types may be used in combination.

[0058] The wetting aids are not particularly limited, and examples thereof include alcohols. 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, and adducts of ethylene oxide or propylene oxide with polyhydric alcohols. The wetting aids may be used alone or in combination of a plurality of types.

[0059] The viscosity of the liquid anti-sticking agent composition for unvulcanized rubber of the present disclosure is not particularly limited. For example, for the reason that it is difficult to separate and has good handleability (handling), the viscosity measured at 25 °C, with a BH-type viscometer, 20 rpm, and after 10 rotations, 3 days after the production of the liquid anti-sticking agent 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 the separation of the liquid anti-sticking agent composition for unvulcanized rubber, it is preferable to set the viscosity of the liquid anti-sticking agent composition for unvulcanized rubber to 3,000 mPa·s or more. From the viewpoint of suppressing or preventing the deterioration of handling such as becoming difficult to take out from the container, it is preferable to set the viscosity of the liquid anti-sticking agent composition for unvulcanized rubber to 25,000 mPa·s or less.

[0060] [2. Method for producing the liquid anti-sticking agent composition for unvulcanized rubber] The method for producing the liquid anti-sticking agent composition for unvulcanized rubber of the present disclosure is not particularly limited. For example, it can be produced by mixing all the components of the liquid anti-sticking agent composition for unvulcanized rubber (the above components (A) to (E) and water, and optional components blended as required). The mixing order, the apparatus and equipment used for mixing, etc. are not particularly limited. For example, there is a method of mixing water and a water-soluble polymer (the above component (A), the above component (D)), a surfactant (the above component (C)), an antifoaming agent (the above component (E)), and then mixing a metal soap (the above component (B)) and other optional components. As the apparatus used for mixing, as described above, it is not particularly limited. For example, an apparatus having a configuration with stirring blades in a container can be used. Specifically, for example, general liquid mixers, vortex mixers, static mixers, homogenizers, line homomixers, and other liquid mixers can be mentioned.

[0061] [3. Method of use, etc. of the liquid anti-sticking agent composition for unvulcanized rubber] The method of using the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure is not particularly limited, and for example, it may be the same as or similar to the method of using a general liquid anti-adhesive agent composition for unvulcanized rubber. Specifically, the method of using the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure is, for example, as follows, but is not limited thereto.

[0062] The method for anti-adhesive treatment of unvulcanized rubber using the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure may, for example, as described above, have an anti-adhesive treatment step of attaching the components (A) to (E) in the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure to the surface of the unvulcanized rubber for anti-adhesive treatment. The attachment to the surface of the unvulcanized rubber can be carried out, for example, by the wet method described later. The anti-adhesive treated unvulcanized rubber thus anti-adhesively treated can be stored, for example, by stacking or folding, without the unvulcanized rubbers adhering to each other. Further, such a method for anti-adhesive treatment of unvulcanized rubber can also be said to be, for example, a method for producing anti-adhesive treated unvulcanized rubber.

[0063] The liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure may be used as it is, or may be further diluted with water and used in the state of an aqueous dilution (aqueous dispersion). In the liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure, the concentration at the time of attaching to the surface of the unvulcanized rubber is not particularly limited, but the total mass of the components other than water is, for example, 0.5% by mass or more, 1% by mass or more, or 2% by mass or more with respect to the total mass of the liquid anti-adhesion agent composition for unvulcanized rubber, and may be, for example, 15% by mass or less, 10% by mass or less, or 5% by mass or less. If the concentration is not too high, for example, the effects of low scattering property and fast drying can be obtained. If the concentration is not too low, for example, the effects of high anti-adhesion property and high lubricity can be obtained. The liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure can exhibit high anti-adhesion property even when the concentration at the time of attaching to the surface of the unvulcanized rubber is low, and thus can exhibit high anti-adhesion property with a small adhesion amount. Also, the viscosity at the time of attaching to the surface of the unvulcanized rubber 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, 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, the effects of low scattering property and fast drying can be obtained. If the viscosity is not too low, for example, the effects of high anti-adhesion property and high lubricity can be obtained.

[0064] The anti-adhesion treatment step is, for example, as described above, attaching the liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure or the aqueous dilution of the liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure to the surface of the unvulcanized rubber, and further volatilizing water to attach the components (A) to (E) in the liquid anti-adhesion agent composition for unvulcanized rubber of the present disclosure to the surface of the unvulcanized rubber. More specifically, the anti-adhesion treatment step may include, for example, a step of attaching the liquid anti-adhesion agent composition for unvulcanized rubber to the surface of the unvulcanized rubber and a drying step of drying the liquid anti-adhesion agent composition on the surface of the unvulcanized rubber to form a film on the surface of the unvulcanized rubber. Such an anti-adhesion treatment step is, for example, called a wet method. The wet method is not particularly limited, and can be carried out in the same manner as the wet method in a general liquid anti-adhesion agent composition for unvulcanized rubber.

[0065] In the step of attaching the liquid anti-adhesion agent composition for the unvulcanized rubber, for example, it is preferable to attach the liquid anti-adhesion agent composition for the unvulcanized rubber to the unvulcanized rubber in a high-temperature state (for example, about 80 to 150 °C) due to the heat when formed into a sheet shape or the like.

[0066] As specific methods for the step of attaching the liquid anti-adhesion agent composition for the unvulcanized rubber, for example, there are a method of spraying the liquid anti-adhesion agent composition for the unvulcanized rubber onto the unvulcanized rubber with a shower device, a dip method of immersing the unvulcanized rubber in a tank containing the liquid anti-adhesion agent composition for the unvulcanized rubber for a short time, and the like. Also, a method of applying the liquid anti-adhesion agent composition for the unvulcanized rubber to the unvulcanized rubber using a coating device may be adopted, or these methods may be used in combination as appropriate.

[0067] According to the liquid anti-adhesion agent composition for the unvulcanized rubber of the present disclosure, as described above, it is excellent in anti-adhesion effect and defoaming property.

[0068] There is no particular limitation on the rubber types to which the liquid anti-adhesion agent composition for the unvulcanized rubber of the present disclosure can be applied, and any unvulcanized rubber may be used. Examples of the rubber types include rubbers such as natural rubber (NR), butadiene rubber (BR), styrene-butadiene rubber (SBR), IIR (butyl rubber), EPDM (ethylene-propylene rubber), and rubbers in which a plurality of these are mixed.

Example

[0069] Next, examples of the present disclosure will be described. However, the present disclosure is not limited to the following examples.

[0070] [Example 1] The liquid anti-adhesion agent composition for the unvulcanized rubber of Example 1 was produced as follows.

[0071] 820 g of water was placed in a reaction vessel and heated to 80°C or higher. Then, 40 g of hydroxypropylmethylcellulose (Methocel 60SH-4000, degree of methoxy group substitution 1.9, number of moles 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 hydroxypropylmethylcellulose is a water-soluble polymer and corresponds to the component (A) in the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure. After cooling the mixture obtained by mixing for 2 hours to 30°C or lower, further, 15 g of calcium laurate (manufactured by Taihei Chemical Industry Co., Ltd.), 15 g of magnesium myristate (manufactured by Taihei Chemical Industry Co., Ltd.), 0.5 g of gellan gum (Kelcogel, manufactured by Sumitomo Pharma Food & Chemical Co., Ltd.), 0.3 g of oleic acid amide (manufactured by Kanto Chemical Co., Inc.), 10 g of coconut alcohol EO adduct (Leox (registered trademark) CC-150, manufactured by Lion Specialty Chemicals Co., Ltd.), 5 g of sodium alpha olefin sulfonate (Lipolan (registered trademark) LB-840, manufactured by Lion Specialty Chemicals Co., Ltd.), and 1 g of a preservative (Slaoff EX, manufactured by Osaka Gas Chemical Co., Ltd.) were added and stirred to obtain a liquid anti-adhesive agent composition for unvulcanized rubber. The calcium laurate is a metal soap and corresponds to the component (B-1) in the liquid anti-adhesive agent 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 agent composition for unvulcanized rubber of the present disclosure. The gellan gum corresponds to the component (D) in the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure. The oleic acid amide is an antifoaming agent and corresponds to the component (E) in the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure. Both the coconut alcohol EO adduct and the sodium alpha olefin sulfonate are surfactants and correspond to the component (C) in the liquid anti-adhesive agent composition for unvulcanized rubber of the present disclosure. The preservative corresponds to an optional component other than the components (A) to (E).

[0072] [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 described below, liquid anti-adhesive agent 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 trade names (product names), manufacturers, and characteristics (compositions) of the respective raw materials used in the production of the liquid anti-adhesive agent compositions for unvulcanized rubber of Examples 2 to 35 and Comparative Examples 1 to 5 are shown in Table 1 below.

[0073]

Table 1

[0074] [Manufacture and Performance Evaluation of Aqueous Dilution of Liquid Anti-Adhesive Agent Composition for Unvulcanized Rubber] The liquid anti-adhesive agent compositions for unvulcanized rubber of the respective Examples and Comparative Examples were diluted 20-fold (mass ratio) with water to produce an aqueous dilution of the liquid anti-adhesive agent composition for unvulcanized rubber (anti-adhesive agent suspension). Using this aqueous dilution of the liquid anti-adhesive agent composition for unvulcanized rubber, an anti-adhesive treatment of the unvulcanized rubber was performed, and the respective performances of anti-adhesion, foaming property (defoaming property), lubricity, scattering property, stability, and viscosity were evaluated. The anti-adhesive treatment method and the evaluation methods for the respective performances are shown below.

[0075] <Evaluation> (1) Rubber for Evaluation For various evaluations, the following unvulcanized SBR rubber and unvulcanized NR rubber were used as the rubber for evaluation. (Unvulcanized SBR Rubber) To 100 parts by mass of SBR (manufactured by Asahi Kasei Corporation, trade name "Tufdene 4850"), 30 parts by mass of SAF carbon (manufactured by Mitsubishi Chemical Corporation, trade name "Diablack A"), 15 parts by mass of JSR AROMA (process oil) (manufactured by Nippon Sun Oil Co., Ltd., trade name "Aroma 790"), 3 parts by mass of zinc white (manufactured by Hakusuitech Co., Ltd., zinc white No. 2), 1 part by mass of stearic acid (manufactured by NOF Corporation, Tsubaki), 1 part by mass of 6PPD (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name "Nocrack 6C"), 1 part by mass of CBS (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name "Noxeller CZ-G"), and 1.5 parts by mass of sulfur (manufactured by Tsurumi Chemical Co., Ltd.) were blended (total 152.5 parts by mass), and unvulcanized SBR rubber was used.

[0076] Unvulcanized NR rubber Based on 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 "Seast 6"), 15 parts by mass of JSR AROMA (process oil) (manufactured by Nippon Sun Oil Co., Ltd., trade name "Aroma 790"), 3 parts by mass of zinc oxide (manufactured by Hakusuitech Co., Ltd., zinc oxide type 2), 1 part by mass of stearic acid (manufactured by NOF Corporation, Tsubaki), 1 part by mass of 6PPD (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name "Nocrack 6C"), 1 part by mass of CBS (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name "Noxeller CZ-G"), and 1.5 parts by mass of sulfur (manufactured by Tsurumi Chemical Co., Ltd.) were blended (total 162.5 parts by mass), and unvulcanized NR rubber was used.

[0077] (2) Evaluation of anti-adhesion property The above unvulcanized rubber was kneaded on an open roll at a temperature of 80 to 120 °C to obtain a rubber sheet (thickness: 5 to 8 mm, 60 cm × 15 cm). Immediately after being fed out, the rubber sheet was immersed in 1 L of a liquid anti-adhesion agent composition aqueous dilution (anti-adhesion agent suspension, temperature 40 °C) obtained by diluting the liquid anti-adhesion agent composition for unvulcanized rubber obtained in Examples 1 to 35 and Comparative Examples 1 to 5 with water 20-fold for about 1 second. Then, the rubber sheet was quickly pulled up vertically and left standing vertically at room temperature for natural drying. In this way, the anti-adhesion treatment of the rubber sheet (unvulcanized rubber) was carried out.

[0078] The rubber sheet after the anti-adhesion treatment was cut into 6 cm × 15 cm and two pieces were overlapped to form a test piece in a laminated state. A load of 1 t / m 2 was applied to the test piece in the laminated state in the vertical direction from one side, and it was left at 60 °C for 12 hours.

[0079] After that, the test piece was returned to room temperature, and a 180° peel test was carried out using a tensile testing machine [AGS-500D type, SHIMADZU], and the peel resistance (N / cm) was measured at a pulling speed of 300 mm / min. The smaller the peel resistance (N / cm), the better the anti-adhesion property.

[0080] (3) Evaluation of Foaming Property (Defoaming Property) A 1-L anti-adhesive agent suspension (at a temperature of 40 °C) obtained by diluting the liquid anti-adhesive agent composition for unvulcanized rubber 20-fold with water was prepared, and after circulating it for 5 minutes from a height of 40 cm from the liquid surface using a circulation pump, the foam height (mL) was measured. The lower the foam height, the better the foaming property (that is, the better the defoaming property).

[0081] (4) Evaluation of Lubricity The anti-adhesive treatment of the rubber sheet (unvulcanized rubber) was carried out in the same manner as in the evaluation of the anti-adhesion property in (2) above. Next, the dried unvulcanized rubber sheet after the anti-adhesive 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 inclination angle at the time of sliding and falling was measured. The lower the sliding start angle, the better the lubricity.

[0082] (5) Evaluation of Scattering Property The anti-adhesive treatment of the rubber sheet (unvulcanized rubber) was carried out in the same manner as in the evaluation of the anti-adhesion property in (2) above. Next, the dried unvulcanized rubber sheet after the anti-adhesive treatment was cut into a rectangle of 6 × 15 cm and its weight was measured. The front and back surfaces of this rubber were brushed 10 times with a brush and then the weight was measured again to calculate the scattering amount. The smaller the scattering amount, the better the scattering property.

[0083] (6) Evaluation of Stability 100 mL of the liquid anti-adhesive agent composition for unvulcanized rubber before dilution 20-fold (mass ratio) with water was placed in a sealed container and left standing in a constant temperature bath at 20 °C. After standing for 1 week, the appearance was visually checked for the presence or absence of separation. If no separation of the anti-adhesive agent composition for rubber can be visually confirmed, it indicates good stability.

[0084] (7) Evaluation of Viscosity The viscosity of the liquid anti-adhesive agent composition for unvulcanized rubber before dilution 20-fold (mass ratio) with water was measured 3 days after production. For the viscosity measurement, a BH-type viscometer (Tokimec, Inc., trade name "Viscometer BII type") was used, and the viscosity after 10 rotations at 20 rpm at 25 °C was measured.

[0085] The types and compositions of the raw materials in the liquid anti - sticking agent compositions for unvulcanized rubber of Examples 1 to 35 and Comparative Examples 1 to 5, and the evaluation results of the anti - sticking properties and foaming properties evaluated as described above are summarized in Tables 2 to 5 below. In Tables 2 to 5 below, the numerical values indicating the usage amounts of each raw material (including water) are the contents (mass %) with respect to the total mass (including water) of the liquid anti - sticking agent composition for unvulcanized rubber.

[0086]

Table 2

[0087]

Table 3

[0088]

Table 4

[0089]

Table 5

[0090] As shown in Tables 2 to 5 above, the liquid anti-sticking agent compositions for unvulcanized rubber of Examples 1 to 35 had good anti-sticking properties and foaming properties. Also, although not described in Tables 2 to 5 above, the lubricity (75 degrees or less), scattering property (0.5 or less), stability (stable for one week or more), and liquid feeding property (viscosity) (3000 to 25000 mPa·s) were also all good. On the other hand, the liquid anti-sticking agent composition for unvulcanized rubber of Comparative Example 1 that did not use component (A) had significantly inferior anti-sticking properties compared to the examples. The liquid anti-sticking agent composition for unvulcanized rubber of Comparative Example 2 that did not use component (B) had significantly inferior anti-sticking properties compared to the examples. Also, since the lubricity was 90 degrees, it was inferior compared to the examples. The liquid anti-sticking agent composition for unvulcanized rubber of Comparative Example 3 that did not use component (D) had inferior foaming properties compared to the examples. Also, the stability was not stable for one week or more and was inferior compared to the examples. The liquid anti-sticking agent composition for unvulcanized rubber of Comparative Example 4 that did not use component (E) had inferior foaming properties compared to the examples. The liquid anti-sticking agent composition for unvulcanized rubber of Comparative Example 5 that did not use component (C) had significantly inferior anti-sticking properties compared to the examples. Also, since the lubricity was 90 degrees, it was inferior compared to the examples. The stability was not stable for one week or more and was inferior compared to the examples.

[0091] <Supplementary Note> Some or all of the above-described embodiments and examples may be described as follows in the supplementary note below, but are not limited thereto. (Supplementary Note 1) A liquid anti-sticking agent composition for unvulcanized rubber, 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 component (B1) and the following component (B2) (B1) At least one compound selected from the group consisting of calcium fatty acid and lithium fatty acid (B2) At least one compound selected from the group consisting of zinc fatty acid, magnesium fatty acid, and aluminum fatty acid (C) A surfactant other than the above component (B) and the following component (E) 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 mass% aqueous solution at 20°C (E) At least one of the compound represented by the following chemical formula (I) and its salt R 1 -X-Y (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 (CH2) m NR 2 R 3 wherein when X is NH, Y is not H, m is an integer of 2 to 4, R 2 and R 3 are each H, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, R 2 and R 3 may be the same or different. (Appendix 2) The liquid anti-adhesive agent composition for unvulcanized rubber according to Appendix 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 agent composition for unvulcanized rubber according to Appendix 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 agent 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-alkylalkylene diamine and its fatty acid salt (Appendix 5) Based on 100% by mass of the total mass of components other than water, the component (A) is 20% by mass or more, the component (B) is 20 - 60% by mass, the component (C) is 10 - 25% by mass, the component (D) is 0.01 - 10% by mass, the component (E) is 0.2 - 20% by mass, A liquid anti - sticking agent composition for unvulcanized rubber according to any one of Supplementary Notes 1 to 4, containing the above. (Supplementary Note 6) Based on 100% by mass of the total mass of components other than water, the component (A) is 30% by mass or more, A liquid anti - sticking agent composition for unvulcanized rubber according to Supplementary Note 5, containing the above. (Supplementary Note 7) A liquid anti - sticking agent composition for unvulcanized rubber water - dilution liquid, characterized by containing a liquid anti - sticking agent composition for unvulcanized rubber according to any one of Supplementary Notes 1 to 6 and water. (Supplementary Note 8) An unvulcanized rubber, characterized in that the components (A) to (E) in the liquid anti - sticking agent composition for unvulcanized rubber according to any one of Supplementary Notes 1 to 6 adhere to the surface.

[0092] This application claims the priority based on Japanese Patent Application No. 2023 - 064947 filed on April 12, 2023, and incorporates all of its disclosures herein.

Claims

1. A liquid anti-adhesive agent composition for unvulcanized rubber, 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 component (B1) and the following component (B2) (B1) At least one compound selected from the group consisting of calcium fatty acid and lithium fatty acid (B2) At least one compound selected from the group consisting of zinc fatty acid, magnesium fatty acid, and aluminum fatty acid (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 2% by mass aqueous solution at 20 °C of 4.0 or more (E) At least one of a compound represented by the following chemical formula (I) and its salt R １ -X-Y (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 wherein, when X is NH, Y is not H, m is an integer of 2 to 4, R ２ and R ３ is each H, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, R ２ and R ３ may be the same or different.

2. The liquid anti-adhesive agent 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.

3. The liquid anti-adhesive agent composition for unvulcanized rubber according to Claim 1, wherein the component (E) is a compound having a melting point of 80 °C or lower.

4. The liquid anti-adhesive agent 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-alkylalkylene diamine and its fatty acid salt

5. Based on 100% by mass of the total mass of components other than water, the component (A) is 20% by mass or more, the component (B) is 20 to 60% by mass, the component (C) is 10 to 25% by mass, the component (D) is 0.01 to 10% by mass, the component (E) is 0.2 to 20% by mass, The liquid anti-adhesive agent composition for unvulcanized rubber according to Claim 1, which contains.

6. A liquid anti-adhesive agent composition water dilution for unvulcanized rubber, characterized by containing the liquid anti-adhesive agent composition for unvulcanized rubber according to any one of Claims 1 to 5 and water.

7. An unvulcanized rubber, characterized in that the components (A) to (E) in the liquid anti-adhesive agent composition for unvulcanized rubber according to any one of Claims 1 to 5 are adhered to the surface.

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