Anti-adhesive composition for unvulcanized rubber, water-diluted anti-adhesive composition for unvulcanized rubber, and unvulcanized rubber

Abstract

To provide an anti-adhesion agent composition for unvulcanized rubber, containing smectite, and exhibiting superior anti-adhesion performance and redispersibility with reduced risk of solidification.SOLUTION: An anti-adhesion agent composition for unvulcanized rubber comprises the following components (A) to (E), where the mass ratio (B-1) / (B-2) of the component (B-1) to the component (B-2) is 0.2 to 3. (A) Smectite. (B) An inorganic salt comprising the component (B-1) and the component (B-2): (B-1) inorganic sodium salt and (B-2) magnesium carbonate. (C) Surfactant. (D) Metal soap. (E) At least one compound selected from the group consisting of inorganic silicate other than component (A), metal oxide, and calcium carbonate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to an anti-adhesive composition for unvulcanized rubber, a water-diluted anti-adhesive composition for unvulcanized rubber, and unvulcanized rubber. [Background technology]

[0002] BACKGROUND ART In rubber production and processing sites, an anti-adhesion agent is applied to the surface of rubber (for example, unvulcanized rubber) to prevent the rubber from adhering to other surfaces (for example, Patent Document 1, etc.). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-001720 Summary of the Invention [Problem to be solved by the invention]

[0004] Smectite, which is highly effective in improving adhesion resistance, is often used as a component of anti-adhesive agents for unvulcanized rubber. Anti-adhesive agents for unvulcanized rubber containing smectite have high viscosity when used as a treatment liquid (aqueous dilution of an anti-adhesive agent composition for unvulcanized rubber). When dried, they can form a strong dry film (anti-adhesive coating), resulting in excellent adhesion resistance. On the other hand, if the smectite content (amount) in the anti-adhesive agent for unvulcanized rubber is high, the agent may bind due to water absorption, potentially resulting in solidification (blocking). Furthermore, when the anti-adhesive agent for unvulcanized rubber is dispersed in water for use, the smectite tends to aggregate, resulting in so-called splinters, which can lead to poor dispersion and require a long time to achieve uniform dispersion and dissolution. On the other hand, if the smectite content (amount) in the anti-adhesive agent for unvulcanized rubber is reduced, adhesion resistance and other properties tend to decrease.

[0005] Therefore, an object of the present disclosure is to provide an anti-adhesive composition for unvulcanized rubber, an aqueous dilution of the anti-adhesive composition for unvulcanized rubber, and unvulcanized rubber, which contain smectite and have excellent solidified disintegration strength, anti-adhesion properties, and re-dispersibility. [Means for solving the problem]

[0006] In order to achieve the above object, the anti-adhesive composition for unvulcanized rubber of the present disclosure comprises: Contains the following components (A) to (E), The composition is characterized in that the mass ratio (B-1) / (B-2) of the following component (B-1) to the following component (B-2) is 0.2 to 3. (A) Smectite (B) an inorganic salt containing the following component (B-1) and the following component (B-2): (B-1) Inorganic sodium salt (B-2) Magnesium carbonate (C) Surfactant (D) Metal soap (E) At least one compound selected from the group consisting of inorganic silicates, metal oxides, and calcium carbonate other than the component (A).

[0007] The water-diluted solution of the anti-adhesive composition for unvulcanized rubber of the present disclosure is characterized by containing the anti-adhesive composition for unvulcanized rubber of the present disclosure and water.

[0008] The unvulcanized rubber of the present disclosure is characterized in that the components (A) to (E) in the anti-adhesive composition for unvulcanized rubber of the present disclosure are adhered to the surface. [Effects of the Invention]

[0009] According to the present disclosure, it is possible to provide an anti-adhesive composition for unvulcanized rubber, an aqueous dilution of the anti-adhesive composition for unvulcanized rubber, and unvulcanized rubber, which contain smectite and have excellent solidified product disintegration strength, anti-adhesion properties, and re-dispersibility. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to the following description.

[0011] In the present disclosure, "alkyl" includes, for example, straight-chain or branched alkyl. In the present disclosure, the alkyl group is not particularly limited, but 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, 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, and an icosyl group.

[0012] In the present disclosure, "alkylene" includes, for example, a straight-chain alkylene (methylene or polymethylene) or a branched alkylene. In the present disclosure, the alkylene group is not particularly limited, but 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, and a decamethylene group.

[0013] [1. Anti-adhesive composition for unvulcanized rubber] As described above, the anti-adhesive composition for unvulcanized rubber of the present disclosure contains the following components (A) to (E), and is characterized in that the mass ratio (B-1) / (B-2) of the following component (B-1) to the following component (B-2) is in the range of 0.2 to 3. (A) Smectite (B) an inorganic salt containing the following component (B-1) and the following component (B-2): (B-1) Inorganic sodium salt (B-2) Magnesium carbonate (C) Surfactant (D) Metal soap (E) At least one compound selected from the group consisting of inorganic silicates, metal oxides, and calcium carbonate other than the component (A).

[0014] [1-1. Component (A): Smectite] In the anti-adhesive agent for unvulcanized rubber of the present disclosure, the smectite (hereinafter sometimes referred to as "smectite (A)") as component (A) is not particularly limited, and examples thereof include smectites such as montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, and stevensite, as well as bentonite containing montmorillonite. Component (A) may contain only one type of smectite, or two or more types of smectite may be used in combination.

[0015] The component (A) functions, for example, as a component responsible for anti-adhesion properties. Specifically, it is believed that the component (A) can exhibit anti-adhesion properties by forming a coating. The content of the component (A) in the anti-adhesion agent for unvulcanized rubber of the present disclosure is not particularly limited and can be selected depending on the purpose. For example, the content may be 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more, relative to 100% by mass of the total mass of the components (A) to (E). For example, the content of the component (A) of 10% by mass or more relative to 100% by mass of the total mass of the components (A) to (E) is preferably 10% by mass or more, since good anti-adhesion properties can be obtained. On the other hand, the content of the component (A) of 65% by mass or less is preferably 10% by mass or more, since blocking of the product can be suppressed. The content (amount) of the component (A) in the anti-adhesive agent for unvulcanized rubber of the present disclosure is not particularly limited, and may be, for example, 10 to 65 mass %, 15 to 60 mass %, or 20 to 50 mass % relative to the total mass of the anti-adhesive agent composition for unvulcanized rubber of the present disclosure.

[0016] The component (A) (smectite) may be used in the form of an inorganic compound containing smectite (e.g., powder of the inorganic compound). In this case, the method for measuring the smectite content in the inorganic compound is not particularly limited, but can be measured, for example, by the following measurement method.

[0017] (Method for measuring smectite content) Inorganic compounds containing smectite are analyzed by X-ray diffraction, and the smectite content is calculated from the intensity of the diffraction peak due to smectite that appears around 2θ = 7°. The analytical conditions for X-ray diffraction when quantifying the smectite content are as follows: X-ray diffraction analysis conditions Measurement device: X'Pert PRO MRD (PANalytical) Target: Cu Tube voltage: 45kV ·Tube current: 40mA Scan axis: Goniometer Scanning range: 5°~60° Step size: 0.03° Step time: 12.7 seconds Divergence slit: 1 / 2° Scattering slit: 1° Receiving slit: None

[0018] [1-2. Component (B): Inorganic salt (component (B-1) and component (B-2))] In the anti-adhesive agent for unvulcanized rubber of the present disclosure, the inorganic salt of component (B) (hereinafter sometimes referred to as "inorganic salt (B)") includes, as described above, an inorganic sodium salt (component (B-1)) and magnesium carbonate (component (B-2)). The inorganic sodium salt (component (B-1)) is not particularly limited and includes, for example, the following:

[0019] The component (B-1) may be, for example, at least one inorganic sodium salt selected from sodium carbonate, sodium chloride, sodium phosphate, and sodium sulfate. Sodium carbonate, sodium chloride, and sodium phosphate are particularly preferred in terms of their effectiveness in improving adhesion prevention.

[0020] It is believed that the combined use of an inorganic sodium salt (component (B-1)) and magnesium carbonate (component (B-2)), for example, increases the viscosity of the aqueous diluted solution of the anti-adhesive agent for unvulcanized rubber of the present disclosure, thereby increasing the adhesion amount and improving the anti-adhesive properties, and promotes the aggregation of component (A), thereby improving the redispersibility. The content of component (B-1) in the anti-adhesive agent for unvulcanized rubber of the present disclosure is not particularly limited and can be selected depending on the purpose. It may be, for example, 0.2% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.2% by mass or more, or 1.5% by mass or more, or, for example, 10% by mass or less, 5% by mass or less, 4% by mass or less, or 3.5% by mass or less, relative to 100% by mass of the total mass of components (A) to (E). The content of component (B-2) in the anti-adhesive agent for unvulcanized rubber of the present disclosure is not particularly limited and can be selected depending on the purpose. For example, it may be 0.2% by mass or more, 0.5% by mass or more, 1% by mass or more, 1.2% by mass or more, or 1.5% by mass or more, relative to 100% by mass of the total mass of components (A) to (E). It may also be 10% by mass or less, 5% by mass or less, 4% by mass or less, or 3.5% by mass or less, relative to 100% by mass of the total mass of components (A) to (E). It is preferable that the content of each of components (B-1) and (B-2) is 0.2% by mass or more, since this improves adhesion prevention and redispersibility. On the other hand, it is preferable that the content of each of components (B-1) and (B-2) is 10% by mass or less, since this improves both adhesion prevention and redispersibility. The total content of the components (B-1) and (B-2) in the anti-adhesive agent for unvulcanized rubber of the present disclosure is not particularly limited, and may be, for example, 1 to 12 mass%, 1.5 to 10 mass%, or 2 to 8 mass%, relative to the total mass of the anti-adhesive agent composition for unvulcanized rubber of the present disclosure. When the total content of the components (B-1) and (B-2) is, for example, 1 to 12 mass%, 1.5 to 10 mass%, or 2 to 8 mass%, relative to 100 mass% of the total mass of the components (A) to (E), it is preferable because improved adhesion prevention and redispersibility can be obtained.

[0021] On the other hand, since the component (B-1) promotes blocking of the product due to moisture absorption, in order to impart a blocking suppression effect, the mass ratio (B-1) / (B-2) of the component (B-1) to the component (B-2) is set to 0.2 to 3 as described above, and may be, for example, 0.3 to 3, 0.5 to 2, or 0.6 to 1.7.

[0022] [1-3. Component (C): Surfactant] In the anti-adhesive agent for unvulcanized rubber of the present disclosure, the surfactant (C) (component (C)) functions to impart, for example, wettability and dispersibility in water to the anti-adhesive agent for unvulcanized rubber. The surfactant (C) (component (C)) is not particularly limited, and examples thereof include the following (1) to (5). Furthermore, as the surfactant (C), only one type of surfactant may be used, or two or more types may be used in combination. (1) 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 (2) Sulfates such as higher alcohol sulfates, polyoxyalkylene higher alcohol sulfates, alkylphenyl ether sulfates, polyoxyalkylene alkylphenyl ether sulfates, and glycerin fatty acid ester monosulfates. Terephthalate anionic surfactants (3) Sulfonic acid type anionic surfactants such as alkanesulfonates, α-olefinsulfonates, linear alkylbenzenesulfonates, α-sulfofatty acid ester salts, and dialkylsulfosuccinates (4) Phosphate ester-type anionic surfactants such as alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, polyoxyalkylene alkylphenyl phosphate ester salts, and glycerin fatty acid ester monophosphate ester salts. (5) Polyoxyalkylene alkyl ether type nonionic surfactants

[0023] The counter ion of the anionic surfactant is not particularly limited, and 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 of two or more.

[0024] As the anionic surfactant, a sulfonic acid or sulfate type anionic surfactant is preferred, as this will give an anti-adhesive agent suspension (water-diluted solution) that has better wettability with the surface of unvulcanized rubber, and α-olefin sulfonate and dialkyl sulfosuccinate are preferred. As the α-olefin sulfonate, α-olefin sulfonic acid sodium salt "Lipolan (registered trademark) LB-840" (manufactured by Lion Specialty Chemicals Co., Ltd.) is more preferred, and as the dialkyl sulfosuccinate, dioctyl sulfosuccinate sodium salt is more preferred.

[0025] The nonionic surfactant is not particularly limited, and 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), together with the anionic surfactant, is presumed to reduce the surface tension of the anti-adhesive agent suspension (aqueous dispersion) with respect to the surface of the unvulcanized rubber, and also to effectively increase the adhesion of the anti-adhesive agent to the surface of the unvulcanized rubber. However, this presumption does not limit the present disclosure in any way. RO-(AO)nH (1)

[0026] 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. It may be 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 the component (A). AO represents an oxyalkylene group having 2 to 4 carbon atoms, and n is the average number of moles of AO added. n may be, for example, 1 to 30, 1 to 25, or 1 to 20. Specifically, from the viewpoint of preventing a decrease in surface activity and a decrease in the dispersibility of the component (A), n is preferably 1 or greater (i.e., not 0). Furthermore, from the viewpoint of preventing a decrease in adhesion due to excessively high hydrophilicity, n is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less. When n is preferably in the range of 1 to 30, more preferably 1 to 25, and even more preferably 1 to 20, it is presumed that the dispersibility of the component (A) is further improved, and that even when the unvulcanized rubber surface is highly hydrophobic, sufficient viscoelasticity is imparted to the coating, thereby improving adhesion. However, this presumption does not limit the present disclosure in any way.

[0027] An oxyalkylene group having 2 to 4 carbon atoms is, for example, a polymerized unit formed by addition polymerization of an alkylene oxide having 2 to 4 carbon atoms. 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 (EO) in its structure, and may be composed of only an oxyethylene group (EO), or may contain an oxyethylene group (EO) and another oxyalkylene group. When (AO)n contains multiple types of oxyethylene groups (EO), oxypropylene groups (PO), and oxybutylene groups (BO), these groups may be arranged in a block pattern or randomly. (AO)n is preferably composed of only an oxyethylene group (EO) in order to achieve an excellent balance between hydrophilicity and hydrophobicity.

[0028] The content of the surfactant (C) in the anti-adhesive agent for unvulcanized rubber of the present disclosure is not particularly limited and can be selected depending on the purpose. For example, it may be 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more, or 5% by mass or more, relative to 100% by mass of the total mass of the components (A) to (E). It may also be 25% by mass or less, 20% by mass or less, 15% by mass or less, or 12% by mass or less. When the content of the surfactant (C) is equal to or greater than the lower limit, problems such as cissing due to insufficient wettability of the anti-adhesive liquid (water-diluted anti-adhesive composition) to the rubber are unlikely to occur. When the content is equal to or less than the upper limit, problems such as excessive foaming and overflow from equipment during use are unlikely to occur. The content (amount) of the surfactant (C) in the anti-adhesive agent for unvulcanized rubber of the present disclosure is not particularly limited and may be, for example, 1 to 25% by mass, 2 to 20% by mass, or 3 to 15% by mass, relative to the total mass of the anti-adhesive agent composition for unvulcanized rubber of the present disclosure.

[0029] [1-4. Component (D): Metal soap] [Component (D)] The at least one metal soap (D) selected from the group consisting of zinc, magnesium, and aluminum (component (D), hereinafter also referred to as "metal soap (D)") is not particularly limited, and examples thereof include zinc caprylate, magnesium caprylate, zinc caprate, magnesium caprate, zinc laurate, magnesium 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, and aluminum stearate. Examples of suitable metal soaps include at least one selected from the group consisting of zinc leate, 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 tallow fatty acid, magnesium tallow fatty acid, zinc castor oil fatty acid, and magnesium castor oil fatty acid. From the viewpoint of improving adhesion prevention, the metal soap (D) is preferably at least one selected from the group consisting of calcium fatty acids having 12 to 18 carbon atoms and zinc fatty acids having 12 to 18 carbon atoms, with calcium stearate being particularly preferred.

[0030] The metal soap (D) is contained in the anti-adhesive agent for unvulcanized rubber of the present disclosure together with component (A), and is thought to reduce the hardness of the dried coating of the anti-adhesive agent formed on the surface of the unvulcanized rubber while maintaining sufficient anti-adhesive properties, thereby reducing foreign matter in the rubber. Furthermore, the metal soap (D) can also improve anti-adhesive properties, lubricity, and powder flowability.

[0031] The content of component (D) in the anti-adhesive agent for unvulcanized rubber of the present disclosure is not particularly limited and can be selected depending on the purpose. For example, it may be 5% by mass or more, 7% by mass or more, 8% by mass or more, or 10% by mass or more, relative to 100% by mass of the total mass of components (A) to (E). By setting the content of component (D) at or above the lower limit of the total mass of components (A) to (E), 100% by mass of the total mass of components (A) to (E), good anti-adhesive properties can be obtained, and the sliding between the product and its storage container, and between the rubber and equipment, is more likely to be improved. On the other hand, it is preferable for the content of component (D) to be at or below the upper limit, as this leads to cost reduction. The content (amount) of the component (D) in the anti-adhesive agent for unvulcanized rubber of the present disclosure is not particularly limited, but may be, for example, 5 to 30 mass %, 10 to 20 mass %, or 10 to 15 mass % relative to the total mass of the anti-adhesive agent composition for unvulcanized rubber of the present disclosure.

[0032] The mass ratio (A) / (D) of the component (A) to the component (D) is, for example, 0.3 to 10, and may be 0.6 to 7 or 1 to 5. When the mass ratio (A) / (D) is within the above range, the effects of the present invention, such as excellent solidified disintegration strength, anti-adhesion properties, and redispersibility, are easily achieved. The mass ratio (B) / (D) of the component (B) to the component (D) is, for example, 0.03 to 3, and may be 0.06 to 2 or 0.1 to 1. When the mass ratio (B) / (D) is within the above range, the effects of the present invention, such as excellent solidified disintegration strength, anti-adhesion properties, and redispersibility, are easily achieved.

[0033] [1-5. Ingredient (E)] In the anti-adhesive agent for unvulcanized rubber of the present disclosure, at least one compound (E) selected from the group consisting of inorganic silicates, metal oxides, and calcium carbonate (component (E)) other than component (A) is thought to function, for example, mainly as a lubricant (to impart slipperiness) and also contribute to improving powder flowability.

[0034] In the component (E), the inorganic silicate is not particularly limited, and examples thereof include silicates such as kaolin (also called kaolin clay), aluminum silicate, calcium silicate, clay, talc, mica, sericite, nepheline, syenite, etc. The metal oxide is not particularly limited, and examples thereof include metal oxides such as silica, alumina, magnesium oxide, antimony trioxide, titanium oxide, white carbon, and iron oxide.

[0035] The content of component (E) in the anti-adhesive agent for unvulcanized rubber of the present disclosure is not particularly limited and can be selected depending on the purpose, but may be, for example, 0.1% by mass or more, 1% by mass or more, 5% by mass or more, 10% by mass or more, or 20% by mass or more, relative to 100% by mass of the total mass of components (A) to (E). It may also be, for example, 76% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less. When the content of component (E) is equal to or greater than the lower limit, the sliding properties between the product and its storage container, and between the rubber and equipment, tend to be better, and this is preferable because it also leads to cost reduction.

[0036] When calcium carbonate is contained as the component (E), the content of calcium carbonate may be, for example, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 75% by mass or more, or 90% by mass or more, relative to 100% by mass of the total mass of the components (E). When the content of calcium carbonate is equal to or more than the lower limit, for example, the hardness of the dried coating can be lowered, and foreign matter in the rubber can be reduced.

[0037] The mass ratio (D) / (E) of the component (D) to the component (E) may be, for example, 0.1 or more, 0.2 or more, 0.3 or more, or 0.4 or more, and may be, for example, 20 or less, 15 or less, 10 or less, 5 or less, 3 or less, 1 or less, or 0.5 or less. When the mass ratio (D) / (E) is within the above range, for example, both excellent adhesion prevention and reduction of foreign matter can be achieved.

[0038] [1-6. Optional ingredients, etc.] The anti-adhesive composition for unvulcanized rubber of the present disclosure may or may not contain optional components other than the components (A) to (E). For example, the anti-adhesive composition for unvulcanized rubber of the present disclosure may contain additives such as antifoaming agents, preservatives, wettability aids, viscosity aids, and foreign matter reduction aids as optional components, as needed.

[0039] 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 amides and acylate polyamines; mineral oil; and silicone oil. The defoaming agents may be used alone or in combination.

[0040] Examples of preservatives include, but are not limited to, isothiazolinone, pyridine, and iodine derivatives. Examples of isothiazolinone derivatives include, but are not limited to, benzisothiazolinone (BIT), methylisothiazolinone (MIT, MI), chloromethylisothiazolinone (CMIT, CMI), octylisothiazolinone (OIT, OI), dichlorooctylisothiazolinone (DCOIT, DCOI), and derivatives thereof. Examples of pyridine derivatives include, but are not limited to, pyridinethiol and derivatives thereof. Examples of iodine derivatives include, but are not limited to, iodo-2-propargylbutylcarbamic acid and derivatives thereof. For example, the preservatives may be used alone or in combination.

[0041] The wettability aid is not particularly limited, but examples thereof include alcohols, and more specific 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. Only one type of the wettability aid may be used, or multiple types may be used in combination.

[0042] The anti-adhesive agent for unvulcanized rubber of the present disclosure is preferably in the form of powder, granules, or granules. The average particle size of the anti-adhesive agent is preferably 0.003 to 30 mm, more preferably 0.003 to 25 mm, and even more preferably 0.005 to 20 mm. If it is above the lower limit of the above range, it is less likely to scatter, and if it is below the upper limit, it is less likely to solidify. The average particle size of the powdered anti-adhesive agent for unvulcanized rubber is preferably 0.005 to 0.2 mm, and more preferably 0.005 to 0.1 mm.

[0043] [2. Method for producing anti-adhesive composition for unvulcanized rubber] The method for producing the anti-adhesive agent composition for unvulcanized rubber of the present disclosure is not particularly limited. For example, the anti-adhesive agent composition for unvulcanized rubber can be produced by mixing all of the components of the anti-adhesive agent for unvulcanized rubber, i.e., components (A) to (E), with optional components that are blended as needed. Examples of the mixing device include a device equipped with a stirring blade inside a container. Specific examples include powder mixers capable of oscillating or stirring, such as ribbon mixers and vertical screw mixers. Multifunctional powder mixers combining multiple stirring devices, such as Super Mixer (manufactured by Kawata Co., Ltd.), High-Speed ​​Mixer (manufactured by Earth Technica Co., Ltd.), Newgram Machine (manufactured by Seishin Enterprise Co., Ltd.), and SV Mixer (manufactured by Kobelco Eco Solutions Co., Ltd.), can also be used. Dry grinders such as jaw crushers, gyratory crushers, cone crushers, roll crushers, impact crushers, hammer crushers, rod mills, ball mills, vibrating rod mills, vibrating ball mills, disc mills, jet mills, and cyclone mills may also be used.

[0044] [3. Method of use of anti-adhesive composition for unvulcanized rubber] The method of using the adhesion-preventive composition for unvulcanized rubber of the present disclosure is not particularly limited, and may be the same as or equivalent to the method of using a general adhesion-preventive composition for unvulcanized rubber. Specific examples of the method of using the adhesion-preventive composition for unvulcanized rubber of the present disclosure are as follows, but are not limited thereto.

[0045] The method for preventing adhesion of unvulcanized rubber using the adhesion-preventive agent composition for unvulcanized rubber of the present disclosure may, for example, include an adhesion-preventive treatment step in which the components (A) to (E) of the adhesion-preventive agent composition for unvulcanized rubber of the present disclosure are adhered to the surface of the unvulcanized rubber to perform adhesion-preventive treatment, as described above. Adhesion to the surface of the unvulcanized rubber can be performed, for example, by a wet method as described below. Unvulcanized rubber that has been treated for adhesion prevention in this manner will not adhere to each other even when stored, for example, stacked or folded. Furthermore, such an adhesion-preventive treatment method for unvulcanized rubber can also be considered, for example, as a method for producing adhesion-preventive treated unvulcanized rubber.

[0046] The 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 solution (water dilution). In the anti-adhesive composition for unvulcanized rubber of the present disclosure, the concentration when applied to the surface of unvulcanized rubber is not particularly limited. The total mass of components other than water relative to the total mass of the anti-adhesive composition for unvulcanized rubber 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. 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 anti-adhesive properties and high lubricity can be obtained. The anti-adhesive composition for unvulcanized rubber of the present disclosure can exhibit high anti-adhesive properties even when applied to the surface of unvulcanized rubber at a low concentration, and therefore can exhibit high anti-adhesive properties with a small amount of application. The viscosity when applied to the surface of 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, or 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.

[0047] The adhesion-preventing treatment step may be, for example, as described above, a step of adhering the adhesion-preventing composition for unvulcanized rubber of the present disclosure or a water-diluted solution of the adhesion-preventing composition for unvulcanized rubber of the present disclosure to the surface of the unvulcanized rubber, and then volatilizing the water to adhere the components (A) to (E) of the adhesion-preventing composition for unvulcanized rubber of the present disclosure to the surface of the unvulcanized rubber. More specifically, the adhesion-preventing treatment step may include, for example, an adhesion-preventing composition adhering step of adhering the adhesion-preventing composition for unvulcanized rubber of the present disclosure to the surface of the unvulcanized rubber, and a drying step of drying the adhesion-preventing 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-preventing treatment step is referred to, for example, as a wet method. The wet method is not particularly limited and may be performed, for example, in the same manner as a general wet method for adhesion-preventing compositions for unvulcanized rubber.

[0048] In the step of applying the anti-adhesive composition for unvulcanized rubber, it is preferable to apply the anti-adhesive composition for unvulcanized rubber to unvulcanized rubber that is in a high temperature state (for example, about 80 to 150°C) due to the heat generated when the unvulcanized rubber is molded into a sheet or the like.

[0049] Specific methods for the adhesion-preventive composition for unvulcanized rubber application step include, for example, a method in which the adhesion-preventive composition for unvulcanized rubber is sprayed onto the unvulcanized rubber using a shower device, a dipping method in which the unvulcanized rubber is immersed for a short period of time in a tank containing the adhesion-preventive composition for unvulcanized rubber, etc. Alternatively, a method in which the adhesion-preventive composition for unvulcanized rubber is applied to the unvulcanized rubber using an application device may be employed, and these methods may be used in combination as appropriate.

[0050] As described above, the anti-adhesive composition for unvulcanized rubber according to the present disclosure has excellent anti-adhesive effect and anti-foaming property.

[0051] The type of rubber to which the anti-adhesive composition for unvulcanized rubber of the present disclosure can be applied is not particularly limited, as long as it is unvulcanized rubber. Examples of the rubber include natural rubber (NR), butadiene rubber (BR), styrene butadiene rubber (SBR), IIR (butyl rubber), EPDM (ethylene propylene rubber), and the like, as well as a mixture of two or more of these rubbers. [Example]

[0052] Next, examples of the present disclosure will be described, but the present disclosure is not limited to the following examples.

[0053] [Examples 1 to 40 and Comparative Examples 1 to 6] Each component was kneaded in the weight (mass) ratio shown in Tables 1 to 5 below to prepare a powdered anti-adhesive agent for unvulcanized rubber (hereinafter also referred to as anti-adhesive agent) for each example, consisting of a uniform powder. Each resulting anti-adhesive agent was then added to tap water with stirring to prepare a water-diluted anti-adhesive agent composition with a concentration of 3 mass%. In Examples 1 to 40, all of the components (A) to (E) were blended as shown in Tables 1 to 4 below. In contrast, as shown in Table 5 below, of the components (A) to (E), Comparative Example 1 did not blend component (B-1), and Comparative Example 2 did not blend component (B-2). In Comparative Examples 3 to 5, all of the components (A) to (E) were blended, but the mass ratios (B-1) / (B-2) were 5.0, 0.15, and 4.0, respectively. In Comparative Example 6, of the components (A) to (E), component (D) was not blended. The product names (trade names) and manufacturers of each component listed in Tables 1 to 5 below are shown in Table 6 below.

[0054] [Table 1]

[0055] [Table 2]

[0056] [Table 3]

[0057] [Table 4]

[0058] [Table 5]

[0059] [Table 6]

[0060] <Evaluation> (1) Rubber for evaluation For the various evaluations, the following unvulcanized SBR rubber and unvulcanized NR rubber were used as evaluation rubbers.

[0061] (Unvulcanized SBR rubber) The unvulcanized SBR rubber used was 151.5 parts by mass (total: 151.5 parts by mass) blended with 100 parts by mass of SBR (manufactured by Asahi Kasei Corporation, trade name "Tufden 4850"), 30 parts by mass of SAF carbon (manufactured by Mitsubishi Chemical Corporation, trade name "Diablack A"), 15 parts by mass of JSRAROMA (process oil) (manufactured by Japan Sun 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 Corporation, Tsubaki), 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.).

[0062] (Unvulcanized NR rubber) The unvulcanized NR rubber used was 162.5 parts by weight, blended with 100 parts by weight of NR (RSS#3), 10 parts by weight of white carbon (manufactured by Tosoh Silica Corporation, product name "Nipsil VN-3"), 30 parts by weight of ISAF black (manufactured by Tokai Carbon Co., Ltd., product name "Seast 6"), 15 parts by weight of JSRAROMA (process oil) (manufactured by Japan Sun Oil Co., Ltd., product name "Aroma 790"), 3 parts by weight of zinc oxide (manufactured by Hakusui Tech Co., Ltd., zinc oxide type 2), 1 part by weight of stearic acid (manufactured by NOF Corporation, product name "Tsubaki"), 1 part by weight of 6PPD (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., product name "Nocrac 6C"), 1 part by weight of CBS (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., product name "Noccela CZ-G"), and 1.5 parts by weight of sulfur (manufactured by Tsurumi Chemical Co., Ltd.).

[0063] (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). Immediately after being unwound, the rubber sheet was immersed for approximately 1 second in 1 L of an aqueous solution (temperature: 40°C) of an anti-adhesive agent diluted with water, which was obtained by stirring and dispersing the anti-adhesive agent composition for unvulcanized rubber obtained in each of Examples 1 to 40 and Comparative Examples 1 to 6 in water for 1 hour or more to a concentration of 3% by mass. The rubber sheet was then quickly pulled up vertically and allowed to stand in a vertical position at room temperature and allowed to dry naturally. In this way, the anti-adhesive treatment of the rubber sheet (unvulcanized rubber) was carried out. The rubber sheet was then cut into 6 cm x 15 cm pieces, and two pieces were stacked together to form a laminate. The test piece in this laminated state was then subjected to a 1 t / m sieve in the vertical direction from one side. 2 A load of 1000 kJ / cm was applied and the specimen was left at 60°C for 12 hours. After that, the specimen was returned to room temperature and a 180° peel test was performed using a tensile tester (AGS-500D, Shimadzu Corporation) to measure the peel resistance (N / cm) at a pulling rate of 300 mm / min.

[0064] (3) Evaluation of redispersibility An aqueous dilution of the anti-adhesive agent for unvulcanized rubber was prepared in the same manner as in "(2) Evaluation of adhesion prevention properties" above. Next, the aqueous dilution (suspension) of the anti-adhesive agent for unvulcanized rubber was placed in a 100 ml measuring cylinder, shaken up and down 10 times, and then allowed to stand in a thermostatic chamber at 20°C. After 24 hours, the measuring cylinder was shaken up and down, and the number of shakes required until the solid content at the bottom of the measuring cylinder was completely dispersed was measured. The fewer the number of shakes, the better the redispersibility was judged to be.

[0065] (4) Powder discharge performance (powder fluidity) The anti-adhesive compositions for unvulcanized rubber obtained in Examples 1 to 40 and Comparative Examples 1 to 6 were filled into 500 mL resin containers with a discharge port diameter of 2.2 cm and a 50° inclination angle, and the powder surface was smoothed by tapping. The containers were then left to stand in a humid heat storage cabinet (IG-401, YAMATO) adjusted to a temperature of 40°C and a humidity of 90% RH. After 7 days, the containers were removed, and with the discharge port open, they were struck with a metal rod, and the powder discharge behavior was visually observed. The evaluation criteria were as follows: ○: Full amount can be discharged ×: Unable to discharge the entire amount (blocking)

[0066] (5) Solidified material collapse strength (blocking property) The anti-adhesive compositions for unvulcanized rubber obtained in Examples 1 to 40 and Comparative Examples 1 to 6 were filled into a circular resin container with an inner diameter of 3.2 cm and a height of 1.9 cm. After smoothing the powder surface by tapping, the container was left to stand in a humid heat storage cabinet (IG-401, YAMATO) adjusted to a temperature of 40°C and a humidity of 90% RH. After 7 days, the powder solid was removed from the container, and with a circular resin plate with a diameter of 3.2 cm placed on top of the powder solid, it was crushed using a round spring-type rod-shaped tension gauge (Ohba Keiki) and the weight (kg) at the time of collapse was measured.

[0067] The types and compositions of raw materials in the anti-adhesive compositions for unvulcanized rubber of Examples 1 to 40 and Comparative Examples 1 to 6, and the evaluation results of the anti-adhesive properties and foaming properties evaluated as described above, are summarized in Tables 1 to 5.

[0068] As shown in Tables 1 to 5, the adhesion-preventive compositions for unvulcanized rubber of Examples 1 to 40 were all good in adhesion prevention, redispersibility, and solidified product disintegration strength (blocking property). In contrast, the adhesion-preventive compositions for unvulcanized rubber of Comparative Examples 1 and 3 were inferior in redispersibility compared to the Examples. The adhesion-preventive compositions for unvulcanized rubber of Comparative Examples 2, 4, and 6 were inferior in adhesion prevention compared to the Examples. The adhesion-preventive composition for unvulcanized rubber of Comparative Example 5 was inferior in redispersibility and solidified product disintegration strength compared to the Examples. In addition, the adhesion-preventive compositions for unvulcanized rubber of Comparative Examples 5 and 6 were inferior in powder discharge property compared to the Examples.

[0069] <Additional Notes> Some or all of the above embodiments and examples may be described as, but are not limited to, the following supplementary notes. (Appendix 1) Contains the following components (A) to (E), 1. An anti-adhesive composition for unvulcanized rubber, characterized in that the mass ratio (B-1) / (B-2) of the following component (B-1) to the following component (B-2) is 0.2 to 3: (A) Smectite (B) an inorganic salt containing the following component (B-1) and the following component (B-2): (B-1) Inorganic sodium salt (B-2) Magnesium carbonate (C) Surfactant (D) Metal soap (E) At least one compound selected from the group consisting of inorganic silicates, metal oxides, and calcium carbonate other than the component (A). (Appendix 2) With respect to 100% by mass of the total mass of the components (A) to (E), 10 to 50 mass% of the component (A), 1 to 5 mass % of the component (B-1), 1 to 5 mass% of the component (B-2), 2 to 25 mass% of the component (C), 10 to 30 mass% of the component (D), 0.1 to 76% by mass of the component (E), Attachment 1, an anti-adhesive composition for unvulcanized rubber comprising: (Appendix 3) 10. A water-diluted anti-adhesive composition for unvulcanized rubber, comprising the anti-adhesive composition for unvulcanized rubber according to claim 1 or 2, and water. (Appendix 4) 10. An unvulcanized rubber having the components (A) to (E) in the anti-adhesive composition for unvulcanized rubber according to claim 1 or 2 adhered to the surface thereof.

Claims

1. Contains the following components (A) to (E): the mass ratio (B-1) / (B-2) of the following component (B-1) to the following component (B-2) is 0.2 to 3; With respect to 100% by mass of the total mass of the following components (A) to (E), 10 to 50% by mass of the following component (A), 1 to 5% by mass of the following component (B-1), 1 to 5 mass% of the following component (B-2), 2 to 25% by mass of the following component (C), 10 to 30% by mass of the following component (D), 0.1 to 50% by mass of the following component (E), Including, The component (E) contains calcium carbonate, An anti-adhesive composition for unvulcanized rubber, characterized in that the content of the calcium carbonate is 20% by mass or more relative to 100% by mass of the total mass of the component (E). (A) Smectite (B) an inorganic salt containing the following component (B-1) and the following component (B-2): (B-1) Inorganic sodium salt (B-2) Magnesium carbonate (C) Surfactant (D) Metal soap (E) calcium carbonate and, optionally, at least one compound selected from the group consisting of inorganic silicates and metal oxides other than the component (A);

2. An anti-adhesive composition for unvulcanized rubber as described in claim 1, wherein component (D) is a calcium salt of a fatty acid having 12 to 18 carbon atoms.

3. An anti-adhesive composition for unvulcanized rubber according to claim 1, wherein the mass ratio (A) / (D) of component (A) to component (D) is 1 to 5.

4. An anti-adhesive composition for unvulcanized rubber according to claim 1, wherein the mass ratio (D) / (E) of component (D) to component (E) is 0.2 to 1.

5. 5. A water-diluted anti-adhesive composition for unvulcanized rubber, comprising the anti-adhesive composition for unvulcanized rubber according to claim 1 and water.

6. 5. An unvulcanized rubber having the components (A) to (E) in the adhesion preventive composition for unvulcanized rubber according to any one of claims 1 to 4 adhered to the surface thereof.

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