Anti-adhesion agent composition for unvulcanized rubber, aqueous dilution of Anti-adhesion agent 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-adhesion agent composition for unvulcanized rubber, an aqueous dilution of the anti-adhesion 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-adhesion agent is adhered to the surface of the rubber (for example, Patent Document 1, etc.).

Prior Art Documents

Patent Documents

[0003]

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] As a component of the anti-adhesion agent for unvulcanized rubber, smectite having a high effect of improving anti-adhesion property is often used. The anti-adhesion agent for unvulcanized rubber containing smectite has a high viscosity when used as a treatment liquid (aqueous dilution of the anti-adhesion agent composition for unvulcanized rubber), and a strong dried film (anti-adhesion film) can be formed when it is dried, so it has excellent anti-adhesion property. On the other hand, when the content (blending amount) of smectite in the anti-adhesion agent for unvulcanized rubber is increased, it may adhere due to water absorption, which may cause a solidification risk (blocking). In addition, when the anti-adhesion agent for unvulcanized rubber is dispersed in water for use, smectite tends to aggregate, so-called lumping is likely to occur, resulting in poor dispersion, and it may take a long time for uniform dispersion and dissolution. On the contrary, when the content (blending amount) of smectite in the anti-adhesion agent for unvulcanized rubber is decreased, the anti-adhesion property and the like tend to decrease.

[0005] Therefore, an object of the present disclosure is to provide an anti-adhesion agent composition for unvulcanized rubber, an aqueous dilution of the anti-adhesion agent composition for unvulcanized rubber, and unvulcanized rubber, which contain smectite and are excellent in solidified product collapse strength, anti-adhesion property, and redispersibility. [Means for Solving the Problem]

[0006] In order to achieve the above object, the anti-sticking agent 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 0.2 to 3. (A) Smectite (B) 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 aqueous dilution of the anti-sticking agent composition for unvulcanized rubber of the present disclosure is characterized by containing the anti-sticking agent 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-sticking agent composition for unvulcanized rubber of the present disclosure are adhered to the surface. [Advantages of the Invention]

[0009] According to the present disclosure, it is possible to provide an anti-sticking agent composition for unvulcanized rubber, an aqueous dilution of the anti-sticking agent composition for unvulcanized rubber, and unvulcanized rubber, which contain smectite and are excellent in solidified product collapse strength, anti-sticking property, and redispersibility. [Embodiments for Carrying Out the Invention]

[0010] Hereinafter, the present disclosure will be specifically described with examples. However, the present disclosure is not limited by the following description.

[0011] 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.

[0012] 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.

[0013] [[1. Antisticking agent composition for unvulcanized rubber]] As described above, the antisticking agent 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) and the following component (B-2) is in the range of 0.2 to 3. (A) Smectite (B) 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 silicate, metal oxide, and calcium carbonate other than the component (A)

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

[0015] The component (A) functions, for example, as a component responsible for anti-blocking properties. Specifically, for example, it is considered that the anti-blocking property can be exhibited when the component (A) forms a film. The content of the component (A) in the anti-blocking agent for unvulcanized rubber of the present disclosure is not particularly limited and can be selected according to the purpose. However, based on the total mass of 100% by mass of the components (A) to (E), for example, it 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, and may be 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less. When the content of the component (A) is 10% by mass or more based on the total mass of 100% by mass of the components (A) to (E), it is preferable because good anti-blocking properties can be obtained. On the other hand, when the content of the component (A) is 65% by mass or less, it is preferable because the blocking suppression effect of the product can be obtained. The content (blending amount) of the component (A) in the anti-blocking agent for unvulcanized rubber of the present disclosure is not particularly limited, but for example, it may be 10 to 65% by mass, 15 to 60% by mass, or 20 to 50% by mass based on the total mass of the anti-blocking agent composition for unvulcanized rubber of the present disclosure.

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

[0017] (Method for measuring smectite content) An inorganic compound containing smectite is analyzed by X-ray diffraction, and the smectite content is calculated from the diffraction peak intensity derived from smectite that appears near 2θ = 7°. The analysis conditions for X-ray diffraction when quantifying the smectite content shall be as follows. X-ray diffraction analysis conditions · Measuring device: X‘Pert PRO MRD (manufactured by PANalytical) · Target: Cu · Tube voltage: 45 kV · Tube current: 40 mA · Scan axis: Gonio · Scan range: 5° to 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 salts (Component (B-1) and Component (B-2))] In the anti-adhesion agent for unvulcanized rubber of the present disclosure, the inorganic salt (hereinafter, may be referred to as "inorganic salt (B)") which is the component (B) includes an inorganic sodium salt (component (B-1)) and magnesium carbonate (component (B-2)) as described above. The inorganic sodium salt (component (B-1)) is not particularly limited, and for example, it is as follows.

[0019] The component (B-1) may be at least one or more inorganic sodium salts selected from, for example, sodium carbonate, sodium chloride, sodium phosphate, and sodium sulfate. In particular, sodium carbonate, sodium chloride, and sodium phosphate are preferable in terms of the effect of improving anti-adhesion properties.

[0020] The inorganic sodium salt (component (B-1)) and magnesium carbonate (component (B-2)) are considered to improve the anti-adhesion property by, for example, increasing the adhesion amount due to thickening of the water-diluted anti-adhesion agent for unvulcanized rubber of the present disclosure when used in combination, and improving the redispersibility by promoting the aggregation of the component (A). The content of the component (B-1) in the anti-adhesion agent for unvulcanized rubber of the present disclosure is not particularly limited and can be selected according to the purpose. However, based on the total mass of 100% by mass of the components (A) to (E), 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, and may be, for example, 10% by mass or less, 5% by mass or less, 4% by mass or less, or 3.5% by mass or less. The content of the component (B-2) in the anti-adhesion agent for unvulcanized rubber of the present disclosure is not particularly limited and can be selected according to the purpose. However, based on the total mass of 100% by mass of the components (A) to (E), 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, and may be, for example, 10% by mass or less, 5% by mass or less, 4% by mass or less, or 3.5% by mass or less. When the content of the component (B-1) and the component (B-2) is 0.2% by mass or more respectively based on the total mass of 100% by mass of the components (A) to (E), it is preferable because the effect of improving the anti-adhesion property and redispersibility can be obtained. On the other hand, when the content of the component (B-1) and the component (B-2) is 10% by mass or less respectively, it is preferable because the anti-adhesion property and redispersibility can be better balanced. The total content of the component (B-1) and the component (B-2) in the anti-adhesion agent for unvulcanized rubber of the present disclosure is not particularly limited. For example, based on the total mass of the anti-adhesion agent composition for unvulcanized rubber of the present disclosure, it may be 1 to 12% by mass, 1.5 to 10% by mass, or 2 to 8% by mass. When the total content of the component (B-1) and the component (B-2) is, for example, 1 to 12% by mass, 1.5 to 10% by mass, or 2 to 8% by mass based on the total mass of 100% by mass of the components (A) to (E), it is preferable because the effect of improving the anti-adhesion property and redispersibility can be obtained.

[0021] On the other hand, since the component (B-1) promotes the blocking of the product by 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 0.2 to 3 as described above, and for example, it may be 0.3 to 3, 0.5 to 2, or 0.6 to 1.7.

[0022] [1-3. Component (C): Surfactant] In the anti-blocking agent for unvulcanized rubber of the present disclosure, the surfactant (C) (component (C)) functions to impart wettability and dispersibility in water to the anti-blocking agent for unvulcanized rubber, for example. The surfactant (C) (component (C)) is not particularly limited, and examples thereof include the following (1) to (5). Further, the surfactant (C) may use only one type of surfactant, 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 acylaminocarboxylates (2) 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 (3) Sulfonic acid type anionic surfactants such as alkane sulfonates, α-olefin sulfonates, linear alkylbenzene sulfonates, α-sulfo fatty acid esters, and dialkyl sulfosuccinates (4) 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 (5) Polyoxyalkylene alkyl ether type nonionic surfactants

[0023] ​The counter ion of the anionic surfactant is not particularly limited, and alkali metals such as sodium and potassium, and alkanolamines such as monoethanolamine and diethanolamine are preferable. These may be used alone or in combination of two or more.

[0024] As the anionic surfactant, since an anti-adhesive agent suspension (aqueous dilution) with excellent wettability with the surface of the unvulcanized rubber can be obtained, it is preferably a sulfonic acid type or sulfuric acid type anionic surfactant, and α-olefin sulfonate and dialkyl sulfosuccinate are preferable. As the α-olefin sulfonate, sodium α-olefin sulfonate "Lipolan (registered trademark) LB-840" (manufactured by Lion Specialty Chemicals Co., Ltd.) is preferable, and as the dialkyl sulfosuccinate, sodium dioctyl sulfosuccinate is more preferable.

[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) is presumed to have an effect of effectively enhancing the adhesion of the anti-adhesive agent to the surface of the unvulcanized rubber in addition to reducing the surface tension of the anti-adhesive agent suspension (aqueous dispersion) with respect to the surface of the unvulcanized rubber together with the anionic surfactant. However, this presumption does not limit the present disclosure in any way. RO-(AO)n-H (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. Also, it may be either saturated or unsaturated. The carbon number of R is preferably 12 to 16, 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 performance and a decrease in the dispersibility of the component (A), n is preferably 1 or more (i.e., not 0). Further, from the viewpoint of preventing a decrease in adhesion due to excessive hydrophilicity, n is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less. If n is preferably in the range of 1 to 30, more preferably in the range of 1 to 25, and even more preferably in the range of 1 to 20, it is presumed that the dispersibility of the component (A) is further improved, and even when the surface of the unvulcanized rubber is highly hydrophobic, the adhesion is improved by imparting sufficient viscoelasticity to the coating. However, this presumption does not limit the present disclosure in any way.

[0027] The oxyalkylene group having 2 to 4 carbon atoms is, for example, a polymer unit formed by the 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 the addition of ethylene oxide, an oxypropylene group (PO) formed by the addition of propylene oxide, and an oxybutylene group (BO) formed by the addition of butylene oxide. (AO)n contains at least an oxyethylene group (EO) in its structure, and may consist only of the oxyethylene group (EO), or may contain the oxyethylene group (EO) and further other oxyalkylene groups. When (AO)n contains a plurality of types among the oxyethylene group (EO), the oxypropylene group (PO), and the oxybutylene group (BO), these groups may be arranged in a block form or randomly. (AO)n is preferably composed only of the oxyethylene group (EO) from the viewpoint of, for example, excellent balance between hydrophilicity and hydrophobicity.

[0028] The content rate of the said component (C) in the antisticking agent for unvulcanized rubber of this disclosure is not particularly limited and can be selected according to the purpose. However, with respect to 100% by mass of the total mass of the said components (A) to (E), 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, and for example, it may be 25% by mass or less, 20% by mass or less, 15% by mass or less, or 12% by mass or less. If the content rate of the said surfactant (C) is at least the said lower limit value, problems such as repellency occurring due to insufficient wettability of the antisticking liquid (antisticking agent composition water dilution) to the rubber are less likely to occur, and if it is at most the said upper limit value, problems such as an increase in foaming and overflowing from equipment during use are less likely to occur. The content rate (blending amount) of the said component (C) in the antisticking agent for unvulcanized rubber of this disclosure is not particularly limited, but for example, it may be 1 to 25% by mass, 2 to 20% by mass, or 3 to 15% by mass with respect to the total mass of the antisticking agent composition for unvulcanized rubber of this disclosure.

[0029] [1-4. Component (D): Metal Soap] [Component (D)] At least one metal soap (D) (component (D), which may also be referred to as "metal soap (D)" hereinafter) selected from the group consisting of zinc, magnesium, and aluminum is not particularly limited. For example, zinc caprylate, magnesium caprylate, zinc capric acid, magnesium capric acid, zinc laurate, magnesium laurate, zinc myristate, magnesium myristate, zinc palmitate, magnesium palmitate, zinc stearate, magnesium stearate, aluminum stearate, aluminum tristearate, aluminum distearate, aluminum monostearate, 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. At least one metal soap selected from the group consisting of the above can be mentioned. In addition, in terms of the effect of improving the anti-adhesion property, the metal soap (D) is preferably, for example, at least one metal soap 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, and particularly preferably calcium stearate.

[0030] When the metal soap (D) is contained in the anti-adhesion agent for unvulcanized rubber of the present disclosure together with the component (A), it is considered that while having sufficient anti-adhesion property, the hardness of the dry film of the anti-adhesion agent formed on the surface of the unvulcanized rubber is reduced, and foreign matters in the rubber are reduced. In addition, the metal soap (D) can also improve the anti-adhesion property, lubricity, and powder fluidity.

[0031] The content rate of the said component (D) in the anti - sticking agent for unvulcanized rubber of the present disclosure is not particularly limited and can be selected according to the purpose. However, based on 100% by mass of the total mass of the said components (A) - (E), 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, and may be 30% by mass or less, 20% by mass or less, or 15% by mass or less. By setting the content rate of the said component (D) to be not less than the lower limit value based on 100% by mass of the total mass of the said components (A) - (E), good anti - sticking property can be obtained, and it is preferable because the slipperiness between the product and its storage container, and between the rubber and the equipment becomes better. On the other hand, if the content rate of the said component (D) is not more than the upper limit value, it is preferable because it leads to cost reduction. The content rate (blending amount) of the said component (D) in the anti - sticking agent for unvulcanized rubber of the present disclosure is not particularly limited, but for example, it may be 5 - 30% by mass, 10 - 20% by mass, or 10 - 15% by mass based on the total mass of the anti - sticking agent composition for unvulcanized rubber of the present disclosure.

[0032] The mass ratio (A) / (D) of the said component (A) and the said component (D) is, for example, 0.3 - 10, and may be 0.6 - 7, 1 - 5. When the mass ratio (A) / (D) is within the above range, the excellent cured product collapse strength, anti - sticking property, and redispersibility, which are the effects of the invention of the present disclosure, are easily obtained. The mass ratio (B) / (D) of the said component (B) and the said component (D) is, for example, 0.03 - 3, and may be 0.06 - 2, 0.1 - 1. When the mass ratio (B) / (D) is within the above range, the excellent cured product collapse strength, anti - sticking property, and redispersibility, which are the effects of the invention of the present disclosure, are easily obtained.

[0033] [1 - 5. Component (E)] In the anti - sticking agent for unvulcanized rubber of the present disclosure, at least one compound (E) (component (E)) selected from the group consisting of inorganic silicates, metal oxides, and calcium carbonate other than the said component (A) is considered to mainly act as a lubricant (impart slipperiness), and is also considered to contribute to the improvement of powder fluidity.

[0034] In the component (E), the inorganic silicate is not particularly limited, and examples thereof include silicates such as kaolin (also referred to as 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, iron oxide, etc.

[0035] The content of the component (E) in the anti-sticking agent for unvulcanized rubber of the present disclosure is not particularly limited and can be selected according to the purpose. For example, based on 100% by mass of the total mass of the components (A) to (E), it may be 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, and may be 76% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less, for example. When the content of the component (E) is at least the lower limit value, the slipperiness between the product and its storage container and between the rubber and the equipment is more likely to be good, and it is also preferable because it leads to cost reduction.

[0036] When calcium carbonate is included 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 based on 100% by mass of the total mass of the component (E). When the content of calcium carbonate is at least the lower limit value, for example, the hardness of the dry film can be reduced and foreign matters 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 20 or less, 15 or less, 10 or less, 5 or less, 3 or less, 1 or less, or 0.5 or less, for example. When the mass ratio (D) / (E) is within the above range, for example, excellent anti-sticking properties and foreign matter reduction can be achieved simultaneously.

[0038] [1-6. Optional components, etc.] The antisticking agent composition for unvulcanized rubber of the present disclosure may or may not contain optional components other than the above components (A) to (E). For example, the antisticking agent composition for unvulcanized rubber of the present disclosure may contain, as optional components, additives such as defoaming agents, preservatives, wetting aids, tackifiers, and foreign matter reduction aids, as necessary.

[0039] The defoaming agent is not particularly limited. For example, there are oil-based defoaming agents such as castor oil, sesame oil, linseed oil, and animal and vegetable oils; fatty acid ester-based defoaming agents such as isoamyl stearate, distearyl succinate, ethylene glycol distearate, and butyl stearate; alcohol-based defoaming agents such as polyoxyalkylene monohydric alcohol, di-t-amylphenoxyethanol, 3-heptanol, and 2-ethylhexanol; ether-based defoaming agents such as di-t-aminophenoxyethanol, 3-heptyl cellosolve, nonyl cellosolve, and 3-heptyl carbitol; phosphate ester-based defoaming agents such as tributyl phosphate and tris(butoxyethyl) phosphate; amine-based defoaming agents such as diamylamine; amide-based defoaming agents such as polyalkylene amide and acrylate polyamine; mineral oil; silicone oil; and the like. The defoaming agent may be used alone or in combination of two or more.

[0040] The preservative is not particularly limited. For example, there are isothiazolinone, derivatives of pyridine and iodine, and the like. The derivative of isothiazolinone is not particularly limited. For example, there are benzisothiazolinone (BIT), methylisothiazolinone (MIT, MI), chloromethylisothiazolinone (CMIT, CMI), octylisothiazolinone (OIT, OI), dichlorooctylisothiazolinone (DCOIT, DCOI), and their derivatives. The derivative of pyridine is not particularly limited. For example, there are pyridine thiol and their derivatives. The derivative of iodine is not particularly limited. For example, there are iodo-2-propynyl butylcarbamate and their derivatives. For example, the preservative may be used alone or in combination of two or more.

[0041] The wetting aid is not particularly limited, and examples thereof include alcohols. More specifically, examples 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 aid may be used alone or in combination of two or more.

[0042] The shape of the anti-adhesion agent for unvulcanized rubber of the present disclosure is preferably powdery, granular, or particulate. The average particle diameter of the anti-adhesion agent is preferably 0.003 to 30 mm, more preferably 0.003 to 25 mm, and even more preferably 0.005 to 20 mm. When it is above the lower limit value of the above range, it is difficult to scatter, and when it is below the upper limit value, it is difficult to solidify. The average particle diameter of the powdery anti-adhesion agent for unvulcanized rubber is preferably 0.005 to 0.2 mm, more preferably 0.005 to 0.1 mm.

[0043] [2. Method for producing anti-adhesion agent composition for unvulcanized rubber] The method for producing the anti-blocking 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 anti-blocking agent for unvulcanized rubber, that is, components (A) to (E), and optional components that are blended as necessary. As the apparatus used for mixing, for example, an apparatus having a stirring blade in a container can be used. Specifically, for example, powder mixers capable of performing oscillating stirring or stirring, such as ribbon mixers and vertical screw mixers, can be mentioned. Also, multi-functional powder mixers such as super mixers (manufactured by Kawata Co., Ltd.), high-speed mixers (manufactured by Earth Technica Co., Ltd.), new gram machines (manufactured by Seishin Enterprise Co., Ltd.), and SV mixers (manufactured by Kobe Steel Environmental Solutions Co., Ltd.) in which a plurality of stirring devices are combined can also be used. Further, 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, disk mills, jet mills, and cyclone mills may be used.

[0044] [3. Method of using the anti-blocking agent composition for unvulcanized rubber, etc.] The method of using the anti-blocking 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 anti-blocking agent composition for unvulcanized rubber. Specifically, the method of using the anti-blocking agent composition for unvulcanized rubber of the present disclosure is, for example, as follows, but is not limited thereto.

[0045] The method for anti-blocking treatment of unvulcanized rubber using the anti-blocking agent composition for unvulcanized rubber of the present disclosure may, for example, as described above, have an anti-blocking treatment step of attaching the above-mentioned components (A) to (E) in the anti-blocking agent composition for unvulcanized rubber of the present disclosure to the surface of the unvulcanized rubber for anti-blocking treatment. The attachment to the surface of the unvulcanized rubber can be performed, for example, by the wet method described later. The anti-blocking treated unvulcanized rubber thus treated can be stored, for example, by stacking or folding, without the unvulcanized rubbers adhering to each other. Also, such a method for anti-blocking treatment of unvulcanized rubber can also be said to be, for example, a method for producing anti-blocking treated unvulcanized rubber.

[0046] The 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 dilution). In the anti-adhesion agent composition for unvulcanized rubber of the present disclosure, the concentration at the time of adhering 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 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 and fast drying can be obtained. If the concentration is not too low, for example, the effects of high anti-adhesion and high lubricity can be obtained. The anti-adhesion agent composition for unvulcanized rubber of the present disclosure can exhibit high anti-adhesion even when the concentration at the time of adhering to the surface of the unvulcanized rubber is low, for example, and can exhibit high anti-adhesion with a small adhesion amount. Also, the viscosity at the time of adhering 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 and fast drying can be obtained. If the viscosity is not too low, for example, the effects of high anti-adhesion and high lubricity can be obtained.

[0047] The anti-adhesion treatment step is, for example, as described above, a step of adhering the anti-adhesion agent composition for unvulcanized rubber of the present disclosure or the aqueous dilution of the anti-adhesion agent composition for unvulcanized rubber of the present disclosure to the surface of the unvulcanized rubber, and further volatilizing water to adhere the components (A) to (E) in the 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, an anti-adhesion agent composition adhesion step of adhering the anti-adhesion agent composition for unvulcanized rubber of the present disclosure to the surface of the unvulcanized rubber, and a drying step of drying the 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, for example, in the same manner as the wet method in a general anti-adhesion agent composition for unvulcanized rubber.

[0048] In the step of attaching the anti-adhesion agent composition for unvulcanized rubber, for example, it is preferable to attach the anti-adhesion agent composition for unvulcanized rubber to 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.

[0049] As a specific method of the step of attaching the anti-adhesion agent composition for unvulcanized rubber, for example, there are a method of spraying the anti-adhesion agent composition for unvulcanized rubber onto unvulcanized rubber with a shower device, a dip method of immersing unvulcanized rubber in a tank containing the anti-adhesion agent composition for unvulcanized rubber for a short time, etc. In addition, a method of applying the anti-adhesion agent composition for unvulcanized rubber to unvulcanized rubber using a coating device may be adopted, or these methods may be used in combination as appropriate.

[0050] According to the anti-adhesion agent composition for unvulcanized rubber of the present disclosure, as described above, it is excellent in anti-adhesion effect and defoaming property.

[0051] There is no particular limitation on the rubber types to which the anti-adhesion agent composition for 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

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

[0053] [Examples 1 to 40 and Comparative Examples 1 to 6] The components were kneaded at the weight (mass) ratios shown in Tables 1 to 5 below to prepare powdery non-vulcanized rubber anti-sticking agents (hereinafter also referred to as anti-sticking agents) for each example consisting of uniform powders. Then, each of the obtained anti-sticking agents was added to tap water while stirring to prepare an aqueous diluted solution of the anti-sticking agent composition with a concentration of 3% by mass of the anti-sticking agent. 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, among the components (A) to (E), in Comparative Example 1, component (B-1) was not blended, and in Comparative Example 2, component (B-2) was not blended. In Comparative Examples 3 to 5, all of the components (A) to (E) were blended, but the mass ratio (B-1) / (B-2) was set to 5.0, 0.15, and 4.0, respectively. In Comparative Example 6, component (D) among the components (A) to (E) was not blended. The product names (trade names) and manufacturers of the respective components described 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 various evaluations, the following unvulcanized SBR rubber and unvulcanized NR rubber were used as the rubber for evaluation.

[0061] (Unvulcanized SBR rubber) Based on 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 JSRAROMA (process oil) (manufactured by Nippon Sun Oil Co., Ltd., trade name "Aroma 790"), 3 parts by mass of zinc oxide (manufactured by Hakusuitec 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 151.5 parts by mass), and unvulcanized SBR rubber was used.

[0062] (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 JSRAROMA (process oil) (manufactured by Nippon Sun Oil Co., Ltd., trade name "Aroma 790"), 3 parts by mass of zinc oxide (manufactured by Hakusuitec 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.

[0063] (2) Evaluation of anti-adhesion property The above-mentioned unvulcanized rubber was kneaded on an open roll at a temperature of 80 to 120°C to form a rubber sheet (thickness: 5 to 8 mm, 60 cm × 15 cm). Immediately after being fed out, the rubber sheet was immersed in 1 L of an anti-adhesion agent aqueous dilution (temperature 40°C) obtained by stirring and dispersing the anti-adhesion agent composition for unvulcanized rubber obtained in each of Examples 1 to 40 and Comparative Examples 1 to 6 in water to a concentration of 3% by mass for 1 hour or more. Thereafter, the rubber sheet was quickly pulled up vertically, left standing vertically at room temperature, and naturally dried. In this way, the anti-adhesion treatment of the rubber sheet (unvulcanized rubber) was carried out. Thereafter, the rubber sheet was cut into 6 cm × 15 cm and two pieces were overlapped to form 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. Thereafter, the test piece was returned to room temperature, and a 180° peel test was carried out using a tensile tester [AGS-500D, Shimadzu Corporation], and the peel resistance (N / cm) was measured at a pulling speed of 300 mm / min.

[0064] (3) Evaluation of redispersibility An anti-adhesion agent aqueous dilution for unvulcanized rubber was produced in the same manner as in the above-mentioned “(2) Evaluation of anti-adhesion property”. Next, the anti-adhesion agent aqueous dilution (suspension) for unvulcanized rubber was put into a 100 ml graduated cylinder, shaken up and down 10 times, and then left standing in a constant temperature bath at 20°C. After 24 hours, the graduated cylinder was shaken up and down, and the number of shaking times until the solid content at the bottom of the graduated cylinder was completely dispersed was measured. It was determined that the smaller the number of shaking times, the better the redispersibility.

[0065] (4) Powder dischargeability (powder fluidity) The anti-adhesion agent compositions for unvulcanized rubber obtained in each of Examples 1 to 40 and Comparative Examples 1 to 6 were filled into a 500 mL resin container with a discharge port diameter of 2.2 cm and an inclination angle of 50°. After leveling the powder surface by tapping, it was left standing in a humid heat storage [IG-401, YAMATO] adjusted to a temperature of 40°C and a humidity of 90% RH. After 7 days, the container was taken out, and with the discharge port open, the container was struck with a metal bar, and the discharge behavior of the powder was visually observed. The evaluation criteria are as follows. ○: All can be discharged ×: Cannot be completely discharged (blocking)

[0066] (5) Cured product collapse strength (blocking property) The anti-sticking agent compositions for uncured rubber obtained in Examples 1 to 40 and Comparative Examples 1 to 6 were filled into a resin circular container with an inner diameter of 3.2 cm and a height of 1.9 cm. After leveling the powder surface by tapping, it was left standing in a humidity and heat storage chamber [IG-401, YAMATO] adjusted to a temperature of 40 °C and a humidity of 90% RH. After 7 days, the powder solid was taken out from the container, and with a resin circular plate with a diameter of 3.2 cm laid on the upper part of the powder solid, it was crushed with a rod-shaped tension gauge round spring type [Oba Instruments], and the weight (kg) at the time of collapse was measured.

[0067] The types and compositions of the raw materials in the anti-sticking agent compositions for uncured rubber of Examples 1 to 40 and Comparative Examples 1 to 6, and the evaluation results of each performance of the anti-sticking property and foaming property evaluated as described above are summarized in Tables 1 to 5 above.

[0068] As shown in Tables 1 to 5 above, the anti-sticking agent compositions for uncured rubber of Examples 1 to 40 all had good anti-sticking properties, redispersibility, and cured product collapse strength (blocking property). On the other hand, the anti-sticking agent compositions for uncured rubber of Comparative Examples 1 and 3 were inferior in redispersibility compared to the examples. The anti-sticking agent compositions for uncured rubber of Comparative Examples 2, 4, and 6 were inferior in anti-sticking property compared to the examples. The anti-sticking agent composition for uncured rubber of Comparative Example 5 was inferior in redispersibility and cured product collapse strength compared to the examples. In addition, the anti-sticking agent compositions for uncured rubber of Comparative Examples 5 and 6 were inferior in powder dischargeability compared to the examples.

[0069] <Supplementary Note> Some or all of the above embodiments and examples can be described as follows in the supplementary note, but are not limited thereto. (Supplementary Note 1) Containing the following components (A) to (E), An anti-sticking agent composition for uncured 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) Metallic soap (E) At least one compound selected from the group consisting of inorganic silicate, metal oxide, and calcium carbonate other than the component (A) (Appendix 2) Based on 100% by mass of the total mass of the components (A) to (E), The component (A) is 10 to 50% by mass, The component (B-1) is 1 to 5% by mass, The component (B-2) is 1 to 5% by mass, The component (C) is 2 to 25% by mass, The component (D) is 10 to 30% by mass, The component (E) is 0.1 to 76% by mass, An anti-sticking agent composition for unvulcanized rubber according to Appendix 1, containing (Appendix 3) An anti-sticking agent composition aqueous dilution for unvulcanized rubber, characterized by containing the anti-sticking agent composition for unvulcanized rubber according to Appendix 1 or 2 and water (Appendix 4) An unvulcanized rubber, characterized in that the components (A) to (E) in the anti-sticking agent composition for unvulcanized rubber according to Appendix 1 or 2 are adhered to the surface

Claims

1. Contains the following components (A) to (E), The adhesion preventive 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).

2. With respect to 100% by mass of the total mass of the components (A) to (E), 10 to 50% by mass of the component (A), 1 to 5% by mass of the component (B-1), 1 to 5% by mass of the component (B-2), 2 to 25% by mass of the component (C), 10 to 30 mass% of the component (D), 0.1 to 76% by mass of the component (E), The adhesion inhibitor composition for unvulcanized rubber according to claim 1, comprising:

3. 3. 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.

4. 3. An unvulcanized rubber having the components (A) to (E) in the adhesion preventive composition for unvulcanized rubber according to claim 1 or 2 adhered to the surface of the unvulcanized rubber.

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