JP5276822B2 - Anti-curing composition for unvulcanized rubber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesion preventive composition for an unvulcanized rubber which exhibits an excellent adhesion preventive effect and is markedly improved in a dust generating problem in use, to provide its production method, and to provide a method for producing an unvulcanized rubber rendered adhesion preventive by treatment with the adhesion preventive composition. <P>SOLUTION: The adhesion preventive composition for the unvulcanized rubber is a composition comprising wax particles comprising a wax mixture, a surfactant, a water-soluble polymer, a dispersion stabilizer, and water, wherein 1-120 pts.wt. above surfactant, 1-50 pts.wt. above water-soluble polymer, and 1-50 pts.wt. above dispersion stabilizer are added to 100 pts.wt. above wax particles, 100 pts.wt. above wax mixture is constituted from 30-90 pts.wt. component A and 10-70 pts.wt. component B, and the wax particles are in a state dispersed in the water. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to an anti-adhesive composition for unvulcanized rubber. More specifically, an anti-vulcanized rubber anti-adhesive composition in which wax particles comprising a wax mixture are dispersed in water, a method for producing the same, and an anti-adhesion treatment performed using the non-vulcanized rubber anti-adhesive composition The present invention relates to a method for producing an unvulcanized rubber.

A rubber product is usually manufactured by the following steps.
1) First, raw rubber (natural rubber, synthetic rubber or a mixture thereof) is masticated with a kneading roll, a Banbury mixer, a platy skater, etc., to give plasticity to the rubber.
2) Next, while mixing carbon black, sulfur, zinc oxide, an accelerator, an antiaging agent, etc. as a compounding agent in the kneaded rubber, it is sufficiently kneaded using an open roll or a Banbury mixer.
3) Thereafter, rubber products such as tires and tubes are manufactured through processes such as molding and vulcanization according to the use of the rubber.
In the above 3), the rubber product molding method is roughly divided into sheet molding and extrusion molding. Sheet molding is a processing method in which a rubber dough is rolled to a predetermined thickness and width, and a rubber sheet is formed by applying heat and pressure with a large press. The unvulcanized rubber sheet is formed using a calendar roll or an extruder. Extrusion molding includes a ram type and a screw type. The ram extruder is a hydraulic type and is a molding machine that extrudes a rubber lump loaded in a cylinder like a tokoroten. Long continuous rubber products such as hoses, wind seals and tire tubes are often molded with a screw extruder.

In such a rubber production and processing process, unvulcanized rubber may be stored in piles until it moves to the next molding or vulcanization process. In this case, for the purpose of preventing rubber adhesion An adhesion preventive agent (anti-adhesive) is used.
Conventionally, as this adhesion preventive agent, powders of inorganic particles such as talc, mica, calcium carbonate, magnesium carbonate, bentonite and metal soap particles such as zinc stearate and magnesium stearate are used because of their excellent adhesion resistance. Has been. As the method of use, a so-called dry method such as a method of spraying rubber with powder or a method of passing through powder; a method of suspending the powder of inorganic particles in water and spraying the suspension; And so-called wet methods such as a method of spraying on rubber and a method of immersing in a suspension. The purpose of using water in the wet method is to improve the workability and also to cool the rubber. Further, in hollow and thin-walled cylindrical molding such as a tire tube using an extruder, the inner surface of the cylinder is prevented from sticking by extrusion molding while blowing air mixed with an adhesion inhibitor into the tube.

However, such an adhesion preventing agent is basically a foreign substance for rubber products, and becomes a major factor for deteriorating the physical properties of rubber. In particular, advances in performance and diversification of rubber products in recent years have been remarkable, and even a small amount of foreign matter can have a large effect on the physical properties of rubber products, so the amount of adhesion inhibitor to rubber should be as small as possible. Is desirable. In addition, there is a problem in terms of work environment such that the adhesion preventive agent adhering to the rubber surface is pulverized and dust is generated until the next molding, vulcanization and the like. Deterioration of the working environment due to dust generation causes occupational diseases such as pneumoconiosis, so it is desirable that the adhesion amount of the adhesion inhibitor is as small as possible.
Conventional adhesion preventive agents including inorganic particles and metal soap particle powders are used so that a large amount adheres to the rubber surface because the adhesion resistance decreases when the amount attached to the rubber surface is small. Therefore, problems of working environment such as adverse effects on physical properties of rubber products and generation of dust due to powder falling often occur, and improvement is desired. For these reasons, it is desired to develop an adhesion preventive agent that is excellent in adhesion even when the amount of adhesion to the rubber surface is small.

On the other hand, there is an adhesion preventive agent in which components are configured with a concept different from that of an adhesion preventive agent containing powder of inorganic particles or metal soap particles. For example, Patent Document 1 discloses an anti-wear composition comprising 30 to 90 parts by weight of a water-soluble polymer having a film-forming property and 70 to 10 parts by weight of an anionic surfactant or a nonionic surfactant. . This anti-adhesion composition is characterized in that no powder is used. Moreover, since it can be used even if diluted to a concentration of 1 to 10%, adhesion inhibition of the vulcanized rubber can be suppressed. However, in order to produce an effect at a low concentration without using powder, it is necessary to use a water-soluble polymer having a considerably high molecular weight, and it takes a considerable time to completely dissolve them in water. Therefore, handling property is not excellent and is not practical. As a method for shortening the time required for complete dissolution in water, generally, for example, first, a water-soluble polymer is introduced into cold water, and then the water temperature is gradually raised to 70 to 90 ° C. while stirring, and then dissolved. In addition, there are a method of gradually lowering the water temperature, a method of promoting the dissolution by manipulating the pH of water, a method of surface-treating a water-soluble polymer with a specific organic compound in advance, etc. The method is not simple and is not preferable because it requires dedicated equipment.
As an adhesion preventive agent in which fine particles of wax or resin are emulsified or dispersed in an aqueous system, for example, Patent Document 2 discloses low molecular weight polyethylene glycol and microcristan wax as required in a total amount of 10-30. An adhesion inhibitor emulsified in an oil-in-water type with 20% by weight of a fatty acid amide, 20 to 40% by weight of a nonionic surfactant and 80 to 120% by weight of a long chain fatty acid salt is disclosed. This adhesion inhibitor is characterized by the fact that it does not use inorganic particles, but it is necessary to use it at a high concentration in order to exert a sufficient adhesion prevention effect. Due to the problem of lowering the physical properties of rubber, the method of use is limited and the versatility is poor.

Patent Document 3 discloses that 5-30% by weight of a polyethylene resin powder having an average particle diameter of 50 μm or less and a melting point of 150 ° C. or less and 1-10% by weight of a hydrogenated wax resin powder having a melting point of 70 ° C. or more are nonionic interfaces. An adhesion inhibitor dispersed in an aqueous solution of 1 to 10% by weight of activator is disclosed. This adhesion inhibitor is obtained by dispersing both a polyethylene resin powder and a hydrogenated wax resin powder in water. However, considering the characteristics of both resins, a nonionic active agent alone has a dispersion effect as a dispersant. Not enough. That is, polyethylene resin is highly hydrophobic and difficult to disperse in water. The hydrogenated wax contains a hydroxyl group in the molecule, and forms a hydrogen bond between the resin powders in water and easily aggregates. In particular, in an atmosphere of 40 to 50 ° C. above room temperature, the thermal motion of the resin powder becomes intense, the frequency of collision between the resin powders becomes high, and aggregation is likely to occur. Nevertheless, in Patent Document 3, only a nonionic surfactant is used as a dispersant, and in this case, the dispersion system is not sufficiently stable and lacks storage stability. Furthermore, it is difficult to uniformly apply both the polyethylene resin powder and the hydrogenated wax resin powder to the rubber surface with a dispersant containing only a nonionic surfactant.
Patent Document 4 discloses a rubber elastic surface treatment liquid in which 0.1 to 10% by weight of a low molecular weight polyethylene wax having a softening point of 80 to 120 ° C. and an average particle size of 10 μm or less is dispersed or emulsified in water, Alternatively, 100 to 100 parts by weight of a rubber elastic body, in which 0.1 to 10 parts by weight of a vegetable or petroleum wax is added and dispersed or emulsified with respect to 100 parts by weight of the surface treatment liquid A surface treatment liquid in which 0.1 to 10 parts by weight of one or several kinds of dimethylsiloxane-based silicone oil of 10 to 1000 cs is added is disclosed as low molecular weight polyethylene wax or vegetable or petroleum wax. Only candelilla wax, carnauba wax, rice wax, and solid paraffin wax exemplified in this document The soluble poor rubber surface is insufficient, the effect of adhesion prevention can not be magnetic uniformly applied. Further, when a silicone resin-based polymer such as dimethylsiloxane-based silicone oil is added, it is not practical because even a small amount reduces the physical properties of the vulcanized rubber and the cost is high.

Thus, each of the anti-adhesive agents of Patent Documents 1 to 4 has a problem. Accordingly, the current situation is that it is necessary to use a conventional anti-adhesive agent containing inorganic particles and metal soap particles while having problems of adhesion and dust.
JP-A-62-32127 JP-A-60-203649 Japanese Patent Laid-Open No. 1-301736 JP-A-63-8428

  An object of the present invention is to provide an anti-adhesive composition for unvulcanized rubber, which has excellent anti-adhesive properties and greatly reduces the problem of dust generation during use, a method for producing the same, and an anti-adhesive composition for unvulcanized rubber. It is an object to provide a method for producing a non-vulcanized rubber subjected to an adhesion treatment performed using

As a result of intensive studies to solve the above problems, the present inventors have found a composition containing wax particles composed of a wax mixture, a surfactant, a water-soluble polymer, a dispersion stabilizer, and water. If it exists, the knowledge that it can be used as an adhesion preventive agent was obtained, and the composition was further optimized to arrive at the present invention.
An anti-adhesive composition for an unvulcanized rubber according to the present invention includes a wax particle comprising a wax mixture, a surfactant, a water-soluble polymer, a dispersion stabilizer (however, excluding the surfactant) , A composition containing water, wherein the surfactant is at least one selected from a nonionic surfactant, an anionic surfactant and a cationic surfactant, and 100 parts by weight of the wax particles. On the other hand, 1 to 120 parts by weight of a surfactant, 1 to 50 parts by weight of a water-soluble polymer, and 1 to 50 parts by weight of a dispersion stabilizer are blended, and 100 parts by weight of the wax mixture is 30 to 90 parts by weight of the following component A. The wax particles are in a state of being dispersed in the water.
Component A: Hydrogenated wax Component B: At least one selected from plant waxes, animal waxes, mineral waxes, petroleum waxes, synthetic hydrocarbon waxes, modified waxes, fatty acid amides, and phthalic anhydride imides

The melting point of the hydrogenated wax is preferably 60 to 150 ° C.
Of the component B, the penetration of the wax occupying 30% by weight or more is within a range of 10 mm or less (100 g / 5 s) at 25 ° C. and 25 mm or less (100 g / 5 s) at 50 ° C., respectively. preferable. The melting point of the wax occupying 30% by weight or more is more preferably 70 to 150 ° C.

The component A preferably contains at least one selected from hydrogenated castor oil, 12-hydroxystearic acid and derivatives thereof.
The component B preferably contains at least one selected from paraffin wax, microcrystalline wax, candelilla wax, carnauba wax and rice wax.

The wax particles preferably have an average particle size of 0.1 to 50 μm.
The surfactant is preferably a nonionic surfactant and / or an anionic surfactant. The surfactant is at least one selected from polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester and polyoxyethylene hydrogenated castor oil, The ionic surfactant is at least one selected from a fatty acid salt, an alkyl sulfate ester salt, an alkylbenzene sulfonate salt, an alkyl ether sulfate salt, a higher fatty acid amide sulfonate salt, an alkyl ether phosphate ester salt, and a long chain sulfosuccinate salt. More preferably.

The water-soluble polymer is preferably at least one selected from polyethylene glycol, polyethylene oxide, cellulose ether, polyvinyl alcohol, polyvinyl pyrrolidone, gum arabic, guar gum, xanthan gum and sodium polyacrylate.
The dispersion stabilizer is lecithin, rosin, ethylhexyl isononanoate, isononyl isononanoate, isodecyl isononanoate, isotridecyl isononanoate, isodecyl neopentanoate, ethyl isostearate, isopropyl isostearate, alkenyl succinic anhydride, hydrogenated isostearic acid castor oil, dye It is at least one selected from merlinoleic acid hydrogenated castor oil, methylricinoleate, butylricinoleate, ethylene glycol monoricinoleate, trimethylolpropane monoricinoleate, glycerin triacetylricinoleate and ethylene-vinyl acetate copolymer. preferable.

A method for producing an anti-vulcanized rubber composition for an unvulcanized rubber according to the present invention is a method for producing the above-mentioned unvulcanized rubber composition for an unvulcanized rubber, wherein the water-soluble polymer is dissolved in the water. Alternatively, the intermediate raw material is obtained by dispersing and heating above the melting point of the wax mixture to obtain an intermediate raw material, and the wax mixture is melted to obtain a wax molten mixture, and then the wax raw mixture is added to the intermediate raw material. A mixing step in which the surfactant and the dispersion stabilizer are dropped and mixed to be emulsified and dispersed.
The method for producing a non-vulcanized rubber subjected to an adhesion treatment according to the present invention includes a treatment step of attaching the above-mentioned anti-adhesive composition for an unvulcanized rubber or a diluted solution thereof to the surface of the molded unvulcanized rubber. including. Here, inorganic particles and / or metal soap particles are further adhered to the surface of the molded unvulcanized rubber, and the inorganic particles are calcium carbonate, magnesium carbonate, kaolin, clay, talc, mica, sericite and It is at least one selected from bentonite, and the metal soap particles are preferably at least one selected from zinc stearate and magnesium stearate.

The anti-adhesive composition for unvulcanized rubber of the present invention can impart excellent anti-adhesive properties to the unvulcanized rubber, and the problem of dust generation during its use is greatly reduced.
In the method for producing an unvulcanized rubber anti-adhesive composition of the present invention, a stable unvulcanized rubber anti-adhesive composition can be efficiently produced.

  In the method for producing an adhesion-treated unvulcanized rubber according to the present invention, an adhesion-treated unvulcanized rubber having excellent adhesion can be efficiently produced, and the problem of dust generation during production is greatly reduced. To do.

[Adhesive composition for unvulcanized rubber]
The anti-adhesive composition for unvulcanized rubber of the present invention is a composition containing wax particles made of a wax mixture, a surfactant, a water-soluble polymer, a dispersion stabilizer, and water. 1 to 120 parts by weight of a surfactant, 1 to 50 parts by weight of a water-soluble polymer, and 1 to 50 parts by weight of a dispersion stabilizer are blended with 100 parts by weight of wax particles.
First, each component which comprises the adhesion preventive composition for unvulcanized rubber is demonstrated in detail.

(Wax particles)
The wax particles are components that exhibit adhesion to unvulcanized rubber, and are components that do not cause the problem of dust generation when using the anti-vulcanized rubber composition. The wax particles are composed of a wax mixture containing the following components A and B.
Component A: Hydrogenated wax Component B: At least one selected from plant waxes, animal waxes, mineral waxes, petroleum waxes, synthetic hydrocarbon waxes, modified waxes, fatty acid amides, and phthalic anhydride imides

In the present invention, each individual wax particle contains both components A and B. Therefore, the wax particles used in the present invention are clearly different in composition from a mixture of wax particles composed of only the component A and a mixture of wax particles composed of only the component B (mixture of wax particles composed of a single component). In the present invention, compared to the case of using a mixture of wax particles composed of a single component, it is excellent in terms of dispersion stability to water, coating properties on the unvulcanized rubber surface, and adhesion to unvulcanized rubber. ing.
In the present invention, the wax mixture is melt-mixed at a temperature equal to or higher than the melting point of the wax constituting the wax mixture (preferably after being completely melt-mixed), for example, an inversion emulsification method, a D-phase emulsification method, an HLB temperature emulsification method, It is preferable to be processed into wax particles by a method such as emulsification dispersion such as high-pressure emulsification method, membrane emulsification method, ultrasonic dispersion method, etc .;

The melting point of the wax mixture is not particularly limited, but it is preferably around the temperature of the unvulcanized rubber immediately after being kneaded with an open roll or a Banbury mixer and molded. In the production process of industrial rubber products, the treatment for preventing adhesion of unvulcanized rubber is usually carried out immediately after being kneaded and molded by an open roll or Banbury mixer. The temperature of the unvulcanized rubber immediately after being kneaded and molded by an open roll or Banbury mixer is generally in the range of 80 to 160 ° C., although it varies depending on the process. Considering that it is desirable to form a uniform continuous film of the wax mixture on the surface of the unvulcanized rubber, it is preferable to dry the wax particles on the surface of the unvulcanized rubber having a melting point of the wax mixture or higher. If the melting point of the wax mixture is too lower than the assumed temperature of the molded unvulcanized rubber, the strength of the coating will be weak. This also causes the wax particles adhering to the surface of the vulcanized rubber to fall off.
Component A is a hydrogenated wax, and is a component that imparts thixotropic properties to the anti-vulcanizing rubber composition of the present invention.

The amount of component A in 100 parts by weight of the wax mixture is 30 to 90 parts by weight, preferably 40 to 90 parts by weight, more preferably 50 to 90 parts by weight, and particularly preferably 60 to 90 parts by weight. If the amount of component A in 100 parts by weight of the wax mixture is less than 30 parts by weight, the thixotropy may be reduced and it may be difficult to form a uniform film on the unvulcanized rubber surface. On the other hand, if the amount of the component A exceeds 90 parts by weight, the wax particles may lack dispersion stability.
The melting point of the hydrogenated wax as component A is not particularly limited, but is preferably 60 to 150 ° C, more preferably 60 to 130 ° C, particularly preferably 70 to 120 ° C, and most preferably 80 to 100 ° C. is there. If the melting point of the hydrogenated wax is less than 60 ° C., the wax particles may lack sufficient strength to sufficiently withstand the load of unvulcanized rubber. On the other hand, if the melting point exceeds 150 ° C., the uniformity of the coating film on the unvulcanized rubber surface may be lacking.

Examples of the component A include hydrogenated castor oil, 12-hydroxystearic acid, derivatives of 12-hydroxystearic acid, hydrogen such as lauric acid, myristic acid, palmitic acid, behenic acid, sebacic acid, undecylenic acid, heptylic acid, maleic acid, etc. And waxes may be used alone or in combination of two or more.
Hardened castor oil is a hard and brittle white high melting point wax obtained by hydrogenation of castor oil, and is also referred to as castor wax, caster wax, pearl wax and the like. The penetration of cured castor oil at 25 ° C. is as small as 0.2 mm, and the hardness of the cured castor oil is high. The main component of hydrogenated castor oil is glycerin tri-12-hydroxystearate, which contains small amounts of 12-hydroxystearic acid, dihydroxystearic acid and mixed glycerides of stearic acid. The melting point of hardened castor oil shows the highest value among the extremely hardened oils of animal and vegetable oils and fats, which is considered to be due to the fact that the hardened castor oil has many hydroxyl groups in the molecule. In addition, when hardened castor oil particles are dispersed and swollen in a solvent, the three hydroxyl groups in the molecule form weak hydrogen bonds between the particles, forming a network structure and forming a gel, which makes the dispersion liquid thixotropic. Can be granted.

From these properties, the hardened castor oil forms a uniform network structure that is hard and brittle on the rubber surface, and exhibits excellent performance in preventing the adhesion between rubbers.
Saponification of the hardened castor oil yields a light brownish white waxy solid derivative called 12-hydroxystearic acid. 12-Hydroxy stearic acid also contains a hydroxyl group in the same manner as hardened castor oil, and thus forms a weak gel in the solvent. Accordingly, 12-hydroxystearic acid can also form a uniform network structure on the rubber surface, like hardened castor oil, and exhibit performance excellent in the prevention of adhesion between rubbers. Furthermore, various wax-like derivatives can be obtained by amidation and esterification of 12-hydroxystearic acid.

Examples of such 12-hydroxystearic acid derivatives include 12-hydroxystearic amide, N-hydroxyethyl-12-hydroxystearylamide, N, N′-ethylene-bis-12-hydroxystearylamide, N, N′-hexamethylene-bis-12-hydroxystearylamide, N, N′-xylylene-bis-12-hydroxystearylamide, methyl-12-hydroxystearate, propylene glycol-mono-12-hydroxystearate, ethylene glycol -Mono-12-hydroxy stearate etc. can be mentioned and 1 type (s) or 2 or more types may be used together.
The hydrogenated wax of component A is also preferably at least one selected from hydrogenated castor oil, 12-hydroxystearic acid and derivatives thereof, and hydrogenated castor oil is more preferable because it is inexpensive, has few impurities, and is excellent in compatibility.

Next, the component B is at least one selected from plant waxes, animal waxes, mineral waxes, petroleum waxes, synthetic hydrocarbon waxes, modified waxes, fatty acid amides and phthalic anhydride imides.
However, since the hydrogenated wax contains a large number of hydroxyl groups in the molecule, hydrogen bonds are easily formed between the dispersed hydrogenated wax particles and aggregation may occur, and dispersion stability may be lacking. Therefore, the B component is blended for the purpose of improving the dispersion stability.

It is generally known that a wax mixture in which two or more kinds of waxes are uniformly mixed often causes physical property modification as compared with each single case. For example, it is known that when the paraffin wax which is the B component and the hardened castor oil which is the A component are mixed, the melting point is remarkably increased. Therefore, when the B component and the A component are mixed, it is necessary to select a component whose performance is improved as a wax mixture as compared with each single component, or a component which does not impair each other's physical properties. In selecting the A component and the B component, it is preferable to select such that the performance is improved as compared with the case of a single component due to the synergistic effect of the A component and the B component.
The amount of component B in 100 parts by weight of the wax mixture is 10 to 70 parts by weight, preferably 10 to 60 parts by weight, more preferably 10 to 50 parts by weight, and particularly preferably 10 to 40 parts by weight. If the amount of component B in 100 parts by weight of the wax mixture is less than 10 parts by weight, the dispersion stability of the wax particles may be insufficient. On the other hand, if the amount of component B is more than 70 parts by weight, the thixotropy may be reduced and it may be difficult to form a uniform coating film on the unvulcanized rubber surface.

The melting point of the wax occupying 30% by weight or more with the component B is not particularly limited, but is preferably 70 to 150 ° C, more preferably 70 to 130 ° C, particularly preferably 70 to 120 ° C, and most preferably 80. ~ 100 ° C. If the melting point of the wax occupying 30% by weight or more of the B component is less than 70 ° C., the wax particles may lack sufficient strength to sufficiently withstand the load of unvulcanized rubber. On the other hand, if the melting point is higher than 150 ° C., the coating film on the unvulcanized rubber surface may lack uniformity.
In the anti-vulcanizing rubber composition of the present invention, the higher the hardness of each wax constituting the wax mixture is, the more preferable wax particles are formed that can withstand the load of the unvulcanized rubber.

In the present invention, the hardness of the wax is expressed by a commonly used penetration, and the petroleum wax penetration test method (JIS K-2235 5.4) is applied mutatis mutandis. The lower the penetration of the wax, the higher the hardness of the wax, and the non-vulcanized rubber anti-adhesive composition containing the wax is more suitable. In addition, in a factory where unvulcanized rubber is loaded and stored, the temperature is high on average, especially in summer. Moreover, considering that the uncured rubber is molded and the heat is still slightly hot even after a lapse of time, the B component is composed of wax having a low penetration in the temperature range of 25 to 50 ° C. It is preferable.
Therefore, the penetration at 25 ° C. of the wax occupying 30% by weight or more of the B component is preferably 10 mm or less (100 g / 5 s), more preferably 7 mm or less (100 g / 5 s), and particularly preferably 5 mm or less. (100 g / 5 s), most preferably 3 mm or less (100 g / 5 s). Further, the penetration at 50 ° C. of the wax occupying 30% by weight or more of the B component is preferably 25 mm or less (100 g / 5 s), more preferably 20 mm or less (100 g / 5 s), and particularly preferably 15 mm or less. (100 g / 5 s), most preferably 10 mm or less (100 g / 5 s). If the penetration at 25 ° C. and / or 50 ° C. exceeds the respective upper limit value, the wax particles may lack sufficient strength to withstand the load of unvulcanized rubber.

Next, specific examples of the B component will be described in detail. Component B may contain one or more of the following specific components.
The plant-based wax is not particularly limited, and examples thereof include candelilla wax, carnauba wax, rice wax, beeswax, scallop oil, sugar wax, bayberry wax, ocully wax, and esparto wax.

The animal wax is not particularly limited, and examples thereof include beeswax, lanolin, whale wax, insect wax, shellac wax and the like.
The mineral wax is not particularly limited, and examples thereof include montan wax, ozokerite, and ceresin.

The petroleum wax is not particularly limited, and examples thereof include paraffin wax, microcristan wax, and petrolactam.
The synthetic hydrocarbon wax is not particularly limited, and examples thereof include Fischer-Tropsch wax and polyethylene wax.

The modified wax is not particularly limited, and examples thereof include a montan wax derivative, a paraffin wax derivative, and a microcristan wax derivative.
The fatty acid amide is not particularly limited. For example, lauric acid amide, stearic acid amide, oleic acid amide, erucic acid amide, N, N′-xylylenebisstearic acid amide, coconut oil fatty acid monoethanolamide, N -Oleyl stearamide, N, N'-dioleoyl adipamide, and the like.

Among the B components, at least one selected from paraffin wax, microcrystalline wax, candelilla wax, carnauba wax, and rice wax is preferable.
The B component can be further divided into the following two components: B1 component and B2 component. In the B component, the B1 component is an essential component, and the B2 component is preferably a component that may be contained.

Examples of the B1 component include plant waxes, animal waxes, and mineral waxes. In these waxes, the main component is a higher fatty acid ester, and it contains free fatty acids and free alcohols as subcomponents. For this reason, the wax mentioned as B1 component shows the outstanding dispersion stability. Therefore, it is preferable that the B component contains more B1 component because the dispersion stability of the wax mixture is improved.
The amount of the B1 component is not particularly limited, but is preferably 30 to 100 parts by weight, more preferably 40 to 100 parts by weight, particularly preferably 50 to 100 parts by weight, most preferably 100 parts by weight of the B component. Is 60 to 100 parts by weight. When the amount of the B1 component is less than 30 parts by weight with respect to 100 parts by weight of the B component, the wax particles may lack dispersion stability.

The melting point of the B1 component is not particularly limited, but is preferably 70 to 150 ° C, more preferably 70 to 130 ° C, particularly preferably 70 to 120 ° C, and most preferably 80 to 100 ° C. If the melting point of B1 is less than 70 ° C., the wax particles may lack sufficient strength to withstand the load of unvulcanized rubber. On the other hand, if the melting point is higher than 150 ° C., the coating film on the unvulcanized rubber surface may lack uniformity.
The smaller the penetration of the B1 component, the higher the hardness and the more preferable is the formation of wax particles having the strength to withstand the load of rubber. The penetration of B1 component at 25 ° C. is preferably 10 mm or less (100 g / 5 s), more preferably 7 mm or less (100 g / 5 s), particularly preferably 5 mm or less (100 g / 5 s), and most preferably 3 mm or less (100 g / 5s). The penetration at 50 ° C. is preferably 25 mm or less (100 g / 5 s), more preferably 20 mm or less (100 g / 5 s), particularly preferably 15 mm or less (100 g / 5 s), and most preferably 10 mm or less (100 g / 5 s). It is. If the penetration at 25 ° C. and / or 50 ° C. exceeds the respective upper limit value, the wax particles may lack sufficient strength to withstand the load of unvulcanized rubber.

The component B1 is preferably at least one selected from candelilla wax, carnauba wax, and rice wax.
Examples of the B2 component include petroleum wax, synthetic hydrocarbon wax, modified wax, fatty acid amide, and phthalic anhydride imide. When it is desired to further improve the dispersion stability, the B2 component is blended with the B component at an arbitrary ratio. Some of the waxes classified into the B2 component have physical properties that are not suitable for the anti-vulcanized rubber composition for unvulcanized rubber in the present invention, and there are cases in which it is necessary to pay attention not to increase the blending amount. .

The amount of the B2 component is not particularly limited, but is preferably 0 to 70 parts by weight, more preferably 0 to 60 parts by weight, particularly preferably 0 to 50 parts by weight, most preferably based on 100 parts by weight of the B component. Is 0 to 40 parts by weight. If the amount of the B2 component is more than 70 parts by weight with respect to 100 parts by weight of the B component, the wax particles may lack sufficient strength to sufficiently withstand the load of unvulcanized rubber.
The melting point of the B2 component is not particularly limited, but is preferably 60 to 150 ° C, more preferably 60 to 130 ° C, particularly preferably 60 to 120 ° C, and most preferably 60 to 100 ° C. If the melting point of B2 is less than 60 ° C., the wax particles may lack sufficient strength to sufficiently withstand the load of unvulcanized rubber. On the other hand, if the melting point is higher than 150 ° C., the coating film on the unvulcanized rubber surface may lack uniformity.

Among the B2 components, at least one selected from paraffin wax and microcrystalline wax is preferable.
The anti-adhesive composition for unvulcanized rubber of the present invention contains wax particles made of the high melting point wax mixture described above. In general, the solubility of the wax in the solvent is very small. Thus, it is believed that the wax in the solvent can only exist in the dispersion. In the dispersion of wax in a solvent, when the temperature is increased and the solution is completely dissolved and then gradually cooled, some wax precipitates as fine particles and disperses with low viscosity, but most waxes have large precipitated particles. Since it becomes too much and separates, a dispersant is added to make a stable system. In the present invention, the surfactant, water-soluble polymer, dispersion stabilizer and the like described below play a role as a dispersant for wax particles in water. Here, dispersion is defined as a phenomenon in which other substances are scattered as small particles in one substance. Depending on the phase state, the dispersion is further classified as follows. That is, the phenomenon of dispersing a liquid substance as small particles in a liquid is classified as emulsification, while the phenomenon of dispersing a solid substance as small particles in a liquid is classified as suspension. Therefore, the anti-adhesive composition for unvulcanized rubber of the present invention is expressed as an emulsified state because the wax particles are dispersed as a liquid under a temperature condition higher than the melting point of the wax. On the other hand, since the wax solidifies below the melting point at normal temperature, the solid wax particles are dispersed in the liquid. Therefore, it is expressed strictly as a suspended state. The anti-adhesive composition for unvulcanized rubber of the present invention may be either emulsified or suspended.

In the anti-vulcanized rubber composition of the present invention, the advantage that the wax particles are dispersed in water is that in the production process of industrial rubber products, in the work process due to dust generation and in occupational safety and health. It is mentioned that this problem can be reduced. That is, as a method for preventing adhesion of unvulcanized rubber in recent years, a suspension obtained by suspending a powdered anti-wearing composition in water is sprayed on unvulcanized rubber, A so-called wet method such as a method of immersing vulcanized rubber is the mainstream. Dust generated during the preparation of the suspension is a problem in the work process and occupational health and safety. In the anti-vulcanized rubber anti-adhesive composition of the present invention, the anti-wear composition is dispersed in water in advance. If this is done, dust generation during the preparation of the suspension can be suppressed.
The water in which the wax particles are dispersed is not particularly limited and may be any of tap water, ion exchange water, distilled water and the like. Also, the amount is not particularly limited as long as the wax particles can be dispersed.

The particle size of the wax particles may be significantly affected by the type and amount of the surfactant, water-soluble polymer and dispersion stabilizer described below, and an emulsifier and a pulverizer. Therefore, the particle diameter can be freely designed by appropriately setting and selecting these. The smaller the particle size of the wax particles, the more preferable because the surface of the rubber can be sufficiently uniformly applied with a small blending amount in the unvulcanized rubber anti-corrosive composition. Further, it is preferable that the particle diameter is small because the powder particles of the wax particles adhering to the unvulcanized rubber surface are reduced.
The average particle diameter of the wax particles is not particularly limited because it can be designed freely according to the use, but is preferably 0.1 to 100 μm, more preferably 0.1 to 80 μm, and particularly preferably 0.1. It is ˜60 μm, most preferably 0.1 to 50 μm. When the average particle diameter of the wax particles is less than 0.1 μm, it may be difficult to process the wax particles, which is not preferable. On the other hand, when the average particle diameter of the wax particles is more than 100 μm, there are cases where the wax particles adhering to the surface of the unvulcanized rubber increase in powder and are not preferable.

(Surfactant)
As the surfactant, nonionic surfactants, anionic surfactants, cationic surfactants, and the like, may include one or two or more. It is preferable that the surfactant is a nonionic surfactant and / or an anionic surfactant.
Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene cetyl ether and polyoxyethylene lauryl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonyl phenyl ether and polyoxyethylene octyl phenyl ether. Polyoxyethylene fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monooleate; sorbitan fatty acid esters such as sorbitan monopalmitate and sorbitan monooleate; polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan mono Polyoxyethylene sorbitan fatty acid esters such as oleate; glycerin monostearate, glycerin monopalmitate, glycerin Polyoxyethylene hydrogenated castor oil such as nolaurate; polyoxyethylene hydrogenated castor oil; polyoxyethylene sorbitol fatty acid ester; polyglycerin fatty acid ester; alkyl glycerol ether; polyoxyethylene cholesteryl ether; alkyl polyglucoside; sucrose fatty acid ester; An amine; an oxyethylene-oxypropylene block polymer etc. are mentioned, You may use 1 type or 2 types or more together. Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerin fatty acid esters and polyoxyethylenes because of their great dispersion effect on wax particles. At least one selected from hardened castor oil is preferred.

There is no particular limitation on the HLB value of the nonionic surfactant. In general, nonionic surfactants having an HLB value of 8 to 18 are used for oil-in-water emulsification, and nonionic surfactants having an HLB value of 3 to 6 are often used for water-in-oil emulsification. In many cases, a nonionic surfactant having a high HLB value and a nonionic surfactant having a low HLB value are used in combination, but the invention is not limited thereto. In the present invention, the HLB value is a value measured by the Davies method.
Examples of the anionic surfactant include fatty acid salts such as sodium oleate, potassium palmitate and triethanolamine; alkyl sulfate esters such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium stearyl sulfate and sodium cetyl sulfate; Polyoxyethylene alkyl ether acetates such as sodium oxyethylene tridecyl ether acetate; Alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; Polyoxyethylene alkyl ether sulfates; Stearoyl methyl taurine Na, Lauroyl methyl taurine Na, Myristoyl methyl taurine Higher fatty acid amide sulfonates such as Na and palmitoylmethyl taurine Na; N-acyl mons such as lauroyl sarcosine sodium Syn salts; alkyl phosphates such as sodium monostearyl phosphate; polyoxyethylene alkyl ether phosphates such as polyoxyethylene oleyl ether sodium phosphate and polyoxyethylene stearyl ether sodium phosphate; di-2-ethylhexyl sulfosuccinate Long-chain sulfosuccinates such as sodium acid, sodium dioctylsulfosuccinate, long-chain N-acyl glutamates such as sodium monosodium N-lauroylglutamate, disodium N-stearoyl-L-glutamate, etc. More than one species may be used in combination. As an anionic surfactant, fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, polyoxyethylene alkyl ether sulfates, higher fatty acid amide sulfonates, polyoxyethylenes because of their great dispersion effect on wax particles At least one selected from alkyl ether phosphates and long-chain sulfosuccinates is preferred.

An anionic activator can charge the particle interface and repel each other to prevent agglomeration. Moreover, the effect is great when used in combination with a nonionic surfactant.
Examples of the cationic surfactant include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, and cetyltrimethylammonium bromide; dialkyldimethylammonium salts; trialkylmethylammonium salts and alkylamine salts. You may use together 1 type, or 2 or more types.

The amount of the interfacial active agent is not particularly limited, with respect to 100 parts by weight of wax particles, preferably 1 to 120 parts by weight, more preferably 1 to 100 parts by weight, particularly preferably 1 to 80 parts by weight, most Preferably it is 1-60 weight part. When the amount of the surfactant is less than 1 part by weight with respect to 100 parts by weight of the wax particles, the dispersion of the wax particles in water may be insufficient. On the other hand, if the amount of the surfactant is more than 120 parts by weight, a thickening action may occur and handling properties may be lacking.

(Water-soluble polymer)
The water-soluble polymer is mainly adsorbed on the surface of the wax particles in the composition of the present invention for the unvulcanized rubber, imparts repulsive force between the wax particles due to steric hindrance, and prevents their aggregation. It acts as a protective colloid that maintains dispersion stability.
The water-soluble polymer is not particularly limited, and examples thereof include starches, mannan, alginic acids, natural gums, cellulose ethers, proteins, sodium polyacrylate, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, gelatin, and casein. Collagen, water-soluble acrylic resin, water-soluble urethane resin, water-soluble melamine resin, water-soluble epoxy resin, water-soluble butadiene resin, water-soluble phenol resin and the like. These water-soluble polymers may be used alone or in combination of two or more.

The starches are not particularly limited. For example, wheat starch, corn starch, potato starch, candy starch, tapioca starch, flour starch, oxidized starch, acetate starch, phosphate starch, carboxymethyl starch, carboxyethyl starch, and hydroxyethyl starch. , Positive starch, cyanoethylated starch, dialdehyde starch and the like.
The alginic acid is not particularly limited, and examples thereof include alginic acid, sodium alginate, propylene glycol alginate, triethanolamine alginate, ammonium alginate and the like.

The natural gums are not particularly limited, and examples include taracant gum, gum arabic, guar gum, xanthan gum, British gum, glucomannan, gellan gum, tara gum, locust bean gum, carrageenan and the like.
The cellulose ether is not particularly limited, and examples thereof include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose and the like.

The protein is not particularly limited, and examples thereof include gelatin, casein, and collagen.
Among the water-soluble polymers described above, at least one selected from polyethylene glycol, polyethylene oxide, cellulose ether, polyvinyl alcohol, polyvinyl pyrrolidone, gum arabic, guar gum, xanthan gum and sodium polyacrylate is preferable.

  The amount of the water-soluble polymer is not particularly limited, but is preferably 1 to 50 parts by weight, more preferably 1 to 40 parts by weight, particularly preferably 5 to 30 parts by weight, most preferably 100 parts by weight of the wax particles. 5 to 20 parts by weight. If the amount of the water-soluble polymer is less than 1 part by weight with respect to 100 parts by weight of the wax particles, the effect as a protective colloid may be insufficient. On the other hand, when the amount of the water-soluble polymer is more than 50 parts by weight, a remarkable thickening action occurs and handling properties may be lacking.

(Dispersion stabilizer)
In general, a dispersion system containing an oily substance and water is a thermodynamically unstable system and may be separated into two layers of an aqueous phase and an oily substance phase after a long time has passed. Such disruption of dispersion occurs, for example, through phenomena such as creaming, aggregation, and coalescence, in which droplet particles are connected to each other by van der Waals forces to form secondary aggregates. Wax particles are no exception, and after a long period of time, the dispersion breaks down. In the present invention, the dispersion stabilizer is added for the purpose of improving the dispersion stability of the wax particles and preventing the destruction of the dispersion over time.
Examples of the dispersion stabilizer include lecithin; rosin; fatty acid esters such as ethylhexyl isononanoate, isononyl isononanoate, isononyl isononanoate, isotridecyl isononanoate, isodecyl neopentanoate, ethyl isostearate, isopropyl isostearate; dodecenyl succinic anhydride, hexadecenyl succinic anhydride, alkenyl succinic anhydride, such as octadecenyl succinic anhydride; isostearate hydrogenated castor oil, dimerdilinoleic acid hydrogenated castor oil, main Chirurishinoreto, butyl ricinoleate, ethylene glycol monoricinolate, trimethylolpropane monoricinolate, grayed Castor oil derivatives such as lysine triacetyl ricinoleate, ethylene-vinyl acetate copolymer, polyalkyl methacrylate and the like. These dispersion stabilizers may be used alone or in combination of two or more. As the dispersion stabilizer, at least one selected from lecithin, rosin, alkenyl succinic anhydride, castor oil derivative, and ethylene-vinyl acetate copolymer is preferable because the dispersion stabilizing effect on the wax particles is great.

  The amount of the dispersion stabilizer is not particularly limited, but is preferably 1 to 50 parts by weight, more preferably 1 to 40 parts by weight, particularly preferably 5 to 30 parts by weight, most preferably based on 100 parts by weight of the wax particles. Is 5 to 20 parts by weight. When the amount of the dispersion stabilizer is less than 1 part by weight with respect to 100 parts by weight of the wax particles, the dispersion stability effect may be diluted. On the other hand, if the amount of the dispersion stabilizer is more than 50 parts by weight, a thickening action occurs and handling properties may be lacking.

(Other ingredients)
The anti-adhesive composition for unvulcanized rubber of the present invention may further contain an antifoaming agent, a polyhydric alcohol, and the like in addition to the components and water described above.
The antifoaming agent is not particularly limited. For example, an oil-based antifoaming agent such as castor oil, sesame oil, linseed oil, or animal and vegetable oil; a fatty acid antifoaming agent such as stearic acid, oleic acid, or palmitic acid; , Fatty acid ester antifoaming agents such as distearyl succinate, ethylene glycol distearate and butyl stearate; alcohols such as polyoxyalkylene monohydric alcohol di-t-amylphenoxyethanol, 3-heptanol and 2-ethylhexanol Defoaming agents; ether-based antifoaming agents such as di-t-amylphenoxyethanol 3-heptylcellosolvonylcellosolve 3-heptylcarbitol; phosphate ester-based antifoaming agents such as tributyl osphate and tris (butoxyethyl) phosphatate; Such as Mineral defoaming agents; Amide defoaming agents such as polyalkylene amides and acylate polyamines; Sulfate defoaming agents such as sodium lauryl sulfate ester; Mineral oil etc. May be.

The polyhydric alcohol is not particularly limited. For example, glycerin, 1,3-butanediol, propylene glycol, dipropylene glycol, pentylene glycol, hexylene glycol, polyethylene glycol, sorbitol, maltitol, sucrose, erythritol, xylitol. Etc., and one kind or two or more kinds may be used in combination.
Nonvolatile content concentration of the unvulcanized rubber anti-adhesive composition is a residue that has reached a constant weight after weighing 2-3 g of the unvulcanized rubber anti-adhesive composition and keeping it at 110 ° C. for 0.5 hours. It is the weight ratio of the product (hereinafter also referred to as “nonvolatile content”) to the anti-vulcanized rubber composition. The non-volatile content concentration of the anti-vulcanized rubber composition of the present invention is not particularly limited, but is preferably 0.1 to 60% by weight, more preferably 5 to 50% by weight, and particularly preferably 10 to 10% by weight. 50% by weight, most preferably 20-50% by weight. When the non-volatile rubber concentration of the anti-vulcanized rubber composition is less than 0.1% by weight, the concentration of the non-volatile rubber is very dilute, so that the use as an anti-corrosion agent is limited and may not be practical. On the other hand, when the non-volatile content concentration exceeds 50% by weight, the unvulcanized rubber anti-adhesive composition may lack dispersion stability. In the anti-vulcanizing rubber composition of the present invention, the residue that has reached a constant weight after being kept at 110 ° C. for 0.5 hours is composed of wax particles, surfactant, water-soluble polymer and A dispersion stabilizer is included as an essential component, and may further include inorganic particles and / or metal soap particles described below.

The viscosity (measurement temperature: 20 ° C.) of the unvulcanized rubber anti-adhesive composition is not particularly limited, but is preferably 30000 mPa · s or less, and more preferably 20000 mPa · s or less in consideration of ease of handling. Particularly preferably, it is 10000 mPa · s or less, and most preferably 5000 mPa · s or less. The lower limit of the viscosity (measurement temperature: 20 ° C.) is more than 0 mPa · s. When the viscosity (measurement temperature: 20 ° C.) of the unvulcanized rubber anti-adhesive composition is more than 30000 mPa · s, the fluidity of the unvulcanized rubber anti-adhesive composition deteriorates and the handling property is poor. There is.
Although there is no limitation in particular as pH of the unvulcanized rubber adhesion prevention composition, Preferably it is 5-12, More preferably, it is 5-10, Especially preferably, it is 6-9, Most preferably, it is 6-8. When the pH of the anti-vulcanized rubber composition for an unvulcanized rubber is less than 5 or more than 12, the handleability of the unvulcanized rubber composition for an unvulcanized rubber may be insufficient.

[Method for Producing Adhesive Composition for Unvulcanized Rubber]
The method for producing an anti-vulcanized rubber composition for an unvulcanized rubber according to the present invention is a method for producing the above-mentioned composition for an unvulcanized rubber.
As a method for producing an unvulcanized rubber anti-adhesive composition, for example, a wax mixture is emulsified and dispersed in an oil-in-water type with a surfactant, a water-soluble polymer, and a dispersion stabilizer (1), A method (2) in which the wax mixture is pulverized and granulated, and suspended and dispersed in an oil-in-water type using a surfactant, a water-soluble polymer, and a dispersion stabilizer. Here, the wax mixture is completely melt-mixed above the melting point and then processed into particles.

As the method (1), a general method is used and is not particularly limited, and examples thereof include an inversion emulsification method, a D-phase emulsification method, and an HLB temperature emulsification method. The inversion emulsification method is a method in which a surfactant is first dissolved in water, and an oil phase is dropped into the solution while stirring. Conversely, an Agent-in-oil method is also generally known in which a surfactant is added to an oil phase in advance and an aqueous phase is added thereto. The D phase emulsification method is a method in which water is further added to a transparent gel obtained by dripping the oil phase with stirring in water in which a surfactant and a polyhydric alcohol are dissolved. The HLB temperature emulsification method uses a phase inversion temperature by using a nonionic surfactant and is also called a phase inversion temperature emulsification method.
As a method of emulsifying and dispersing the wax mixture, a mechanical method may be used. For example, using a homomixer (for example, manufactured by Special Machine Engineering Co., Ltd.), a homodisper (for example, manufactured by Special Machine Engineering Co., Ltd.), or the like. A static dispersion device such as a stirring method, a high-pressure emulsification method using a microfluidizer (handled by Mizuho Kogyo Co., Ltd.), a homogenizer (Sanwa Machinery Co., Ltd.), or a static mixer (for example, manufactured by Noritake Engineering Co., Ltd.) Examples of the method used include a general dispersion method such as a film emulsification method and an ultrasonic dispersion method. Alternatively, the wax mixture may be coarsely emulsified in advance by an inversion emulsification method or the like, and finely emulsified with a high-pressure emulsifier such as a microfluidizer.

Next, in the method (2), first, wax particles are produced. A pulverizer may be used in the method of producing wax particles by making the wax mixture into particles. The crusher is not particularly limited, but, for example, jaw crusher, gyratory crusher, cone crusher, roll crusher, impact crusher, hammer crusher, rod mill, ball mill, vibration rod mill, vibration ball mill, disk type mill, jet mill, Examples include a dry pulverizer such as a cyclone mill; a wet pulverizer such as a bead mill. A method of suspending and dispersing pulverized wax particles, a surfactant, a water-soluble polymer, and a dispersion stabilizer in water. Although there is no limitation, the method of stirring with a homomixer, a homodisper, etc. is mentioned.

In addition, wax particles, a surfactant, a water-soluble polymer, and a dispersion stabilizer are mixed in advance, and the mixture is suspended and dispersed in water by stirring with a homomixer, homodisper, or the like. Also good. The mixing is not particularly limited, and can be performed using an apparatus having a very simple mechanism such as a container and a stirring blade. Moreover, you may use the powder mixer which can perform a general rocking | swiveling or stirring. Examples of the powder mixer include a powder mixer that can perform rocking stirring or stirring, such as a ribbon mixer and a vertical screw mixer. In recent years, super mixers (manufactured by Kawata Co., Ltd.), high-speed mixers (manufactured by Fukae Co., Ltd.), and Newgram Machines (Seishin Co., Ltd.), which are efficient and multifunctional powder mixers by combining stirring devices Product), SV mixer (manufactured by Shinko Environmental Solution Co., Ltd.), and the like.
Among the production methods for the unvulcanized rubber anti-adhesive composition described above, the method of emulsifying and dispersing (1) is preferred, and the following preparation steps and mixing steps are performed in consideration of the production equipment and the simplicity of work. More preferred is a method comprising.

Preparation step: a step of dissolving or dispersing a water-soluble polymer in water and heating and stirring above the melting point of the wax mixture to obtain an intermediate raw material and melting the wax mixture to obtain a wax melt mixture. Mixing step: A step of dropping and mixing the wax melt mixture, the surfactant and the dispersion stabilizer into an intermediate raw material, and emulsifying and dispersing.

As a preparatory step, first, a water-soluble polymer is dissolved or dispersed in water, and heated and stirred above the melting point of the wax mixture to obtain an intermediate raw material. The method for dissolving or dispersing the water-soluble polymer in water is not particularly limited. For example, 1) a method in which the water-soluble polymer is poured into cold water and gradually heated while stirring, and 2) in hot water Although there is a method of adding a water-soluble polymer, etc., 1) is preferable because the working time can be shortened. The obtained intermediate raw material is in a state in which a water-soluble polymer is dissolved or dispersed in water, and is heated to a temperature equal to or higher than the melting point of the wax mixture to be emulsified. Here, when the temperature is lower than the melting point of the wax mixture, stable emulsification and dispersion cannot be performed. Here, when the melting point of the wax mixture is close to the boiling point of water or the intermediate raw material or higher than the boiling point, the intermediate raw material is heated above the melting point of the wax mixture under pressure.
The temperature of the intermediate raw material is set by the melting point of the wax mixture, but is preferably controlled in the range of 60 to 160 ° C, more preferably 80 to 120 ° C, and particularly preferably 90 to 110 ° C. Although there are no particular limitations on the pressurizing conditions for the intermediate raw material, the gauge pressure is in the range of 0 to 5.0 MPa, more preferably 0.1 to 3.0 MPa, and particularly preferably 0.2 to 2.0 MPa. In addition to the intermediate raw material, the wax mixture is melted to obtain a wax melt mixture.

In the mixing step, there is no particular limitation on the order in which the wax melt mixture, the surfactant and the dispersion stabilizer are dropped into the intermediate raw material and emulsified and dispersed, and the wax melt mixture, the surfactant and the dispersion stabilizer are not limited in advance. After mixing the agent, it may be added dropwise to the intermediate raw material. The time required for the dropwise mixing is not particularly limited, but is preferably about 0.1 to 6 hours.
As an advantage of emulsifying and dispersing the wax mixture, for example, the wax mixture can be finely divided into wax particles, and the particle diameters can be made uniform. Since the wax has a high melting point and high hardness at room temperature, it is difficult to process the wax. Further, if the processed wax particles are rough and the particle diameter is not uniform, the dispersion system becomes unstable. In the case of emulsified dispersion of wax, since the wax is usually completely dissolved and dispersed at a high temperature, it is easy to adsorb lipophilic dispersants and dispersants having a high molecular weight on the interface, and the coating on the wax particle interface can be strengthened. . The strength of the wax particle coating greatly affects dispersion stabilization. Some dispersants have water-insoluble properties. When using such dispersants, melt them in advance and make them liquid, mix them with the melted liquid wax, and drop them into water. Thus, a method for transferring the dispersant to the interface is selected.

[Method for producing non-vulcanized rubber subjected to adhesion treatment]
The method for producing an adhesion-treated unvulcanized rubber according to the present invention comprises a treatment step of adhering the above-mentioned adhesion composition for unvulcanized rubber or a diluted solution thereof to the surface of the molded unvulcanized rubber. Including. Hereinafter, for the sake of simplicity, the “anti-adhesive composition for unvulcanized rubber or a diluted solution thereof” may be referred to as “an anti-adhesive composition or the like”.
In the unvulcanized rubber that has been molded, the molding method, shape, etc. are not particularly limited. Examples of the molding process include a calender roll sheet molding method, a roller head sheet molding method, an extrusion sheet molding method, a ram extrusion molding method, a screw extrusion molding method, a compression molding method, an injection molding method, and an injection molding method. Can do. Examples of the shape include a sheet shape, a film shape, a hose shape, a tube shape, a sponge shape, a packing, a belt, and a shoe sole.

Examples of the adhesion method of the anti-adhesive composition include a method of spraying on the unvulcanized rubber, a method of spraying the unvulcanized rubber in a trickle, a method of immersing the unvulcanized rubber in the anti-adhesive composition and the like Can be mentioned.
In the case where the non-vulcanized rubber subjected to the adhesion treatment manufactured by adhering in this way is accumulated and stored until it moves to the next molding, vulcanization, etc., the adhesion between the unvulcanized rubbers. Can be prevented.
The diluted solution of the unvulcanized rubber anti-adhesive composition is obtained by further diluting and dispersing the anti-vulcanized rubber anti-adhesive composition with water. Here, the non-volatile content concentration of the diluent is a weight ratio of the residue that has reached a constant weight after weighing out 2 to 3 g of the diluent and keeping it at 110 ° C. for 0.5 hours. The residue that has reached a constant weight after maintaining the diluted solution at 110 ° C. for 0.5 hour contains wax particles, a surfactant, a water-soluble polymer and a dispersion stabilizer as essential components. Alternatively, metal soap particles may be further included. The nonvolatile content concentration of the diluent is not particularly limited, but preferably 0.1 to 50% by weight, and more preferably 0.1 to 10% by weight in view of not impairing the physical properties of the vulcanized rubber. Particularly preferred is 0.1 to 5% by weight, and most preferred is 0.1 to 1% by weight.

In the method for producing an adhesion-treated unvulcanized rubber according to the present invention (hereinafter sometimes referred to as “method for producing an unvulcanized rubber” for simplicity), the inorganic particles and / or the metal soap particles are added to the above-described method. It may be further adhered to the surface of the molded unvulcanized rubber. In this case, an anti-adhesive composition or the like containing inorganic particles and / or metal soap particles may be prepared in advance and adhered to the molded unvulcanized rubber in the same manner as described above. In addition to the above, inorganic particles and / or metal soap particles may be separately attached.
The inorganic particles are not particularly limited. For example, carbonates such as calcium carbonate, magnesium carbonate, and barium carbonate; silicic acids such as kaolin, aluminum silicate, calcium silicate, clay, talc, mica, sericite, and bentonite. Salts: sulfates such as calcium sulfate and barium sulfate; metal oxides such as silica, alumina, magnesium oxide, antimony trioxide, titanium oxide, white carbon, iron oxide; aluminum hydroxide, magnesium hydroxide, iron hydroxide, etc. Metal hydroxide; Bengala; Carbon black; Graphite and the like. Among these, it is preferable that the inorganic particles include at least one selected from calcium carbonate, magnesium carbonate, kaolin, clay, talc, mica, sericite, and bentonite because of excellent adhesion to the rubber surface.

The metal soap particles are not particularly limited, and examples thereof include calcium stearate, zinc stearate, magnesium stearate, lead stearate, aluminum stearate, lithium stearate, calcium oleate and the like. Among these, it is preferable that the metal soap particles are made of at least one selected from zinc stearate and magnesium stearate because of excellent adhesion to the rubber surface.
When inorganic particles and / or metal soap particles are used in the method for producing unvulcanized rubber of the present invention, the amount of inorganic particles and / or metal soap particles used can be reduced. Further, since the water-soluble polymer contained in the unvulcanized rubber anti-adhesive composition acts as a binder, it prevents the inorganic particles and / or metal soap particles from falling off. For this reason, the problem of dust generation is greatly reduced.

Accordingly, when inorganic particles and / or metal soap particles are used in the method for producing an unvulcanized rubber of the present invention, the anti-adhesiveness which has been a problem of the conventional anti-adhesive agent containing inorganic particles and metal soap particle powders. The problem of dust and the problem caused by dust can be greatly improved.
The amount of inorganic particles and / or metal soap particles used in the method for producing an unvulcanized rubber of the present invention is not particularly limited. For example, the anti-cured rubber for the unvulcanized rubber of the present invention diluted and dispersed in water. Preferably, 10 to 500 parts by weight of inorganic particles and / or metal soap particles may be further dispersed with respect to 100 parts by weight of the adhesive composition and adhered to the surface of the molded unvulcanized rubber. In view of the fact that the smaller the amount of inorganic particles and / or metal soap particles attached to the rubber surface, the adverse effects on the physical properties of the rubber product and the problem of the working environment due to dust generation can be reduced. 300 parts by weight, particularly preferably 10 to 100 parts by weight, most preferably 10 to 50 parts by weight.

Below, the Example of the anti-adhesive composition for unvulcanized rubber is demonstrated concretely. The present invention is not limited to these examples.
About the composition for unvulcanized rubber prepared in Examples 1 to 19 and the compositions evaluated in Comparative Examples 1 to 19, the physical properties were measured in the following manner, and the performance was further evaluated.

(Measurement of average particle diameter of wax particles)
A laser diffraction particle size distribution analyzer (HEROS & RODOS manufactured by SYMPATEC) was used, and the D50 value was defined as the average particle size of the wax particles.
[Non-volatile content of anti-adhesive composition for unvulcanized rubber]
The uncured rubber anti-adhesive composition A (g) was weighed on an aluminum sheet and measured for the mass of the residue that reached a constant weight after being kept at 110 ° C. for 0.5 hour. there were. However, A (g) was in the range of 2 to 3 g. The nonvolatile content concentration was calculated according to the following formula.
Nonvolatile content concentration of anti-adhesive composition for unvulcanized rubber (wt%) = (B / A) × 100

[Non-volatile content of diluted solution]
Dilution liquid a (g) was weighed on an aluminum sheet, and the mass of the residue that reached a constant weight after being kept at 110 ° C. for 0.5 hour was measured to be b (g). However, a (g) was in the range of 2 to 3 g. The nonvolatile content concentration was calculated according to the following formula.
Nonvolatile content concentration of diluted solution (wt%) = (b / a) × 100
[Measurement of Viscosity of Uncured Rubber Adhesive Composition]
As a measuring device, Brookfield viscometer (BL type, manufactured by Toki Sangyo Co., Ltd.) was used. The measurement was performed under the condition of 3.

(Measurement of peel resistance)
The anti-adhesive composition for unvulcanized rubber is diluted to an arbitrary concentration, and an NR / BR rubber test piece heated to a temperature of 100 ° C. is immersed therein and immediately pulled up. When the test piece is air-dried, the two pieces are overlapped, and a load of 1000 kg / m ² is applied and left in a constant temperature bath at 40 ° C. for 24 hours. The test piece taken out from the thermostat was air-cooled to room temperature, and the peel resistance (N / mm) was measured at a speed of 100 mm / min using a tensile tester Tensilon (PT-200N type, Minebea Co., Ltd.). The smaller the peel resistance, the easier it is to peel off and the higher the anti-adhesion property (adhesion strength). If it is 0.01 N / mm or less as a peeling resistance, unvulcanized rubber can be peeled without a big load, and it is preferable. If the peeling resistance exceeds 0.01 N / mm, the load when peeling unvulcanized rubbers is large, which is not preferable. Furthermore, if the peel resistance exceeds 0.05 N / mm, the rubbers are in close contact with each other and are difficult to peel off.

[Amount of powder adhesion and amount of powder scattering of adhesion-treated rubber]
An NR / BR rubber test piece 10 × 10 cm was prepared, and the initial weight (W ₁ ) was measured. The anti-adhesive composition for unvulcanized rubber was diluted, and a rubber test piece heated to 100 ° C. was dipped twice continuously and immediately pulled up. When the test piece was air-dried, its weight (W ₂ ) was measured. Further, the weight (W ₃ ) of the test piece after each of the six sides of the test piece was rubbed strongly 15 times with a scourer was measured. The powder adhesion amount and the powder scattering amount of the adhesion-preventing rubber are calculated by the following formula.
Amount of powder adhering to adhesion-preventing rubber (mg / 100 cm ² ) = W ₂ −W ₁
Amount of powder scattering of the adhesion-preventing rubber (mg / 100 cm ² ) = W ₂ −W ₃
The greater the amount of powder adhered to the adhesion-treated rubber, the greater the amount of the unvulcanized rubber adhesion-preventing composition mixed into the rubber, which adversely affects the physical properties of the rubber. A powder adhesion amount of less than 10 mg / 100 cm ² is preferred because it does not have a significant adverse effect on the physical properties of the rubber. If the powder adhesion amount exceeds 10 mg / 100 cm ² , the physical properties of rubber may be adversely affected, which is not preferable.
As the powder scattering amount of the adhesion-preventing treatment rubber increases, the problem of scattering due to dust that has fallen from the rubber surface increases. If the amount of powder scattering is less than 3 mg / 100 cm ² , the problem of dust generation can be greatly reduced, which is preferable. If the amount of powder scattering is more than 3 mg / 100 cm ² , scattering due to dust that has fallen from the rubber surface is undesirable.

[Composition of NR / BR rubber for measurement]
The NR / BR rubber (unvulcanized rubber fabric) used for the measurement was produced by mixing the following components and predetermined amounts, respectively.
Natural rubber 60 parts Butadiene rubber 40 parts Carbon GPF 25 parts Carbon FEF 25 parts Aroma oil 8 parts

[Example 1]
Polyvinyl alcohol (3 g), carboxymethyl cellulose (6 g), and gum arabic (3 g) were added to 400 g of ion-exchanged water with stirring, and the solution was gradually heated to 90 ° C. and completely dissolved.
Separately, hardened castor oil 40 g, paraffin wax 140 F 30 g, carnauba wax 30 g, polyoxyethylene (25) lauryl ether 12 g, dicetylsulfosuccinate soda salt 18 g, lecithin 1.5 g, rosin 6 g, ethyl isostearate An oily mixture was prepared by melting and mixing 10 g at 140 ° C., and this was dropped and dispersed in the aqueous solution heated to 90 ° C. with stirring. After stirring at 90 ° C. for 1 hour, the mixture was cooled to 40 ° C. or lower to obtain an unvulcanized rubber anti-adhesive composition.

In the obtained anti-vulcanized rubber composition for an unvulcanized rubber, no aggregation was confirmed, and the average particle diameter of the wax particles was 18.4 μm, the nonvolatile content concentration was 28.6%, and the viscosity was 0.5 Pa · s.
The obtained anti-vulcanized rubber composition for unvulcanized rubber was further diluted with water to obtain a diluted solution having a nonvolatile content concentration of 0.6% by weight. An NRBR rubber test piece heated to 100 ° C. was immersed in this diluted solution and immediately pulled up. When the rubber test piece was air-dried, the two pieces were superposed, and a load of 1000 kg / m ² was applied and left in a constant temperature bath at 40 ° C. for 24 hours. The peel resistance was 0 N / mm, it was possible to peel without load, and the adhesion resistance was excellent. Further, the powder coating weight 5.9 mg / 100 cm ^2, powder scattering amount since it is very low amounts and 1.5 mg / 100 cm ^2, it can be greatly reduced the problem of adverse effects and dust generation giving the physical properties of the rubber .

[Example 2]
Polyvinyl alcohol 6g, methylcellulose 3g, and gum arabic 6g were added to 400g of ion-exchanged water with stirring, and an aqueous solution in which the solution was gradually heated to 110 ° C under a pressure of 0.5MPa and completely dissolved was prepared.
Separately, 50 g of hardened castor oil, 50 g of polyethylene wax A-C629 (manufactured by Honeywell), 12 g of polyoxyethylene (25) lauryl ether, 18 g of dicetylsulfosuccinate soda salt, 8 g of rosin, 2 g of dodecenyl succinic anhydride Then, 8 g of ethyl isostearate was melt-mixed at 140 ° C. to prepare an oily mixture, and this was dropped and dispersed in the aqueous solution heated to 110 ° C. with stirring. After stirring at 110 ° C. for 1 hour, the mixture was cooled to 40 ° C. or lower to obtain an unvulcanized rubber anti-adhesive composition.

Aggregation was not confirmed in the obtained anti-vulcanized rubber composition for unvulcanized rubber, and the wax particles had an average particle size of 20.2 μm, a non-volatile content concentration of 29.2%, and a viscosity of 3.2 Pa · s.
The obtained anti-vulcanized rubber composition for unvulcanized rubber was further diluted with water to obtain a diluted solution having a nonvolatile content concentration of 0.6% by weight. An NRBR rubber test piece heated to 100 ° C. was immersed in this diluted solution and immediately pulled up. When the rubber test piece was air-dried, the two pieces were superposed, and a load of 1000 kg / m ² was applied and left in a constant temperature bath at 40 ° C. for 24 hours. The peel resistance was 0.003 N / mm, it was possible to peel without load, and the adhesion resistance was excellent. In addition, since the powder adhesion amount is 6.2 mg / 100 cm ² and the powder scattering amount is 1.7 mg / 100 cm ^{2, which} is a very small amount, the adverse effects on the physical properties of rubber and the problem of dust generation can be greatly reduced. .

[Examples 3 to 13]
In Examples 3 to 13, except that the compositions were changed as shown in Table 1 and Table 2 in Example 1, emulsification was performed in the same manner as in Example 1 to obtain an unvulcanized rubber anti-adhesive composition. Each was obtained and the physical properties and the like were evaluated in the same manner as in Example 1. The results are shown in Table 1 and Table 2, respectively. They are excellent in anti-adhesion properties and have very little powder adhesion and powder scattering, so that the adverse effects on the physical properties of rubber and the problem of dust generation can be greatly reduced.

Example 14
Polyvinyl alcohol 6g, carboxymethyl cellulose 3g, and gum arabic 6g were added to 400g of ion-exchanged water with stirring, and the mixture was gradually heated to 90 ° C to be completely dissolved.
Separately, hardened castor oil 60 g, rice wax 15 g, carnauba wax 25 g, polyoxyethylene (50) lauryl ether 13 g, dioctylsulfosuccinate soda salt 10 g, rosin 5 g, and isostearic acid hydrogenated castor oil 8 ° C. An oily mixture was prepared by melting and mixing, and this was dropped and dispersed in the aqueous solution heated to 90 ° C. with stirring. After stirring at 90 ° C. for 1 hour, the mixture was cooled to 40 ° C. or lower to obtain an unvulcanized rubber anti-adhesive composition. Aggregation was not confirmed in the obtained anti-vulcanized rubber composition for unvulcanized rubber, and the wax particles had an average particle size of 16.2 μm, a non-volatile content concentration of 27.5%, and a viscosity of 2.1 Pa · s.

The obtained anti-vulcanized rubber composition for an unvulcanized rubber was diluted with water so that the non-volatile concentration was 0.5% by weight, and then calcium carbonate was added to obtain a diluted solution. In addition, since the addition amount of calcium carbonate was adjusted to be 0.5% by weight of the diluted solution, the nonvolatile content concentration of the diluted solution was 1.0% by weight. An NRBR rubber test piece heated to 100 ° C. was immersed in this diluted solution and immediately pulled up. When the rubber test piece was air-dried, the two pieces were superposed, and a load of 1000 kg / m ² was applied and left in a constant temperature bath at 40 ° C. for 24 hours. The peel resistance was 0 N / mm, it was possible to peel without load, and the adhesion resistance was excellent. Further, the powder coating weight 4.8 mg / 100 cm ^2, powder scattering amount since it is very low amounts and 1.1 mg / 100 cm ^2, it can be greatly reduced the problem of adverse effects and dust generation giving the physical properties of the rubber .

[Examples 15 to 19]
Examples 15 to 19 were prepared in the same manner as in Example 14 except that the compositions were changed as shown in Table 3 in Example 14 to obtain unvulcanized rubber anti-adhesive compositions. Next, dilutions were obtained in the same manner as in Example 14, and physical properties and the like were evaluated. The results are shown in Table 3, respectively. Since they are excellent in anti-adhesion properties and have very small amounts of powder adhesion and powder scattering, the adverse effects on the physical properties of rubber and the problem of dust generation can be greatly reduced.

[Comparative Example 1]
To 400 g of ion-exchanged water, 10 g of polyvinyl alcohol, 5 g of carboxymethylcellulose, and 3 g of gum arabic were added with stirring, and an aqueous solution in which the solution was gradually heated to 90 ° C. and completely dissolved was prepared.
100 g of polyethylene wax A-C629, 10 g of polyoxyethylene (25) lauryl ether, 13 g of dicetylsulfosuccinate soda salt, 1 g of lecithin and 4 g of rosin were melt-mixed at 100 ° C. or higher to prepare an oily mixture. The mixture was dropped and dispersed in ion-exchanged water heated to 90 ° C. with stirring. After stirring at 90 ° C. for 1 hour, the mixture was cooled to 40 ° C. or lower to obtain a comparative composition.

Aggregation was not confirmed in the obtained comparative composition, and the average particle diameter of the wax particles was 20.5 μm, the nonvolatile content concentration was 26.9%, and the viscosity was 3.8 Pa · s.
The obtained comparative composition was further diluted with water to obtain a comparative diluted solution having a nonvolatile content concentration of 0.6% by weight. An NRBR rubber test piece heated to 100 ° C. was immersed in this comparative dilution and immediately pulled up. When the rubber test piece was air-dried, the two pieces were superposed, and a load of 100 kg / m ² was applied and left in a constant temperature bath at 40 ° C. for 24 hours. When the peel resistance was measured, the peel resistance was more than 0.05 N / mm, and it was not possible to adhere and peel. Moreover, the powder adhesion amount was 5.8 mg / 100 cm ² , and the powder scattering amount was 1.5 mg / 100 cm ² . Compared with Examples 1-13, although the amount of powder adhesion and the amount of powder scattering were the same and small, peeling resistance was large and it was not excellent in adhesion resistance.

[Comparative Examples 2-6]
In Comparative Examples 2 to 6, except that the composition was changed as shown in Table 4 in Comparative Example 1, emulsification was performed in the same manner as in Comparative Example 1 to obtain comparative compositions, and physical properties and the like were evaluated. . The results of physical properties and the like of the obtained comparative composition are also shown in Table 4. Compared with Examples 1-13, although the amount of powder adhesion and the amount of powder scattering were the same and small, peeling resistance was all over 0.01 N / mm and was not excellent in adhesion resistance.

[Comparative Example 7]
The comparative compositions prepared in Comparative Example 2, Comparative Example 3 and Comparative Example 4 were mixed in equal amounts to prepare a comparative composition containing each of paraffin wax particles, carnauba wax particles and hardened castor oil particles. .
The obtained comparative composition was further diluted with water to obtain a comparative diluted solution having a nonvolatile content concentration of 0.6% by weight. An NRBR rubber test piece heated to 100 ° C. was immersed in this comparative dilution and immediately pulled up. When the rubber test piece was air-dried, the two pieces were superposed, and a load of 1000 kg / m ² was applied and left in a constant temperature bath at 40 ° C. for 24 hours. The peel resistance was 0.04 N / mm. Moreover, the powder adhesion amount was 5.8 mg / 100 cm <2>, and the powder scattering amount was 1.8 mg / 100 cm < ² >. Compared to the results of Example 1, the adhesion was not excellent.

[Comparative Example 8]
The comparative compositions prepared in Comparative Example 1 and Comparative Example 4 were mixed in equal amounts, and the unvulcanized rubber adhesion containing each of polyethylene wax A-C629 (manufactured by Honeywell) particles and hardened castor oil particles. An agent composition was prepared.
The obtained comparative composition was further diluted with water to obtain a comparative diluted solution having a nonvolatile content concentration of 0.6% by weight. An NRBR rubber test piece heated to 100 ° C. was immersed in this comparative dilution and immediately pulled up. When the rubber test piece was air-dried, the two pieces were superposed, and a load of 1000 kg / m ² was applied and left in a constant temperature bath at 40 ° C. for 24 hours. The peel resistance was 0.05 N / mm. Moreover, the powder adhesion amount was 5.9 mg / 100 cm ² , and the powder scattering amount was 1.9 mg / 100 cm ² . Compared with the results of Example 2, the adhesion was not excellent.

[Comparative Example 9]
New Aid STR-25 (manufactured by Seiko Chemical Co., Ltd.), which is a commercially available anti-vulcanizing rubber composition, was further diluted with water to obtain a comparative diluted solution. In addition, in order to compare with the Examples 1-13, the non volatile matter density | concentration of the comparison dilution liquid was adjusted to 0.6 weight%. An NRBR rubber test piece heated to 100 ° C. was immersed in this comparative dilution and immediately pulled up. When the rubber test piece was air-dried, the two pieces were superposed, and a load of 1000 kg / m ² was applied and left in a constant temperature bath at 40 ° C. for 24 hours. When the peel resistance was measured, the peel resistance was more than 0.05 N / mm, and it was not possible to adhere and peel. Moreover, the powder adhesion amount was 7.5 mg / 100 cm ² , and the powder scattering amount was 2.1 mg / 100 cm ² . Compared with Examples 1-13, although the amount of powder adhesion and the amount of powder scattering were the same and small, peeling resistance was large and it was not excellent in adhesion resistance.

[Comparative Examples 10-12]
In Comparative Examples 10 to 12, the same procedure as in Comparative Example 9 was conducted except that a commercially available anti-vulcanized rubber composition for anti-vulcanized rubber (manufactured by Seiko Chemical Co., Ltd.) was changed as shown in Table 5. It was prepared and evaluated for physical properties and the like. The results of physical properties and the like of the obtained comparative composition are also shown in Table 5. Compared with Examples 1-13, although the amount of powder adhesion and the amount of powder scattering were the same and small, peeling resistance was large and it was not excellent in adhesion resistance.

[Comparative Example 13]
A comparative composition comprising 20 g of calcium carbonate, 50 g of bentonite as inorganic particles, 10 g of clay, 5 g of polyoxyethylene (25) lauryl ether, 6 g of dicetylsulfosuccinate soda salt and 6 g of sodium oleate as a surfactant. Got. The obtained blend was diluted and dispersed with water so that the nonvolatile content concentration was 0.6% by weight to obtain a comparative diluted solution. An NRBR rubber test piece heated to 100 ° C. was immersed in this comparative dilution and immediately pulled up. When the rubber test piece was air-dried, the two pieces were superposed, and a load of 1000 kg / m ² was applied and left in a constant temperature bath at 40 ° C. for 24 hours. When the peel resistance was measured, the peel resistance was more than 0.05 N / mm, and it was not possible to peel. Moreover, the powder adhesion amount was 8.7 mg / 100 cm ² , and the powder scattering amount was 4.1 mg / 100 cm ² . Compared with Examples 1-19, peeling resistance was large and was not excellent in adhesion resistance.

[Comparative Examples 14-19]
In Comparative Examples 14 to 19, the same composition as Comparative Example 13 was used except that the composition and the non-volatile content concentration of the diluent were changed as shown in Table 6 in Comparative Example 13 to obtain comparative compositions. The physical properties were evaluated. The results of physical properties and the like of the obtained comparative composition are also shown in Table 6. These results showed a large peel resistance and were not excellent in adhesion resistance compared with Examples 1-19. In Comparative Examples 17 to 19, the nonvolatile content concentration of the comparative composition was increased stepwise. Increasing the nonvolatile content concentration decreased the peel resistance and improved the adhesion, but increased the amount of powder adhesion and powder scattering, and there are concerns about the adverse effects on the physical properties of rubber and the problem of dust generation. There's a problem. Like Examples 1-19, although it was a small amount of powder adhesion and a powder scattering amount, it was not able to express the outstanding adhesion prevention.

In the above Tables 1 to 4, the penetration is a numerical value at 25 ° C. applied to JIS K-2235 5.4, and its unit is mm (100 g / 5 s).
In the said Tables 1-6, POE (n) means polyoxyethylene (the number of repeating units of oxyethylene: n).

Claims (14)

A composition comprising wax particles made of a wax mixture, a surfactant, a water-soluble polymer, a dispersion stabilizer (excluding the surfactant) , and water,
The surfactant is at least one selected from a nonionic surfactant, an anionic surfactant and a cationic surfactant;
1 to 120 parts by weight of a surfactant, 1 to 50 parts by weight of a water-soluble polymer, and 1 to 50 parts by weight of a dispersion stabilizer are blended with respect to 100 parts by weight of the wax particles.
100 parts by weight of the wax mixture is composed of 30 to 90 parts by weight of the following component A and 10 to 70 parts by weight of component B,
The wax particles are dispersed in the water.
Anti-adhesive composition for unvulcanized rubber.
Component A: Hydrogenated wax Component B: At least one selected from plant waxes, animal waxes, mineral waxes, petroleum waxes, synthetic hydrocarbon waxes, modified waxes, fatty acid amides, and phthalic anhydride imides   The anti-adhesive composition for unvulcanized rubber according to claim 1, wherein the hydrogenated wax has a melting point of 60 to 150 ° C.   Of the component B, the penetration of the wax occupying 30% by weight or more is within a range of 10 mm or less (100 g / 5 s) at 25 ° C. and 25 mm or less (100 g / 5 s) at 50 ° C., respectively. The anti-adhesive composition for unvulcanized rubber according to claim 1 or 2.   The anti-adhesive composition for unvulcanized rubber according to claim 3, wherein the melting point of the wax occupying 30% by weight or more is 70 to 150 ° C.   The said A component contains at least 1 sort (s) chosen from hardened castor oil, 12-hydroxystearic acid, and its derivative (s) in any one of Claims 1-4.   The said B component contains at least 1 sort (s) chosen from a paraffin wax, a micro christan wax, a candelilla wax, a carnauba wax, and a rice wax, The adhesion preventive composition for unvulcanized rubbers in any one of Claims 1-5. object.   The anti-adhesive composition for unvulcanized rubber according to any one of claims 1 to 6, wherein the wax particles have an average particle diameter of 0.1 to 50 µm.   The anti-adhesive composition for unvulcanized rubber according to any one of claims 1 to 7, wherein the surfactant is a nonionic surfactant and / or an anionic surfactant.   The nonionic surfactant is at least one selected from polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester and polyoxyethylene hydrogenated castor oil, The anionic surfactant is at least one selected from fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl ether sulfates, higher fatty acid amide sulfonates, alkyl ether phosphate esters and long chain sulfosuccinates. The anti-adhesive composition for unvulcanized rubber according to claim 8, which is a seed.   The water-soluble polymer is at least one selected from polyethylene glycol, polyethylene oxide, cellulose ether, polyvinyl alcohol, polyvinyl pyrrolidone, gum arabic, guar gum, xanthan gum and sodium polyacrylate. An anti-adhesive composition for unvulcanized rubber as described in 1. The dispersion stabilizer is lecithin, rosin, ethylhexyl isononanoate, isononyl isononanoate, isodecyl isononanoate, isotridecyl isononanoate, isodecyl neopentanoate, ethyl isostearate, isopropyl isostearate, alkenyl succinic anhydride, hydrogenated isostearic acid castor oil, dye Merlinoleic acid hydrogenated castor oil, methylricinoleate, butylricinoleate, ethylene glycol monoricinoleate, trimethylolpropane monoricinoleate, glycerin triacetylricinoleate and ethylene-vinyl acetate copolymer, The anti-adhesive composition for unvulcanized rubber according to any one of claims 1 to 10. A method for producing the unvulcanized rubber anti-adhesive composition according to any one of claims 1 to 11, comprising:
The water-soluble polymer is dissolved or dispersed in the water, heated and stirred above the melting point of the wax mixture to obtain an intermediate raw material, and the wax mixture is melted to obtain a wax melt mixture,
Next, the intermediate raw material includes a mixing step in which the wax melt mixture, the surfactant and the dispersion stabilizer are dropped and emulsified and dispersed.
A method for producing an anti-adhesive composition for unvulcanized rubber.   An anti-adhesion treatment comprising an anti-adhesion composition for unvulcanized rubber according to any one of claims 1 to 11 or a diluting solution thereof attached to the surface of a molded unvulcanized rubber. A method for producing unvulcanized rubber.   Inorganic particles and / or metal soap particles are further adhered to the surface of the molded unvulcanized rubber, and the inorganic particles are selected from calcium carbonate, magnesium carbonate, kaolin, clay, talc, mica, sericite and bentonite. The method for producing a non-vulcanized rubber subjected to adhesion prevention treatment according to claim 13, wherein the metal soap particles are at least one selected from zinc stearate and magnesium stearate.