JP6025577B2 - Release agent composition for molding vulcanization of rubber products and method for producing rubber products - Google Patents

Description

  The present invention relates to a release agent composition for molding and vulcanizing rubber products and a method for molding and vulcanizing rubber products. More specifically, the present invention forms a good releasable film in a short time on the surface of a bladder used when molding and vulcanizing rubber products such as bicycles, automobiles and other tires and aircraft tires. Therefore, the number of molding vulcanizations performed using the same bladder increases, and the defective rate of the rubber product obtained can be reduced. It relates to a sulfur process.

When molding and vulcanizing a rubber product, a rubber bag called a bladder or airbag (hereinafter sometimes referred to as a bladder) is inserted inside the raw rubber that is the rubber product before molding and vulcanizing, and the inside of the bladder Introducing a high-temperature and high-pressure gas (for example, steam at about 180 ° C.) or a liquid to expand the bladder, press the raw rubber against the mold, heat and pressurize, and perform molding vulcanization to obtain a rubber product. May be manufactured.
When the rubber product is a tire, the bladder is inserted inside the tire before molding and vulcanization (hereinafter sometimes referred to as a green tire), the bladder is inflated, and the green tire is pressed against the mold and heated. Pressing and molding vulcanization. In this case, since both the bladder and the inner surface of the green tire are made of rubber, a release agent is necessary between them.

Conventionally, in tire molding vulcanization, for example, a water-based or solvent-based release agent called inside paint is applied to the inner surface of the green tire each time, and a bladder is used to improve the peeling between the green tire and the bladder. A method of applying a silicone release agent to the surface has been performed.
For example, Patent Document 1 proposes an aqueous diorganopolysiloxane emulsion in which an inorganic silicate whose surface has been hydrophobized by reaction with an organosilicon compound is dispersed as an inside paint. Patent Document 2 proposes a powder release agent composition comprising a copolymer of dialkylpolysiloxane and polyalkylene glycol and mica or talc. However, the method of applying the inside paint to the inner surface of the green tire each time has a problem that the process becomes complicated and stains around the device occur during application. Also, as a problem larger than this problem, troubles such as inside paint entering the joint part of the tire inner liner and peeling of the inner liner joint part to cause tire failure may occur, or the tire after applying the inside paint There is a problem that an enormous space is required for the stock point until it is put into the molding process.

Therefore, as a method different from the inside paint, there is a method of applying a silicone release agent to the surface of the bladder in order to improve the peeling between the green tire and the bladder. As a release agent composition for a bladder, for example, Patent Document 3 proposes a lubricant composition that self-crosslinks with a carbon dioxide gas containing an aminoalkyl group-modified organopolysiloxane and a surfactant. In Patent Document 4, a mixture of a silicone rubber and a silicone release agent that polymerizes under the action of moisture or heat is applied to the bladder and exposed to moisture-containing air or heat, thereby releasing the release agent film on the bladder. Has been proposed. Further, Patent Document 5 discloses a two or more release lubricant layers in which a room temperature curable silicone layer having adhesiveness to a bladder is applied to the innermost layer and a condensation type silicone resin layer is formed on the outermost layer. A bladder with it has been proposed. Patent Document 6 proposes a method using a vulcanizing bladder surface-treated with a silicone composition containing organopolysiloxane, methylhydrogenpolysiloxane, silica, and metal organic acid salt. However, in the method of applying a silicone-based release agent to the bladder surface, it is difficult to form a good release film in a short time with a technique using a silicone-based aqueous release agent. In addition, the adhesion between the release agent film and the bladder is insufficient, so the release property during the molding vulcanization process is weak, especially when continuously molded and vulcanized, the release film deteriorates in a short time and manufactured. There is also a problem that defects occur in the rubber product inside. In the technique using a solvent-based release agent, a good release film can be formed in a relatively short time.
Thus, each of the release agents of Patent Documents 1 to 6 has a problem. However, the current situation is that conventional inside paint release agents and bladder release agent compositions have to be used while having releasability problems, workability problems, and VOC problems. It was.

JP-A-53-42243 JP 52-86477 A JP-A-60-229719 JP 59-106948 A JP-A-6-339927 JP-A-62-275711

  An object of the present invention is to provide a release agent for molding vulcanization of rubber products, which can quickly form an elastic coating on the surface of the bladder, has excellent mold releasability during the molding vulcanization process of rubber products, and can be continuously molded and vulcanized. An object of the present invention is to provide a composition and a method for producing a rubber product that is efficiently performed using the mold release composition for molding vulcanization.

A release agent composition for molding vulcanization of a rubber product of the present invention is a release agent containing the following components (A) to (D), a surfactant, and water. ) Is 100 parts by weight, the respective compounding amounts are 1 to 50 parts by weight of component (B), 1 to 50 parts by weight of component (C), and 1 to 50 parts by weight of component (D). Part, surfactant is 0.1 to 50 parts by weight, and water is 100 to 20000 parts by weight.
Component (A): Hydrogen polysiloxane Component (B): Dimethyl polysiloxane Component (C): Organopolysiloxane having an aminoalkyl group Component (D): Organoalkoxysilane

It is preferable that the release agent composition for molding and vulcanization of rubber products further has at least one selected from the following structural requirements (1) to (3).
(1) The organoalkoxysilane of component (D) is an epoxyalkoxysilane.
(2) The viscosity (measurement temperature: 25 ° C.) of the dimethylpolysiloxane of component (B) is in the range of 1000 to 30000.

(3) The surfactant is a nonionic surfactant and / or an anionic surfactant. Here, the nonionic surfactant is polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyalkylene silicone ether, polyoxyalkylene castor oil and It is at least one selected from polyoxyalkylene hydrogenated castor oil, and the anionic surfactant is a fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, polyoxyalkylene alkyl ether sulfate, higher fatty acid amide sulfonate, poly More preferably, it is at least one selected from oxyalkylene alkyl ether phosphates and long-chain sulfosuccinates.
The method for producing a rubber product according to the present invention is a method for producing a rubber product by molding and vulcanizing a raw rubber, wherein the release agent composition is adhered to the rubber on the bladder surface to form a release film. The raw rubber is disposed between the process, the rubber product mold and the treated bladder obtained in the treatment step, the treated bladder is heated and expanded, and the release bladder has a release coating. A molding vulcanization step of molding and vulcanizing the raw rubber by pressing the raw rubber against the mold while heating. Here, the rubber product is preferably a tire.

The release agent composition for molding vulcanization of rubber products according to the present invention quickly forms an elastic coating on the surface of the bladder, has excellent mold releasability during the molding vulcanization process of rubber products, Can be continuously vulcanized.
Since the method for producing a rubber product of the present invention uses the release agent composition for molding and vulcanization of the rubber product, the rubber product can be produced efficiently.

The release agent composition for molding vulcanization of rubber products of the present invention is a release agent containing the following components (A) to (D), a surfactant, and water.
Component (A): Hydrogen polysiloxane Component (B): Dimethylpolysiloxane Component (C): Organopolysiloxane having aminoalkyl group Component (D): Organoalkoxysilane First, a mold release vulcanization agent for rubber products Each component constituting the composition will be described in detail. Among the components, the components (A) to (C) are all classified into polysiloxanes when paying attention to the chemical structure. Therefore, the points common to these components will be described together. Hereinafter, the “mold release agent composition for molding vulcanization of rubber products” may be simply referred to as “mold release agent composition for molding vulcanization”.

[Components (A) to (C); polysiloxane]
Components (A) to (C) are all polysiloxanes and are components that impart film-forming properties and release properties.
Polysiloxane has a structure in which a siloxane bond (—Si—O—) is a main skeleton and a functional group is bonded to a side chain and / or a terminal thereof. Here, the functional group means a functional atom group such as a hydrogen atom group (—H), an amino group, a hydroxyl group, a carboxyl group, a polyether group, a phenyl group and an epoxy group; a hydrocarbon group bonded to these functional atom groups. A simple hydrocarbon group or the like is meant. Polysiloxanes are classified into the following four types of structures shown in 1) to 4) depending on, for example, the positions where functional groups are bonded.

1) Side chain-modified polysiloxane having a functional group bonded to a part of the side chain of polysiloxane (for example, polysiloxane represented by the following general formula (1))
2) Both-end modified polysiloxane having functional groups bonded to both ends of polysiloxane (for example, polysiloxane represented by the following general formula (2))
3) One-end-type modified polysiloxane having a functional group bonded to one end of polysiloxane (for example, polysiloxane represented by the following general formula (3))
4) Side chain double-end modified polysiloxane having functional groups bonded to both ends and both ends of polysiloxane (for example, polysiloxane represented by the following general formula (4))

(However, in the general formulas (1) to (4), X is a functional group. M is an integer of 1 to 10,000, and n is an integer of 1 to 10,000.)
The polysiloxane of components (A) to (C) may be any of the polysiloxanes classified by the general formulas (1) to (4).

The molecular weight of the polysiloxanes of the components (A) to (C) can usually be expressed by either a number average molecular weight or a weight average molecular weight. The ratio of the number average molecular weight to the weight average molecular weight is the dispersion ratio. The closer this is to 1, the narrower the molecular weight distribution is and it is close to monodispersion. However, there is no particular limitation on the molecular weight distribution of polysiloxane. Or may be polydispersed.
The number average molecular weight of the polysiloxanes of the components (A) to (C) is preferably 1000 to 10000000, more preferably 1500 to 8000000, particularly preferably 2000 to 6000000, and most preferably 3000 to 5000000. is there. When the number average molecular weight exceeds 10000000, the handling property of the release agent composition for molding vulcanization of the rubber product of the present invention may be lowered. On the other hand, if the number average molecular weight is less than 1000, the film-forming property of the release agent composition for molding vulcanization of the rubber product of the present invention may be lowered.
Hereinafter, the polysiloxanes of the components (A) to (C) will be described in detail.

[Component (A): Hydrogen Polysiloxane]
The component (A), hydrogen polysiloxane, is a component imparting releasability, and is rich in reactivity and excellent in film formation. When component (A) is represented by general formulas (1) to (4), X is H, and in any case, it has a structure in which a hydrogen atom is directly bonded to a silicon atom, that is, a Si-H structure.

Although there is no limitation in particular as a functional group equivalent of a component (A), Preferably it is 3-3000 g / mol, More preferably, it is 3-2000 g / mol, More preferably, it is 3-1000 g / mol, Most preferably, it is 3- 500 g / mol, most preferably 10 to 500 g / mol. The functional group equivalent of the component (A) indicates the mass of the component (A) containing 1 mol of H forming the Si—H structure. Here, the smaller the functional group equivalent value, the larger the amount of H that forms the Si—H structure contained per unit mass of the polysiloxane.
The viscosity of the component (A) (measurement temperature: 25 ° C.) is not particularly limited, but is preferably 10 to 30000 mPa · s, more preferably 10 to 25000 mPa · s, particularly preferably 10 to 20000 mPa · s, and most preferably. Is 100 to 20000 mPa · s.

[Component (B): Dimethylpolysiloxane]
The component (B), dimethylpolysiloxane, is a component that imparts releasability and is a component that improves the durability of the coating. When the component (B) is represented by the general formulas (1) to (4), examples of X include simple hydrocarbon groups such as a methyl group and an ethyl group.
Although there is no limitation in particular as a viscosity (measurement temperature: 25 degreeC) of a component (B), Preferably it is 10-30000 mPa * s, More preferably, it is 100-30000 mPa * s, Most preferably, it is 1000-30000 mPa * s, Most preferably Is 1000-20000 mPa · s.

  About the compounding quantity of a component (B), when the compounding quantity of a component (A) is 100 weight part, it is 1-50 weight part, Preferably it is 2-40 weight part, More preferably, it is 3-30 weight part Particularly preferred is 5 to 25 parts by weight. When the amount of component (B) is more than 50 parts by weight, the reactivity becomes poor and the film-forming ability is lowered. On the other hand, when the compounding amount of the component (B) is less than 1 part by weight, the effect of improving the durability of the coating film becomes poor and the mold release performance is lowered.

[Component (C): Polysiloxane having an aminoalkyl group]
The polysiloxane having an aminoalkyl group as the component (C) is a component imparting excellent reactivity, adsorptivity and releasability. In particular, since the amino group of the aminoalkyl group is excellent in adsorption capacity, the adsorption power of the bladder to the rubber surface can be increased. In the case where the component (C) is represented by the general formulas (1) to (4), X is —RNH ₂ (wherein R is a divalent organic group, and the carbon number thereof is preferably 1 to 30, Preferably it is 1-20.).
Although it does not specifically limit as a functional group equivalent of a component (C), Preferably it is 100-20000 g / mol, More preferably, it is 100-15000 g / mol, More preferably, it is 100-10000 g / mol, Most preferably, it is 100- 5000 g / mol, most preferably 1000 to 5000 g / mol. The functional group equivalent of the component (C) indicates the mass of the component (C) containing 1 mol of an amino group.

Although there is no limitation in particular as a viscosity (measurement temperature: 25 degreeC) of a component (C), Preferably it is 10-20000 mPa * s, More preferably, it is 10-15000 mPa * s, Most preferably, it is 10-10000 mPa * s, Most preferably Is 100 to 10,000 mPa · s.
About the compounding quantity of a component (C), when the compounding quantity of a component (A) is 100 weight part, it is 1-50 weight part, Preferably it is 2-40 weight part, More preferably, it is 3-30 weight part Particularly preferred is 5 to 25 parts by weight. When the blending amount of the component (B) is more than 50 parts by weight, the durability of the coating film is lowered. On the other hand, when the blending amount of the component (B) is less than 1 part by weight, the reactivity is poor and the film forming ability is lowered.

[Other polysiloxanes]
The release agent composition for molding vulcanization of the present invention may contain other polysiloxanes other than the components (A) to (C) described above. Examples of such other polysiloxanes include, but are not limited to, for example, hydroxy groups, carboxyl groups, polyether groups, phenyl groups, fluoroalkyl groups, higher fatty acid ester groups, long chain alkyl groups, higher fatty acid ester groups, Examples thereof include polysiloxanes having an organic group such as a mercapto group, a methoxy group, and a vinyl group, and one kind or two or more kinds may be used in combination. Among these, it is preferable that the polysiloxane is at least one selected from polysiloxanes having a hydroxy group, a polyether group, a phenyl group, a higher fatty acid ester group, and a long-chain alkyl group because of excellent emulsion stability.

[Component (D): Organoalkoxysilane]
Component (D), organoalkoxysilane, is a component that improves the film-forming ability of polysiloxane. It is considered that the alkoxysilyl group of the organoalkoxysilane is decomposed in the presence of water, converted into a silanol group, and then crosslinked with the polysiloxane. When component (D) is contained in the release agent composition for molding vulcanization, the time until each of the polysiloxanes of components (A) to (C) forms a film can be significantly shortened. Moreover, a film can be formed in a short time even in a low temperature atmosphere. When the component (D) undergoes a crosslinking reaction with each of the polysiloxanes of the components (A) to (C), the strength, heat resistance, expansion stability, vulcanization durability and the like of the coating can be improved.
Although there is no limitation in particular as a number average molecular weight of a component (D), Preferably it is 50-999, More preferably, it is 60-900, Most preferably, it is 70-800, Most preferably, it is 100-700. When the number average molecular weight of the organoalkoxysilane is 1000 or more, the film-forming ability of the release agent composition for molding vulcanization may be lowered. On the other hand, when the number average molecular weight of the component (D) is less than 50, the releasability may be lowered.

Although there is no limitation in particular as an alkoxy group of a component (D), For example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a methoxyethoxy group etc. are mentioned.
The organoalkoxysilane of component (D) may have a functional group. Such functional groups are not particularly limited. For example, amino groups, ureido groups, epoxy groups, sulfide groups, vinyl groups, methacryloxy groups, acryloxy groups, mercapto groups, amino groups, alkyl groups, phenyl groups, fluoro groups. Groups and the like.

The component (D) is not particularly limited, and examples thereof include 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminomethyldimethoxysilane, 1,2-ethanediamine, N- {3- (trimethoxysilyl) propyl}-, N-{(ethenylphenyl) methyl}, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3-aminopropyl Aminoalkoxysilanes such as trimethoxysilane and 3-phenylaminopropyltrimethoxysilane; 3-ureidopropyltriethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycid Xylpropylmethyldiethoxysilane, 3-glycidoxyp Epoxy alkoxysilanes such as pyrmethyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetra Sulfide alkoxysilane such as sulfide; Vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltris (methoxyethoxy) silane, allyltrimethoxysilane and other vinylalkoxysilanes; methacryloxypropyltrimethoxy Acryloxy such as silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane Alkoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl alkoxy silane such as mercaptopropyltriethoxysilane and the like, may be used alone or in combination of two or more. Among these, it is preferable that the component (D) is an epoxyalkoxysilane because of excellent reactivity with the polysiloxanes of the components (A) to (C).
About the compounding quantity of a component (D), when the compounding quantity of a component (A) is 100 weight part, 1-50 weight part, Preferably it is 2-45 weight part, More preferably, it is 3-40 weight part, Especially it is 3-40 weight part. Preferably it is 5-30 weight part. When the amount of component (D) is more than 50 parts by weight, the handling property is not excellent, which is not preferable. On the other hand, when the compounding amount of the component (D) is less than 1 part by weight, the reactivity becomes poor and the film forming ability is lowered.

[Surfactant]
The surfactant is a component that assists “wetting” the rubber on the bladder surface. By including the surfactant in the mold release composition for molding vulcanization of the rubber product of the present invention, it is possible to uniformly form the components (A) to (D) on the rubber on the bladder surface.
Here, “wetting” is defined as a phenomenon in which one fluid on the surface of a solid or liquid is replaced with another liquid in surface chemistry. For example, when a solid / gas interface is replaced with a solid / liquid interface, the solid is said to be wet with liquid. Accordingly, when the release agent composition for molding vulcanization of rubber products of the present invention is expressed as wet with respect to the rubber on the bladder surface, the rubber / air interface on the bladder surface is the rubber / molding vulcanization on the bladder surface. It means that it was replaced with the interface of the release agent composition for use. When it is expressed that the release agent composition for molding vulcanization of rubber products of the present invention is not sufficiently wet with the rubber on the bladder surface, the rubber / air interface on the bladder surface is the rubber / molding additive on the bladder surface. It means that the interface of the release agent composition for sulfur is not completely replaced.

Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and may include one or more. It is preferable that the surfactant is a nonionic surfactant and / or an anionic surfactant.
Nonionic surfactants include, for example, polyoxyalkylene alkyl ethers such as polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene polyoxypropylene lauryl ether; polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl Polyoxyalkylene alkyl phenyl ethers such as ethers; polyoxyalkylene fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene monooleate, polyoxyethylene polyoxypropylene monolaurate; sorbitan monopalmitate, sorbitan monooleate Sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate Polyoxyalkylene sorbitan fatty acid esters such as glycerin monostearate, glycerin monopalmitate, glycerin monolaurate and other glycerin fatty acid esters; polyoxyalkylene castor oil; polyoxyalkylene hardened castor oil; polyoxyalkylene sorbitol fatty acid ester; Examples include esters, alkyl glycerin ethers, polyoxyalkylene cholesteryl ethers, alkyl polyglucosides, sucrose fatty acid esters, polyoxyalkylene alkyl amines, and oxyethylene-oxypropylene block polymers. Good. Among them, the nonionic surfactant is at least one selected from polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, glycerin fatty acid ester, and polyoxyalkylene hydrogenated castor oil. It is preferable because it exhibits excellent wetting on the bladder rubber surface.

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; Polyoxyalkylene alkyl ether acetates such as sodium oxyethylene tridecyl ether acetate; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; polyoxyalkylene 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 salts such as lauroyl sarcosine sodium Cosine salts; alkyl phosphates such as sodium monostearyl phosphate; polyoxyalkylene alkyl ether phosphates such as sodium polyoxyethylene oleyl ether and sodium polyoxyethylene stearyl ether 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. Among these, anionic surfactants include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, polyoxyalkylene alkyl ether sulfates, higher fatty acid amide sulfonates, polyoxyalkylene alkyl ether phosphate esters and long chains. It is preferable that at least one selected from sulfosuccinates expresses excellent wetting on the bladder rubber surface.
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.

Examples of amphoteric surfactants include 2-undecyl-N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, and the like. Imidazoline-based amphoteric surfactants; 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauryldimethylaminoacetic acid betaine, amidopropylbetaine, alkylbetaine, amidebetaine, sulfobetaine and other amphoteric surfactants Agents: Examples include amino acid-type amphoteric surfactants such as N-laurylglycine, N-lauryl β-alanine, and N-stearyl β-alanine, and one or more of them may be used in combination.
The compounding amount of the surfactant contained in the release agent composition for molding vulcanization is 0.1 to 50 parts by weight, preferably 0.000 when the compounding amount of the component (A) is 100 parts by weight. It is 2 to 40 parts by weight, more preferably 0.5 to 35 parts by weight, and particularly preferably 1 to 30 parts by weight. If the amount of the surfactant is more than 50 parts by weight, foaming is likely to occur, which is not preferable. On the other hand, when the compounding amount of the surfactant is less than 0.1 parts by weight, the effect of improving the wetting on the bladder rubber surface may be reduced.

〔water〕
The water contained in the release agent composition for molding vulcanization of the rubber product of the present invention may be any of tap water, ion exchange water, distilled water and the like.
The amount of water contained in the release agent composition for molding vulcanization of rubber products of the present invention is 100 to 20000 parts by weight, preferably 200 to 200 parts by weight when the amount of component (A) is 100 parts by weight. The amount is 10,000 parts by weight, more preferably 250 to 5000 parts by weight, and particularly preferably 300 to 3500 parts by weight. If the amount of water is more than 20000 parts by weight, the wettability to rubber may be insufficient and the releasability may deteriorate. On the other hand, when the blending amount of water is less than 100 parts by weight, the amount of coating on the surface of the bladder rubber is increased, and the time required for drying the moisture is increased, which is not practical.

[Other ingredients]
The release agent composition for molding vulcanization of rubber products of the present invention may further contain an antifoaming agent, a metal catalyst, inorganic particles, etc. in addition to the components described above.
The antifoaming agent is not particularly limited. For example, an oil-based antifoaming agent such as castor oil, sesame oil, linseed oil, animal or vegetable oil; a fatty acid antifoaming agent such as stearic acid, oleic acid, or palmitic acid; isoamyl stearate 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) phosphato Amine-based antifoaming agent Polyalkylene amides, amide-based defoaming agents such acylate polyamine; sulfate-based defoaming agents such as sodium lauryl sulfate; mineral oils and the like, may be used alone or in combination of two or more.

The metal catalyst is not particularly limited. For example, bis (2-ethylhexanoate) tin, bis (neodecanoate) tin, di-n-butyltin (2-ethylhexylmalate) tin, di-n-butyltin ( 2,4-pentanedionate) tin, di-n-butylbutoxychlorotin, di-n-butyldiacetoxytin, di-n-butyldilauratetin, dimethyldinedecanoatetin, dimethylhydroxy (oleate) ) Tin catalysts such as tin and dioctyl dilaurate; hexachloroplatinum (IV) hexahydrate, dinitrodiammineplatinum (II), tetraamminedichloroplatinum (II), bis (acetylacetonato) platinum (II), trans- Diamminedichloroplatinum (II), cis-diamminedichloroplatinum (II), tetraammine Gold (II) chloride monohydrate, platinum (II) chloride, platinum (IV) chloride (pentahydrate), ammonium tetrachloroplatinate (II), potassium tetrachloroplatinate (II), tetrachloroplatinum (II) sodium acid, tetrachloroplatinum (IV) potassium, tetrachloroplatinum (IV) ammonium, tetrachloroplatinum (IV) sodium, tetrachloroplatinum (IV) hydrogen hexahydrate, tetracyanoplatinum (II) ) Potassium, tetracyanoplatinum (II) cesium, sodium tetracyanoplatinum (II), barium tetracyanoplatinum (II), rubidium tetracyanoplatinum (II), potassium tetranitroplatinum (II), hexabromoplatinum (IV) Platinum catalysts, such as potassium, etc. are mentioned, You may use 1 type (s) or 2 or more types together.
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, and sericite because of excellent adhesion to the surface of the bladder rubber.

[Physical properties of release agent composition for molding vulcanization]
Although there is no limitation in particular about the viscosity at 25 degreeC of the mold release agent composition for shaping | molding vulcanization | cure, Preferably it is 0.1-20000 mPa * s, More preferably, it is 0.1-10000 mPa * s, Most preferably, it is 0.1. ˜5000 mPa · s, most preferably 0.1 to 3000 mPa · s. When the viscosity of the release agent composition for molding vulcanization is more than 20000 mPa · s, the amount of the component coated on the rubber surface increases, and the time required to dry the moisture may become longer and may not be practical. On the other hand, when the viscosity is less than 0.1 mPa · s, the wettability with respect to the bladder rubber surface is deteriorated, and the releasability may be lowered.
The pH of the release agent composition for molding vulcanization is not particularly limited, but is preferably 3 to 12, more preferably 3 to 10, particularly preferably 3 to 7, and most preferably 3 to 6. If the pH of the release agent composition for molding vulcanization is less than 3 or more than 12, the handleability of the release agent composition for molding vulcanization may be lacking.

[Form and manufacturing method of mold release composition for molding vulcanization]
The method for producing the release agent composition for molding vulcanization of rubber products is not particularly limited, and a method of mixing components (A) to (D), surfactant and water, (other components as appropriate), etc. Can be mentioned. In the method of producing a release agent composition for molding vulcanization of rubber products, there is no particular limitation on the order of mixing, etc., all the components may be mixed simultaneously, may be mixed in order for each component, These components may be mixed and the remaining components may be added and mixed later.
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. Other examples include dry crushers such as 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, cyclone mill, etc. May be used.

[Production method of rubber products]
The method for producing a rubber product of the present invention includes a processing step and a molding vulcanization step. Here, the rubber product is preferably a tire.
The treatment step is a step of forming a release coating by adhering the release agent composition for molding vulcanization to the rubber on the bladder surface.

The bladder is inserted into the raw rubber when molding and vulcanizing the raw rubber described later (when the rubber product is a tire, it is called a green tire), and a high temperature and high pressure gas (for example, about This is a rubber bag used for performing molding vulcanization by introducing a vapor or the like at 180 ° C. or a liquid, expanding a bladder, pressing a raw rubber against a mold, heating and pressing.
There is no particular limitation on the shape of the bladder. The shape can include, for example, a sheet shape, a film shape, a hose shape, a tube shape, a sponge shape, a packing, a belt, etc., even if a groove for escaping air to the outside during vulcanization molding is engraved. Good.

The method for adhering the mold vulcanizing release agent composition to the rubber on the bladder surface is not particularly limited, for example, a method of spraying the rubber on the bladder surface using a spray gun and applying it in a mist form, Examples thereof include a method of spraying the rubber on the surface of the bladder with a trickle, a method of applying the rubber on the surface of the bladder with a brush, and a method of immersing the rubber on the surface of the bladder in the release agent composition for molding vulcanization.
The bladder to which the release agent composition for molding vulcanization is applied may take a curing period until a complete film is formed on the surface thereof. The curing period until the complete film is formed is not particularly limited, but is preferably 0.01 to 168 hours, more preferably 0.01 to 48 hours, particularly preferably 0.01 to 10 hours, most preferably Preferably it is 0.01-2 hours. If the curing period until the film is completely formed is longer than 168 hours, the working efficiency is unfavorable. On the other hand, if the curing period is less than 0.1 hour, the film may not be completely coated, which is not preferable because it is not excellent in releasability.

The coating amount of the mold vulcanization release agent composition per unit area is not particularly limited, but is preferably 1 to 150 g / m ² , more preferably 5 to 130 g / m ² , and particularly preferably 5 to 100 g. / M ² , most preferably 10 to 100 g / m ² . If the coating amount of the release agent composition for molding vulcanization per unit area is more than 150 g / m ² , the cost is increased, which is not preferable. If the coating amount of the release agent composition for molding vulcanization per unit area is less than 1 g / m ² , the mold release property is not excellent and this is not preferable.
The atmosphere temperature for curing the bladder surface until a complete film is formed is not particularly limited, but is preferably -20 to 200 ° C, more preferably 0 to 150 ° C, particularly preferably 20 to 140 ° C, most preferably Preferably it is 40-120 degreeC. If the atmospheric temperature exceeds 200 ° C., it is necessary to prepare a high-temperature thermostatic bath facility, which is not preferable. If the atmospheric temperature is less than −20 ° C., the drying property of the coating is not excellent, which is not preferable.

The thickness of the film after curing is not particularly limited, but is preferably 0.01 to 1000 μm, more preferably 0.01 to 500 μm, particularly preferably 0.01 to 250 μm, and most preferably 0.1 to 100 μm. is there. When the thickness of the coating after curing is more than 1000 μm, the cost increases, which is not preferable. If the thickness of the coating after curing is less than 0.01 μm, the release property is not excellent, which is not preferable.
The coating weight per unit area after curing is not particularly limited, but is preferably 1 to 100 g / m ² , more preferably 1 to 80 g / m ² , particularly preferably 1 to 60 g / m ² , most preferably it is a 5~40g / ^{m 2.} If the coating weight per unit area after curing is more than 100 g / m ² , the cost is increased, which is not preferable. If the coating weight per unit area after curing is less than 1 g / m ² , the mold release property is not excellent and this is not preferable.

Thus, the treated bladder obtained in the treatment step is used in the next molding vulcanization step, expresses good releasability, and increases the number of molding vulcanization times of rubber products using the same bladder, The defective rate of rubber products can be reduced.
In the molding vulcanization process, raw rubber is placed between the rubber product mold and the treated bladder obtained in the treatment process, the treated bladder is heated and expanded, and the raw material is passed through the release coating of the treated bladder. This is a step of molding and vulcanizing the raw rubber by pressing the rubber against the mold while heating.

Examples of the molding process in the molding vulcanization 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. The law etc. can be mentioned.
The rubber product obtained by the production method of the present invention is not particularly limited, but tires, hoses, anti-vibration rubber, automobile belts, seals, anti-mold agents, conveyor belts, elastic sleepers, rubber pads, rubber mats, seismic isolation Rubber, sealing material, waterproofing agent, rubber electric wire, rubber cable, condom, rubber gloves, rubber balloon, gasket, packing, rubber ball and the like can be mentioned, and tires are preferred.

There are no particular limitations on the tire, but automobile tires for passenger cars, automobile tires for trucks and buses, automobile tires for sports cars, racing car tires, aircraft tires, motorcycle tires, bicycle tires, buggy Tire, agricultural tire, rubber crawler and the like.
Although there is no limitation in particular as temperature at the time of tire molding, Preferably it is 100-300 degreeC, More preferably, it is 120-280 degreeC, Especially preferably, it is 140-260 degreeC, Most preferably, it is 160-240 degreeC.
The pressure at the time of tire molding is not particularly limited, but is preferably 0.1 to 50 MPa, more preferably 0.2 to 30 MPa, particularly preferably 0.3 to 20 MPa, and most preferably 0.5 to 10 MPa. .

Below, the Example and comparative example of a mold release agent composition for shaping | molding vulcanization | cure of rubber products are demonstrated concretely. The present invention is not limited to these examples.
First, a method for evaluating physical properties of a release agent composition for molding vulcanization will be described.

[Non-volatile content of release agent composition for molding vulcanization]
A (g) of mold release vulcanizing agent composition is weighed on an aluminum sheet (however, a (g) is in the range of 2 to 3 g) and reaches a constant weight after being kept at 110 ° C. for 0.5 hours. The mass of the residue obtained is b (g). The non-volatile content of the release agent composition for molding vulcanization is calculated according to the following formula.
Nonvolatile content concentration (wt%) of mold release composition for molding vulcanization = (b / a) × 100

[Evaluation of film formability]
Apply 15 g / m ² of a mold vulcanization release agent composition to the rubber on the bladder surface, heat it to a temperature of 100 ° C. to accelerate the reaction, form a film on the rubber on the bladder surface and dry it. Measure visually. If it is less than 2 hours until the film is formed and dried, the waiting time until the film is formed is small, and the film formability is good. If the time until the coating is formed and dried is 5 hours or longer, the waiting time until the coating is formed is long, and the workability is hindered. The evaluation criteria for film forming properties are as follows.
◯: The time until the film is formed and dried is less than 2 hours.
(Triangle | delta): Time until it forms a film and dries is less than 5 hours.
X: Time until the film is formed and dried is 5 hours or more.

[Evaluation of releasability]
Applying 15 g / m ^{2 of} mold release agent composition to rubber on the bladder surface, heating to 100 ° C. to promote the reaction, forming a film on the rubber on the bladder surface, and treating the bladder Got. The treated bladder and unvulcanized SBR rubber were superposed and press vulcanized at 180 ° C. and 2 MPa for 20 minutes. After vulcanization, the bladder 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 evaluation criteria for releasability are as follows.
A: The peel resistance is less than 0.01 N / mm.
X: Peeling resistance is 0.01 N / mm or more.

[Evaluation of repetitive release properties]
Using the treated bladder used in the evaluation of releasability, vulcanization was repeated by the same method as described above, and the number of times that releasability was maintained was measured. The more times that vulcanization can be repeated, the better the releasability. The evaluation criteria for repeated releasability are as follows.
◯: Even if vulcanization is repeated 30 times or more, the releasability is good continuously.
(Triangle | delta): Between 10 times and less than 30 times, it can repeat vulcanization with favorable mold release property.
X: The vulcanization can be repeated repeatedly with good releasability for less than 10 times.

[Evaluation of molding vulcanization test for passenger car tires]
15 g / m ^{2 of} mold release agent composition for molding vulcanization bladder surface (surface area: 6000 cm ² ) of passenger car tires is applied to the rubber and heated to a temperature of 100 ° C. to accelerate the reaction and bladder rubber A film was formed on the surface to obtain a treated bladder. Using this treated bladder, molding tires for passenger cars were repeatedly subjected to a molding vulcanization test, and the number of times that a tire could be produced without problems was measured. The evaluation criteria for the molding vehicle vulcanization test are as follows.
◯: Even if the molding vulcanization is repeated 100 times or more, the releasability is good continuously.
(Triangle | delta): Between 30 times and less than 100 times, repetitive shaping | molding vulcanization can be performed with favorable mold release property.
X: Repeated molding vulcanization can be performed with good releasability for less than 30 times.

[Evaluation of molded tire vulcanization test]
15 g / m ² of a mold vulcanization release agent composition is applied to rubber on the surface of a molded vulcanization bladder (surface area: 1500 cm ² ) of a bicycle tire, and heated to a temperature of 100 ° C. to accelerate the reaction and to make a bladder rubber A film was formed on the surface to obtain a treated bladder. Using this treated bladder, a molding tire vulcanization test was repeatedly performed, and the number of times that the tire could be produced without problems was measured. The evaluation criteria for bicycle tire molding vulcanization tests are as follows.
◯: Even if the molding vulcanization is repeated 100 times or more, the releasability is good continuously.
(Triangle | delta): Between 30 times and less than 100 times, repetitive shaping | molding vulcanization can be performed with favorable mold release property.
X: Repeated molding vulcanization can be performed with good releasability for less than 30 times.

[Composition of measurement bladder]
The bladder used for the measurement was produced by mixing the following components and predetermined amounts.
IIR rubber: 100 parts ZnO: 3 parts S _8: 2 parts Stearic acid: 1 part oil furnace black: 50 parts accelerator TT (tetramethylthiuram disulfide): 1 part

[Composition of unvulcanized SBR rubber for measurement]
The unvulcanized SBR rubber used for the above measurement was produced by mixing the following components and predetermined amounts.
SBR Rubber: 100 parts ZnO: 3 parts S _8: 2 parts Stearic acid: 1 part Carbon black: 50 parts accelerator NS (N-t-butyl-2-benzothiazolyl sulfenamide): 1 part

[Preparation of components (A) to (D)]
The physical properties of components (A) to (D) used in Examples and Comparative Examples are shown below.
1) Component (A)
Hydrogen polysiloxane 1: Polysiloxane in which X is H in the general formula (1), viscosity 20 mPa · s, functional group equivalent 60 g / mol
Hydrogen polysiloxane 2: Polysiloxane in which X is H in the general formula (1), viscosity 20 mPa · s, functional group equivalent 150 g / mol
2) Component (B)
Dimethylpolysiloxane 1: Viscosity 100 mPa · s
Dimethylpolysiloxane 2: Viscosity 10,000 mPa · s
3) Component (C)
Polysiloxane having aminoalkyl group 1: Polysiloxane having aminoalkyl group in X in general formula (2), viscosity 100 mPa · s, functional group equivalent 2200 g / mol
Polysiloxane 2 having aminoalkyl group: Polysiloxane having aminoalkyl group in X in formula (1), viscosity 800 mPa · s, functional group equivalent 1500 g / mol

4) Component (D)
Epoxy alkoxysilane: molecular weight 236.3
Aminoalkoxysilane: molecular weight 222.4
Mercaptoalkoxysilane: molecular weight 238.4
Sulfide alkoxysilane: molecular weight 539.0
Vinyl alkoxysilane: molecular weight 190.3
Acryloxyalkoxysilane: molecular weight 234.3
5) Other polysiloxane methylphenyl polysiloxane: polysiloxane containing phenyl group in X in the general formula (2), viscosity 1000 mPa · s, functional group equivalent 1500 g / mol
Polysiloxane having a polyether group: polysiloxane having a polyether group in X in formula (2), viscosity 1600 mPa · s, functional group equivalent 10000 g / mol
Polysiloxane having an alkyl group: polysiloxane having an alkyl group in X in the general formula (2), viscosity 60 mPa · s, functional group equivalent 1600 g / mol

[Example 1]
100 g of hydrogenpolysiloxane 1 as component (A), 10 g of dimethylpolysiloxane 1 as component (B), 10 g of polysiloxane 1 having an aminoalkyl group as component (C), and component (D) 18 g of epoxyalkoxysilane, 5 g of POE (25) lauryl ether, 5 g of dicetylsulfosuccinate soda salt, and 600 g of ion-exchanged water were mixed to obtain a release agent composition for molding vulcanization. This release agent composition for molding vulcanization had a nonvolatile content concentration of 19.8 wt%.
15 g / m ² of a mold vulcanization release agent composition was applied to the rubber on the bladder surface and heated to a temperature of 100 ° C. to accelerate the reaction. It took 1 hour to form a coating on the bladder surface and dry it, and a treated bladder with good coating formation (evaluation: ◯) was obtained.

The obtained treated bladder and unvulcanized SBR rubber were superposed and press vulcanized at 180 ° C. and 200 kgf / cm ² for 20 minutes, and then the treated bladder was air-cooled to room temperature. The peel resistance was 0.004 N / mm, it was possible to peel without load, and the release property was excellent (evaluation: ◯). Subsequently, continuous vulcanization was repeatedly performed using a treated bladder, and the releasability was maintained 30 times or more, and the repetitive releasability was excellent (evaluation: ◯).

[Examples 2 to 8]
In Examples 2 to 8, except that the composition was changed as shown in Table 1 in Example 1, a mold release agent composition for molding vulcanization was obtained in the same manner as in Example 1, and physical properties and the like were also implemented. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1, respectively. They were excellent in film-forming properties, releasability, lubricity and repetitive releasability.

Example 9
15 g / m ^{2 of} the mold vulcanization mold release agent obtained in Example 1 was applied to each of the molding vulcanization bladder for passenger car tires and the molding vulcanization bladder for bicycle tires. Heated to temperature to form a coating to obtain each treated bladder.
Using each treated bladder, tire vulcanization tests were repeated, and the number of times that a tire could be produced without problems was 120 for passenger car tires and 215 for bicycle tires. It was excellent (each evaluation: ○).

[Comparative Example 1]
100 g of hydrogenpolysiloxane 1 as component (A), 100 g of dimethylpolysiloxane 1 as component (B), 10 g of polysiloxane 1 having an aminoalkyl group as component (C), component (D) 18 g of epoxyalkoxysilane, 5 g of POE (25) lauryl ether, 5 g of dicetylsulfosuccinate soda salt, and 1000 g of ion-exchanged water were mixed to obtain a release agent composition for comparative molding vulcanization. The mold release agent composition for comparative molding vulcanization had a nonvolatile content concentration of 19.2 wt%.
15 g / m ^{2 of a} release agent composition for comparative molding vulcanization was applied to the rubber on the bladder surface and heated to a temperature of 100 ° C. to accelerate the reaction. It took 6 hours to form a film on the surface of the bladder and dry it, and a comparatively processed bladder with poor film formation (evaluation: x) was obtained.

The obtained comparatively processed bladder and unvulcanized SBR rubber were superposed and press vulcanized for 20 minutes under the conditions of 180 ° C. and 200 kgf / cm ² , and then the treated bladder was air-cooled to room temperature. The peel resistance was 0.1 N / mm, and the releasability was poor (evaluation: x). Subsequently, continuous vulcanization was repeated using a comparatively processed bladder, and the releasability could be maintained only 3 times, and the releasability was not good (evaluation: x).
Comparative Example 1 was inferior to Examples 1 to 8 in terms of film forming properties, releasability, and repetitive releasability.

[Comparative Examples 2 to 8]
In Comparative Examples 2 to 8, a comparative mold vulcanization release agent composition was obtained in the same manner as in Comparative Example 1 except that the composition was changed as shown in Table 2 in Comparative Example 1, and the physical properties and the like were also obtained. Evaluation was performed in the same manner as Comparative Example 1. The results of physical properties and the like obtained are also shown in Table 2. Compared with Examples 1-8, all were inferior in the point of film forming property, mold release property, and repetitive mold release property.

[Comparative Example 9]
15 g / m ^{2 of} the mold vulcanization mold release agent obtained in Comparative Example 1 was applied to each of the molding tire vulcanization bladder for passenger car tires and the molding tire vulcanization bladder for bicycle tires. Heated to temperature to form a coating to obtain each treated bladder.
When the tire vulcanization test was repeatedly performed using each of the comparatively processed bladders, the number of times that the tire can be produced without defects is 3 times for the passenger car tire and 6 times for the bicycle tire. Example 9 In comparison with, the releasability was inferior (each evaluation: x).

  In the above table, “POE (n)” means “polyoxyethylene in which the number of repeating oxyethylene groups is n”. For example, “POE (25) lauryl ether” means “oxyethylene” It means “polyoxyethylene lauryl ether having 25 repeating groups”.

Claims (7)

A release agent containing the following components (A) to (D), a surfactant, and water, and the amount of each component (A) is 100 parts by weight. 1 to 50 parts by weight of component (B), 1 to 50 parts by weight of component (C), 1 to 50 parts by weight of component (D), 0.1 to 50 parts by weight of surfactant, and 100 of water. A release agent composition for molding vulcanization of rubber products, which is ˜20,000 parts by weight.
Component (A): Hydrogen polysiloxane Component (B): Dimethyl polysiloxane Component (C): Organopolysiloxane having an aminoalkyl group Component (D): Organoalkoxysilane   The release agent composition for molding vulcanization of rubber products according to claim 1, wherein the organoalkoxysilane of the component (D) is an epoxyalkoxysilane.   The release agent composition for molding vulcanization of rubber products according to claim 1 or 2, wherein the viscosity (measurement temperature: 25 ° C) of dimethylpolysiloxane of component (B) is in the range of 1000 to 30000.   The mold release vulcanization composition for rubber products according to any one of claims 1 to 3, wherein the surfactant is a nonionic surfactant and / or an anionic surfactant.   The nonionic surfactant is polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyalkylene silicone ether, polyoxyalkylene castor oil and polyoxy At least one selected from alkylene hydrogenated castor oil, and the anionic surfactant is a fatty acid salt, an alkyl sulfate ester salt, an alkylbenzene sulfonate, a polyoxyalkylene alkyl ether sulfate, a higher fatty acid amide sulfonate, a polyoxy The rubber product molding vulcanization release according to claim 4, which is at least one selected from an alkylene alkyl ether phosphate salt and a long-chain sulfosuccinate. Composition. A method of producing rubber products by molding and vulcanizing raw rubber,
A treatment step of attaching the release agent composition according to any one of claims 1 to 5 to rubber on a bladder surface to form a release film;
A raw rubber is arranged between a rubber product mold and the treated bladder obtained in the treatment step, the treated bladder is heated and expanded, and the raw rubber is passed through the release coating of the treated bladder. A molding vulcanization step of molding and vulcanizing the raw rubber by pressing against the mold while heating,
Manufacturing method of rubber products.   The method for producing a rubber product according to claim 6, wherein the rubber product is a tire.