WO2022130890A1 - Agent de démoulage pour surfaces internes en caoutchouc, procédé de production d'un agent de démoulage pour surfaces internes en caoutchouc, dispersion aqueuse d'agent de démoulage pour surfaces internes en caoutchouc, procédé de production de produit en caoutchouc, procédé de production de pneu, produit en caoutchouc, et pneu - Google Patents

Agent de démoulage pour surfaces internes en caoutchouc, procédé de production d'un agent de démoulage pour surfaces internes en caoutchouc, dispersion aqueuse d'agent de démoulage pour surfaces internes en caoutchouc, procédé de production de produit en caoutchouc, procédé de production de pneu, produit en caoutchouc, et pneu Download PDF

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Publication number
WO2022130890A1
WO2022130890A1 PCT/JP2021/042422 JP2021042422W WO2022130890A1 WO 2022130890 A1 WO2022130890 A1 WO 2022130890A1 JP 2021042422 W JP2021042422 W JP 2021042422W WO 2022130890 A1 WO2022130890 A1 WO 2022130890A1
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WO
WIPO (PCT)
Prior art keywords
rubber
release agent
mass
mold release
component
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PCT/JP2021/042422
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English (en)
Japanese (ja)
Inventor
純 小林
宗一 下原
Original Assignee
ライオン・スペシャリティ・ケミカルズ株式会社
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Publication of WO2022130890A1 publication Critical patent/WO2022130890A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/02—Moulds or cores; Details thereof or accessories therefor with incorporated heating or cooling means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/60—Releasing, lubricating or separating agents
    • B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
    • B29C33/64—Silicone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)

Definitions

  • the present invention relates to a rubber inner surface mold release agent, a rubber inner surface mold release agent manufacturing method, a rubber inner surface mold release agent water dispersion, a rubber product manufacturing method, a tire manufacturing method, a rubber product and a tire.
  • a mold release agent for the inner surface of rubber is widely used in the manufacture of rubber products.
  • Examples of the release agent for the inner surface of rubber include a release agent for the inner surface of a tire (Patent Documents 1 and 2).
  • the mold release agent for the inner surface of the tire is used, for example, as follows. That is, in the tire manufacturing process, in the vulcanization molding of an unvulcanized raw tire, a rubber bag called a bladder is placed inside the unvulcanized raw tire, and the bladder is expanded with warm air, hot water or steam. As a result, the unvulcanized raw tire is pressed against the inside of the mold, and vulcanization is performed together with press-fit molding. In order to smoothly carry out this process, a mold release agent for the inner surface of the tire is spray-coated in advance on the inner liner surface (inner surface) of the raw tire (inside paint).
  • the film of the mold release agent for the inner surface of the tire needs to have a mold release property (peeling performance).
  • the film of the mold release agent for the inner surface of the tire needs to have slipperiness (slip performance). There is.
  • the mold release agent for the inner surface of rubber can exhibit mold release and slipperiness by blending, for example, talc, mica, or the like.
  • particles such as talc and mica are white in color, they may spoil the appearance of the final rubber product. Therefore, there is a need for a mold release agent for the inner surface of a tire that can provide high mold release and slipperiness without spoiling the appearance of the rubber product.
  • the mold release agent for the inner surface of rubber contains a large amount of filler (also referred to as powder or powder), powder fluidity in the product form is also required from the viewpoint of handleability.
  • the present invention relates to a rubber inner surface mold release agent, a method for producing a rubber inner surface mold release agent, and a rubber inner surface release agent, which have high mold release and slipperiness and are excellent in powder fluidity and appearance of rubber products.
  • the purpose is to provide a mold release liquid, a method for manufacturing a rubber product, a method for manufacturing a tire, a rubber product and a tire.
  • the rubber inner surface mold release agent of the present invention contains the following components (A) to (D), and the following components are relative to the total mass of the following components (A) to (D). It is characterized by containing 0.1 to 50% by mass of (D).
  • the method for producing a rubber inner surface mold release agent of the present invention is the method for producing the rubber inner surface mold release agent of the present invention.
  • the rubber inner surface mold release agent water dispersion of the present invention is characterized by containing the rubber inner surface mold release agent of the present invention and water.
  • the method for producing a rubber product of the present invention includes a pretreatment step for removing a mold, in which the water dispersion of the release agent for the inner surface of the rubber of the present invention is directly or indirectly adhered to the inner surface of the rubber and further volatilizes the water. It is characterized by.
  • the method for manufacturing a tire of the present invention A mold release pretreatment step of adhering the release agent water dispersion for the rubber inner surface of the present invention to at least one of the inner surface of the unsulfurized rubber raw tire and the outer surface of the bladder to further volatilize the water.
  • the bladder housed in the raw tire is expanded in the mold to press the outer surface of the raw tire against the inner surface of the mold, and the raw tire is heated in that state.
  • Vulcanization process and vulcanization process It is characterized by including.
  • the rubber product of the present invention is characterized in that the components (A) to (D) in the rubber inner surface mold release agent of the present invention are adhered to the rubber inner surface.
  • the first tire of the present invention is characterized in that the components (A) to (D) in the rubber inner surface mold release agent of the present invention are attached to the inner surface of the tire.
  • the second tire of the present invention is characterized in that the rubber inner surface mold release agent of the present invention is adhered to the inner surface of a raw tire and vulcanized.
  • the first tire of the present invention and the second tire of the present invention may be collectively referred to as "the tire of the present invention”.
  • a release agent for a rubber inner surface a method for producing a release agent for a rubber inner surface, and a release for a rubber inner surface, which have high mold release property and slipperiness and are excellent in powder fluidity and appearance of a rubber product. It is possible to provide a mold release liquid, a method for manufacturing a rubber product, a method for manufacturing a tire, a rubber product and a tire.
  • the rubber inner surface mold release agent of the present invention may be, for example, a rubber inner surface mold release agent that does not contain glass beads as the component (A).
  • the total mass of the component (D) may be 0.1 to 800% by mass with respect to the total mass of the component (A).
  • the component (A) may contain calcium carbonate.
  • the rubber inner surface mold release agent of the present invention may be, for example, a tire inner surface mold release agent.
  • the rubber inner surface mold release agent of the present invention which is a tire inner surface mold release agent, may be referred to as "the tire inner surface mold release agent of the present invention”.
  • the release agent for the inner surface of rubber of the present invention contains the following components (A) to (D), and the following component (D) is added to the total mass of the following components (A) to (D). It is characterized by containing 0.1 to 50% by mass.
  • particles such as talc and mica which are components that impart mold release and slipperiness to the rubber inner surface mold release agent, are white in color and may impair the appearance of the final rubber product. be.
  • graphite is used as the component (D) of the release agent for the inner surface of rubber. That is, since graphite is black, according to the release agent for the inner surface of rubber of the present invention containing graphite as the component (D), the whiteness of the film after coating becomes conspicuous, which impairs the appearance of the rubber product. This can be suppressed or prevented.
  • the release agent for the inner surface of rubber of the present invention high mold release property and slipperiness and excellent powder fluidity can be obtained. Further, according to the present invention, for example, it is possible to provide a tire inner surface mold release agent having good handleability, good quality and high versatility.
  • Each component in the rubber inner surface mold release agent of the present invention is not particularly limited, and is, for example, as follows.
  • the component (A) is the component (D), that is, an inorganic substance other than graphite.
  • the inorganic substance (A) (component (A)) is not particularly limited and is arbitrary, but is, for example, an inorganic substance used in a general release agent for the inner surface of rubber or a release agent for the inner surface of a tire. May be good.
  • the inorganic substance (A) may be contained in only one kind or a plurality of kinds in combination.
  • Examples of the inorganic substance contained in the inorganic substance (A) include talc, clay, mica, water-swellable clay mineral, hectorite, calcium carbonate, zeolite, montmorillonite, byderite, nontronite, saponite, and hectorite. Examples thereof include hectorite, bentonite containing montmorillonite, magnesium aluminum silicate, silicic anhydride and the like, and these may be natural products or synthetic products. Further, each of these components may or may not be contained in the component (A).
  • the talc contains as little crystalline silica as possible from the viewpoint of reducing friction.
  • the talc may have a crystalline silica content of, for example, 20% by mass or less, 10% by mass or less, 5% by mass or less, or 1% by mass or less.
  • the lower limit of the content of crystalline silica in the talc is not particularly limited, but is, for example, a value exceeding 0% by mass or 0% by mass, and may be, for example, 0.01% by mass or more.
  • the bulk density (bulk specific gravity) of the talc is not particularly limited, but may be, for example, 0.05 g / mL or more, 0.1 g / mL or more, or 0.15 g / mL or more, for example, 2.0 g. It may be / mL or less, 1.0 g / mL or less, or 0.5 g / mL or less. For the reason of reducing friction, it is preferable that the bulk density of the talc is high. For the reason of powder fluidity, it is preferable that the bulk density of the talc is low.
  • the weight average particle size of the talc is not particularly limited, but may be, for example, 0.1 ⁇ m or more, 0.2 ⁇ m or more, 0.5 ⁇ m or more, or 1 ⁇ m or more, and for example, 100 ⁇ m or less, 80 ⁇ m or less, 60 ⁇ m or less. , Or may be 50 ⁇ m or less.
  • the weight average particle size of the talc is large.
  • the weight average particle size of the talc is small.
  • the content of the talc is not particularly limited, but is, for example, 10% by mass or more and 15% by mass with respect to the total mass of the components (A) to (D). As mentioned above, it may be 20% by mass or more, or 30% by mass or more, and may be, for example, 96% by mass or less, 94% by mass or less, 92% by mass or less, or 88% by mass or less.
  • the bentonite is not particularly limited, and examples thereof include Na-type bentonite, Ca-type bentonite, Mg-type bentonite, organic bentonite, and composite bentonite.
  • the content of the bentnite is not particularly limited, but is, for example, 0.05% by mass or more, 0, based on the total mass of the components (A) to (D). It may be 1% by mass or more, or 0.2% by mass or more, and may be, for example, 20% by mass or less, 10% by mass or less, or 5% by mass or less.
  • the component (A) may or may not contain hectorite, for example.
  • the hectorite acts as a thickener, for example.
  • the thickener is, for example, when the rubber inner surface release agent of the present invention is dispersed in water to obtain the rubber inner surface release agent water dispersion of the present invention, the rubber inner surface release agent of the present invention is water-dispersed. It works to increase the viscosity of the liquid and make it easier to adhere to the inner surface of the rubber.
  • the component (A) contains hectrite
  • the content of the hectrite is not particularly limited, but is, for example, 0.05% by mass or more with respect to the total mass of the components (A) to (D). , 0.1% by mass or more, or 0.2% by mass or more, and may be, for example, 20% by mass or less, 10% by mass or less, or 5% by mass or less.
  • the component (A) may or may not contain calcium carbonate, but preferably contains calcium carbonate. Since graphite has low water absorption, the powder release agent for the inner surface of rubber may contain graphite, so that the powder fluidity may be lower than that in the case where graphite is not contained. However, by using calcium carbonate in combination, high powder fluidity can be obtained even if the release agent for the inner surface of rubber contains graphite.
  • the content of the calcium carbonate is not particularly limited, but is, for example, 0.05% by mass or more with respect to the total mass of the components (A) to (D). , 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, or 3% by mass or more, for example, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass. % Or less, or 10% by mass or less.
  • the component (A) may or may not contain mica.
  • the mica is not particularly limited, and examples thereof include muscovite, sericite, muscovite, biotite, phlogopite, illite, and color mica.
  • the component (A) contains mica, only one type of mica may be used, or a plurality of types may be used in combination.
  • the content of the mica is not particularly limited, but is, for example, 5% by mass or more and 10% by mass with respect to the total mass of the components (A) to (D). As mentioned above, it may be 15% by mass or more, or 20% by mass or more, and may be, for example, 60% by mass or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less.
  • the content of the component (A) in the mold release agent for the inner surface of the rubber of the present invention is not particularly limited, but is, for example, 10% by mass or more with respect to the total mass of the components (A) to (D). It may be 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more, for example, 96% by mass or less, 94% by mass or less, 92% by mass or less, 90% by mass or less, or 88. It may be mass% or less.
  • the hydrophobic silicone (B) functions, for example, as a component responsible for improving releasability.
  • the component (B) is not particularly limited, and examples thereof include organopolysiloxanes.
  • the organopolysiloxanes are a concept including silicone oil, silicone rubber, and silicone resin.
  • the organopolysiloxanes include, for example, [1] alkylpolysiloxanes such as [1] dimethylpolysiloxane, diethylpolysiloxane, methylisopropylpolysiloxane, and methyldodecylpolysiloxane, and [2] methylphenylpolysiloxane.
  • Alkylphenylpolysiloxane such as dimethylsiloxane / methylphenylpolysiloxane copolymer, dimethylsiloxane / diphenylsiloxane copolymer, etc.
  • Alkylaralkyl polysiloxane such as methyl (phenylethyl) polysiloxane, methyl (phenylpropyl) polysiloxane , [4] 3,3,3-trifluoropropylmethylpolysiloxane and the like.
  • silicone oil such as dimethylpolysiloxane and dimethylsilicone oil are preferable.
  • the silicone component may be used alone or in combination of two or more.
  • the content of the component (B) in the mold release agent for the inner surface of the rubber of the present invention is not particularly limited, but is, for example, 0.1% by mass with respect to the total mass of the components (A) to (D). It may be 1% by mass or more, 3% by mass or more, 5% by mass or more, or 7% by mass or more, for example, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, Alternatively, it may be 12% by mass or less.
  • the component (C) is a surfactant.
  • the component (C) is not particularly limited, and may be at least one selected from the group consisting of, for example, an anionic surfactant, a nonionic surfactant, and a cationic surfactant.
  • the component (C) may contain, for example, one or both of an anionic surfactant and a nonionic surfactant.
  • the component (C) may or may not contain an anionic surfactant.
  • the type of the anionic surfactant is not particularly limited, and one or more of them may be used or a plurality of types may be used in combination.
  • the anionic surfactant may or may not contain, for example, a sulfate ester type anionic surfactant.
  • the sulfate ester-type anionic surfactant is not particularly limited, and examples thereof include alkyl sulfates, alkenyl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, and the like. It may be used alone or in combination of multiple types.
  • the alkyl sulfate ester salt is not particularly limited, and examples thereof include alkyl sulfate ester salts having 10 to 20 or 12 to 18 carbon atoms such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium myristyl sulfate, sodium stearyl sulfate, and sodium cetyl sulfate. Be done.
  • the alkenyl sulfate ester salt is not particularly limited, and examples thereof include alkenyl sulfate ester salts having 10 to 20 or 12 to 18 carbon atoms such as sodium oleyl sulfate.
  • the polyoxyalkylene alkyl ether sulfate is not particularly limited, but for example, the average number of moles of the oxyalkylene group (AO) added is 0 to 4, preferably 0.1 to 3.5, and more preferably 0.3 to 0.3.
  • EO average number of moles of oxyalkylene group
  • the polyoxyalkylene alkenyl ether sulfate is not particularly limited, but for example, the average number of moles of the oxyalkylene group (AO) added is 0 to 4, preferably 0.1 to 3.5, and more preferably 0.3 to 0.3.
  • the alkyl group of the alkyl sulfate ester salt and the polyoxyalkylene alkyl ether sulfate preferably has 10 to 20 carbon atoms, and more preferably 12 to 18 carbon atoms.
  • the alkenyl group of the alkenyl sulfate ester salt and the polyoxyalkylene alkenyl ether sulfate preferably has 10 to 20 carbon atoms, and more preferably 12 to 18 carbon atoms.
  • the anionic surfactant may or may not contain, for example, a sulfonic acid type anionic surfactant.
  • the sulfonic acid type anionic surfactant is not particularly limited, and examples thereof include olefin sulfonates, ⁇ -sulfo fatty acid ester salts, dialkyl sulfosuccinates, alkyl sulfonates, alkylbenzene sulfonates, and the like. Only one type may be used or a plurality of types may be used in combination.
  • the olefin sulfonate is not particularly limited, but is, for example, an ⁇ -olefin sulfonate obtained by sulfonated and neutralized an ⁇ -olefin having 12 to 20 carbon atoms, preferably 14 to 18 carbon atoms, preferably 12 to 20 carbon atoms.
  • Examples include an internal olefin sulfonate obtained by sulfonated and neutralized 14 to 18 internal olefins.
  • the ⁇ -sulfo fatty acid ester salt is not particularly limited, and examples thereof include an ⁇ -sulfo fatty acid methyl ester salt having 10 to 18 carbon atoms, preferably 14 to 18 carbon atoms in the fatty acid residue.
  • the dialkyl sulfosuccinate is not particularly limited, and examples thereof include disetyl sulfosuccinate, dioctyl (2-ethylhexyl) sulfosuccinate, and the like.
  • the content of the anionic surfactant is not particularly limited, but for example, 0. It may be 05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more, for example, 10.0% by mass or less, 8.0% by mass or less, 6. It may be 0% by mass or less, 4.0% by mass or less, or 2.0% by mass or less.
  • the component (C) may or may not contain a nonionic surfactant.
  • the type of the nonionic surfactant is not particularly limited, and one or more or a plurality of types may be used in combination.
  • the nonionic surfactant is not particularly limited, but for example, a nonionic surfactant represented by the following chemical formula (1) can be used.
  • R is an aliphatic hydrocarbon group, for example, an aliphatic hydrocarbon group having 8 to 22 carbon atoms.
  • the aliphatic hydrocarbon group may be linear or branched. Further, the aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group (alkyl group) or an unsaturated aliphatic hydrocarbon group.
  • the number of carbon atoms of R may be, for example, 8 to 22, 8 to 18, 10 to 16 or 12 to 14 from the viewpoint of the dispersibility of the hydrophobic component.
  • AO represents an oxyalkylene group having 2 to 4 carbon atoms, and n is the average number of moles of AO added. n is, for example, 1 to 50, 1 to 40, 1 to 30, 1 to 25, or 1 to 10 from the viewpoint of the dispersibility of the hydrophobic component.
  • the oxyalkylene group having 2 to 4 carbon atoms is, for example, a polymerization unit to which an alkylene oxide having 2 to 4 carbon atoms is added (formed by addition polymerization).
  • Specific examples of the oxyalkylene group having 2 to 4 carbon atoms include an oxyethylene group (EO) to which ethylene oxide is added, an oxypropylene group (PO) to which propylene oxide is added, and butylene oxide.
  • EO oxyethylene group
  • PO oxypropylene group
  • B oxybutylene group
  • AO n contains at least an oxyethylene group in its structure.
  • (AO) n contains a plurality of types of an oxyethylene group (EO), an oxypropylene group (PO), and an oxybutylene group (BO), these groups may be arranged in a block shape. , May be randomly arranged.
  • Preferred (AO) n is composed of only an oxyethylene group (EO) because it has an excellent balance between hydrophilicity and hydrophobicity.
  • the nonionic surfactant is not particularly limited, and is, for example, [1] polyoxyalkylene alkyl ethers such as polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, and polyoxyethylene lauryl ether, and [2] polyoxyethylene nonyl.
  • Polyoxyalkylene alkyl phenyl ethers such as phenyl ethers and polyoxyethylene octyl phenyl ethers, polyoxyalkylene fatty acid esters such as [3] polyoxyethylene monolaurates and polyoxyethylene monooleates, and [4] polyoxyethylene sorbitan monos.
  • Polyoxyalkylene sorbitan fatty acid esters such as stearate and polyoxyethylene sorbitan monooleate, [5] polyoxyalkylene-cured castor oil, [6] polyoxyalkylene sorbitol fatty acid ester, [7] polyglycerin fatty acid ester, [8] alkyl.
  • the content of the nonionic surfactant is not particularly limited, but for example, 0. It may be 05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, or 0.5% by mass or more, for example, 18% by mass or less, 15% by mass or less, 12% by mass or less, or. It may be 10% by mass or less.
  • the surfactant (C) functions as, for example, a component responsible for imparting emulsion stability.
  • the "emulsification stability” refers to the stability of the emulsion when the water dispersion of the release agent for the inner surface of the rubber of the present invention is an emulsion.
  • the emulsion is preferably an emulsion in which the components (A) to (D) are dispersed in water.
  • Such an emulsion is, that is, an oil-in-water emulsion.
  • the release agent water dispersion for the inner surface of rubber of the present invention may be a water-in-oil emulsion, but is an oil-in-water emulsion from the viewpoints of sprayability, adhesion, releasability and the like. Is preferable.
  • the content of the component (C) in the mold release agent for the inner surface of the rubber of the present invention is not particularly limited, but is, for example, 0.1% by mass with respect to the total mass of the components (A) to (D). It may be 0.2% by mass or more, 0.5% by mass or more, or 1% by mass or more, for example, 18% by mass or less, 15% by mass or less, 12% by mass or less, or 10% by mass or less. There may be.
  • the component (D) is graphite.
  • the type of graphite is not particularly limited, and only one type or a plurality of types may be used in combination.
  • the graphite may contain, for example, one or both of artificial graphite and natural graphite.
  • Natural graphite is preferable as the graphite from the viewpoint of versatility.
  • the natural graphite is not particularly limited, and examples thereof include scaly graphite, scaly graphite, semi-scaly graphite, earthy graphite, spheroidal graphite, expanded graphite, lump graphite, and expanded graphite.
  • the graphite used for the rubber inner surface mold release agent of the present invention is preferably scaly graphite, scaly graphite, semi-scaly graphite, or earthy graphite.
  • Such graphite tends to be excellent in cleavability and self-lubricating property due to its shape and / or properties such as crystals. Therefore, such graphite reduces the friction generated when the bladder is expanded inside the raw tire, for example, and also acts as a film during vulcanization molding to prevent contact between the inner surface of the tire and the bladder. .. It is preferable that the graphite contains as little crystalline silica as possible from the viewpoint of reducing friction.
  • the graphite may have a crystalline silica content of, for example, 20% by mass or less, 10% by mass or less, 5% by mass or less, or 1% by mass or less.
  • the lower limit of the content of crystalline silica in the graphite is not particularly limited, but is, for example, a value exceeding 0% by mass or 0% by mass, and may be, for example, 0.01% by mass or more.
  • the content of the component (D) in the rubber inner surface mold release agent of the present invention is 0.1 to 50% by mass with respect to the total mass of the components (A) to (D). be. If the content of the component (D) is too low, the effect of improving the appearance of the rubber product cannot be obtained. If the content of the component (D) is too high, the powder fluidity of the release agent product for the inner surface of rubber may deteriorate.
  • the content of the component (D) is, for example, 0.1% by mass or more, 0.2% by mass or more, 0.5% by mass or more, based on the total mass of the components (A) to (D). Alternatively, it may be 1% by mass or more, and may be, for example, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, or 10% by mass or less.
  • the total mass of the component (D) may be, for example, 0.1 to 800% by mass with respect to the total mass of the component (A) as described above.
  • the total mass of the component (D) is 0. It is preferably 1% by mass or more.
  • the total mass of the component (D) is 800% by mass or less with respect to the total mass of the component (A).
  • the total mass of the component (D) is, for example, 0.1% by mass or more, 0.105% by mass or more, 0.2% by mass or more, 0.5% by mass or more with respect to the total mass of the component (A). , Or 1% by mass or more, for example, 500% by mass or less, 200% by mass or less, 100% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, or. It may be 10% by mass or less.
  • the component (D), that is, graphite is a black component as described above, it has an effect of improving the appearance of the rubber product. Further, graphite can contribute to the improvement of the release property of the release agent for the inner surface of rubber. Specifically, graphite has (1) a weaker force acting between layers and is easier to cleave than, for example, mica, talc, etc., and (2) has a larger number of layers that can be cleaved when compared with particles of the same thickness. , Has the characteristic of. Graphite can contribute to the improvement of the mold release property of the rubber inner surface mold release agent as a mold release component superior to mica, talc and the like due to the characteristics of the above (1) and (2), for example. However, if the content of graphite in the rubber inner surface mold release agent is too high, the powder fluidity of the rubber inner surface mold release agent may deteriorate as described above.
  • the release agent for the inner surface of rubber of the present invention may or may not contain any component other than the components (A) to (D).
  • the optional component include a water retention agent, a thickener, a polyhydric alcohol, water, a silicone-based defoaming agent, a mineral oil-based defoaming agent, and the like, which can contribute to improving the transparency of the defoaming agent film for the inner surface of rubber.
  • Various antifoaming agents, various preservatives and the like can be mentioned.
  • the polyvalent alcohol is not particularly limited, and is, for example, [1] polyethylene glycols such as [1] diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, and hexaethylene glycol, and [2] dipropylene glycol and tripropylene glycol.
  • Polybutylene glycols such as tetrapropylene glycol, pentapropylene glycol, hexapropylene glycol, [3] polybutylene glycols such as dibutylene glycol, tributylene glycol, tetrabutylene glycol, pentabutylene glycol, hexabutylene glycol, [4] Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,6-hexane Glycol, 1,2-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonan Gly
  • the water-retaining agent is not particularly limited, and examples thereof include the polyhydric alcohol, methyl cellulose, methyl ethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, polyacrylic acid, polyurethane, and polyamide, and only one type may be used. , Multiple types may be used together.
  • the polyhydric alcohol may, for example, have a role as the water retention agent and a role of contributing to the improvement of the transparency of the release agent film for the inner surface of rubber.
  • the content of the optional component is not particularly limited, but the content of the components (A) to (D) is not particularly limited.
  • it may be 0.01% by mass or more, 0.02% by mass or more, 0.05% by mass or more, 0.1% by mass or more, or 0.2% by mass or more with respect to the total mass.
  • it may be 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less.
  • the method for producing the release agent for the inner surface of rubber of the present invention is not particularly limited. Specifically, for example, all the components of the release agent for the inner surface of rubber of the present invention may be simply mixed. Further, the rubber inner surface mold release agent of the present invention may be produced, for example, by the above-mentioned method for producing the rubber inner surface mold release agent of the present invention.
  • the method for producing the rubber inner surface mold release agent of the present invention described above can be carried out, for example, as follows.
  • a first mixing step (hereinafter, also referred to as "pre-mixing step") is performed to obtain a mixture by mixing a part of the component (C) and the component (B).
  • pre-mixing step for example, the affinity between the component (B) (hydrophobic silicone) and the component (A) (inorganic component) is enhanced, and the effect of suppressing or preventing oil spots is further enhanced.
  • the portion of the component (C) used in the first mixing step is not particularly limited, but may be, for example, a part or all of the sulfonic acid type anionic surfactant.
  • the method of mixing a part of the component (C) and the component (B) is not particularly limited, and for example, the mixture may be stirred and mixed using an emulsifier or the like.
  • the emulsifying machine is not particularly limited and may be a general emulsifying machine, and examples thereof include a homomixer and a homodisper (both are trade names).
  • the speed and time of the stirring are also not particularly limited, and for example, stirring may be performed at 500 to 16000 rpm (for example, 5000 rpm) for 0.5 to 20 minutes (for example, 10 minutes).
  • the mixture obtained in the first mixing step is, for example, a silicone emulsion.
  • a second mixing step of mixing the balance of the component (C), the component (A) and the component (D) with the mixture obtained in the first mixing step is performed.
  • any component other than the components (A) to (D) may be further mixed.
  • the optional component is not particularly limited, but is, for example, as described above.
  • the method for performing the second mixing step is not particularly limited, but may be, for example, as follows. That is, first, the mixture obtained in the first mixing step and the component (A) are placed in a Henschel mixer and stirred at 50 to 4000 rpm (for example, 200 rpm) for 3 to 50 minutes (for example, 3 minutes). And mix.
  • the remainder of the component (C), the component (D), and optionally any component other than the components (A) to (D) are added to the Henschel mixer to add 100 to 4000 rpm (for example, for example). Stir and mix at 600 rpm for 10-30 minutes (eg, 10 minutes).
  • the order of addition of the remainder of the component (C), the component (D), and any component other than the components (A) to (D) is not particularly limited.
  • a stirrer capable of rotating at high speed like the Henschel mixer for example, a mold release agent for a rubber inner surface having a high bulk density can be obtained.
  • a stirring device capable of rotating at high speed for example, a Radige mixer, a high speed mixer, a Nauter mixer, a Newgra machine, a sugar mixer, a Proshare mixer, a Spartan mixer, a Pug mixer, a Turbulizer, etc.
  • a horizontal cylindrical mixer, a kneading extruder, a horizontal continuous kneader, a closed type compaction processing device, or the like may be used.
  • the mold release agent for the inner surface of rubber of the present invention can be produced.
  • the number of stirring fluids in stirring after the addition of all the components may be, for example, 0.5 to 25 or 0.9 to 20.
  • the stirring Froude number (Fr) is defined by the following formula (1), for example.
  • the average particle size of the produced rubber inner surface mold release agent may be, for example, 0.1 to 10 mm or 0.2 to 8 mm.
  • the average particle size is, for example, a 50% diameter in a mass-based integrated fraction measured using a sieving method.
  • the average particle size is, for example, a six-stage sieve having an opening of 16000 ⁇ m (16 mm), 9500 ⁇ m (9.5 mm), 5000 ⁇ m (5.0 mm), 1000 ⁇ m, 500 ⁇ m, and 100 ⁇ m (0.10 mm).
  • Measure by classification operation using a saucer In the classification operation, a sieve having a small opening and a sieve having a large opening are stacked in this order, a sample (a mold release agent for the inner surface of rubber) of 100 g / time is put from the top of the uppermost sieve, and the lid is closed.
  • the opening of the first sieve whose cumulative mass frequency is 50% or more is "a ( ⁇ m)"
  • the opening of the sieve one step larger than a ( ⁇ m) is "b (".
  • the average particle size (50% by mass particle size) obtained by the following formula (2) is defined as the average particle size.
  • Average particle size (50% by mass particle size) 10 [50- ⁇ cd / (logb-loga) ⁇ logb ⁇ ] / ⁇ d / (logb-loga) ⁇ (2)
  • the proportion of particles that do not pass through a sieve having an opening of 9.5 mm is preferably less than 50% by mass, and more preferably less than 30% by mass.
  • the proportion of particles passing through a sieve having an opening of 0.10 mm is preferably less than 50% by mass, and more preferably less than 30% by mass.
  • the method of using the release agent for the inner surface of rubber of the present invention is not particularly limited, but for example, it can be dispersed in water and used as the water dispersion liquid of the release agent for the inner surface of rubber of the present invention.
  • the form of the release agent for rubber inner surface of the present invention is not particularly limited, but for example, the release agent for rubber inner surface of the present invention is an emulsion (water dispersion) dispersed in water. Is preferable.
  • the method for producing (preparing) the release agent for rubber inner surface of the present invention is not particularly limited, and for example, it is sufficient to mix and disperse the release agent for rubber inner surface of the present invention in water.
  • the concentration of the release agent for the inner surface of rubber of the present invention is not particularly limited, and is, for example, 20 to 75% by mass, 30 to 70% by mass, or 30 to 30. It may be 65% by mass.
  • the method of using the rubber inner surface mold release agent of the present invention is not particularly limited, and may be, for example, the same as a general rubber inner surface mold release agent.
  • the release agent water dispersion for the inner surface of rubber of the present invention is applied to at least one of the inner surface and the outer surface of the bladder of rubber (for example, raw rubber made of unvulcanized rubber) by using a spray. Just do it.
  • the release agent water dispersion for the inner surface of rubber of the present invention may be an emulsion.
  • the average particle size of the emulsion is not particularly limited and may be, for example, 50 to 2000 nm, 100 to 1500 nm, or 150 to 1300 nm.
  • the average of the emulsions from the viewpoint of preventing deterioration of adhesion and mold release due to an increase in the required blending amount of the surfactant, and from the viewpoint of preventing adhesion inhibition when the mold release agent enters the bonding portion.
  • the particle size is preferably 50 nm or more.
  • the average particle size of the emulsion is 2000 nm or less. Is preferable.
  • the average particle size of the emulsion is determined by measuring the volume distribution of the emulsified particles using, for example, a submicron particle analyzer (laser diffraction / scattering method) manufactured by BECKMAN. The average particle size can be calculated based on the volume distribution.
  • this measuring method is an example, and the present invention is not limited to this measuring method.
  • Rubber product manufacturing method, tire manufacturing method, rubber products and tires The method for manufacturing a rubber product, the method for manufacturing a tire, the rubber product and the tire of the present invention are as described above. There are no particular restrictions on these as well.
  • the method for producing a rubber product of the present invention replaces a general rubber inner surface mold release agent or rubber inner surface mold release agent water dispersion liquid, and instead of the present invention's rubber inner surface mold release agent or rubber inner surface mold release agent. It can be carried out in the same manner as a general method for producing a rubber product, except that the agent water dispersion is used.
  • the method for manufacturing a tire of the present invention is, for example, instead of a general tire inner surface mold release agent or tire inner surface mold release agent water dispersion liquid, the tire inner surface mold release agent or tire inner surface release agent of the present invention. It can be carried out in the same manner as a general tire manufacturing method except that a mold release liquid is used.
  • examples of the molding die include a mold and the like.
  • a mold release treatment is performed between the vulcanized tire and the bladder and between the vulcanized tire and the molding die. It may have a mold release processing step.
  • Examples 1 to 9 and Comparative Examples 1 to 5 The release agent for the inner surface of rubber and the water dispersion of the release agent for the inner surface of rubber of Examples 1 to 9 and Comparative Examples 1 to 5 were produced as follows, and their characteristics were evaluated.
  • the rubber inner surface mold release agents of Examples 1 to 9 and Comparative Examples 1 to 5 were produced as follows. First, the component (B) shown in Table 1 or 2 below and the anionic surfactant (a part of the component (C)) described as "preliminary mixing step" in Table 1 or 2 below are mixed with a homomixer (commodity). The first mixing step (preliminary mixing step) was performed by stirring and mixing at 5000 rpm for 10 minutes. Thereby, in this way, a silicone emulsion (silicone emulsion) which is a mixture of a part of the component (C) and the component (B) was obtained. Next, a second mixing step was performed.
  • the silicone emulsion obtained in the first mixing step (preliminary mixing step) and the components (A) and (D) were placed in a Henschel mixer, stirred at 200 rpm for 3 minutes, and mixed. Further, the component (C) and other components (arbitrary components) were added to the Henschel mixer while stirring in sequence, and then further stirred at 600 rpm for 10 minutes to mix.
  • the powdery rubber inner surface mold release agents (tire inner surface mold release agents) of Examples 1 to 9 and Comparative Examples 1 to 5 were produced. Further, the powder fluidity of the rubber inner surface mold release agents of Examples 1 to 9 and Comparative Examples 1 to 5 produced in this manner was evaluated by the following method.
  • the amount of the release agent water dispersion for each tire inner surface (tire inner surface release agent treatment liquid) applied to an unvulcanized inner liner rubber sheet of 4 cm ⁇ 7 cm ⁇ 0.2 cm after drying is 10 g / m 2 .
  • the spray was applied.
  • a bladder rubber sheet of the same size is superposed on the spray-coated surface of this unvulcanized rubber sheet, set in a tabletop test press machine, and the mold temperature is 180 ° C. and the pressure is 20 kg / cm 2 for 20 minutes. Pressurized and vulcanized. Then, the vulcanized rubber sheet was peeled off (released).
  • the peelability is 5th grade for those that can be easily released without adhesion, 4th grade for those that can be released, and 3rd grade for those that have a large release drag but can be released. Those that are difficult to mold are evaluated as grade 2, and those that are in close contact with the entire surface and cannot be released are evaluated as grade 1.
  • the rubber inner surface mold release agents of Examples 1 to 9 contained all the components (A) to (D).
  • the component (D) graphite.
  • Comparative Examples 1 and 2 do not contain the carbon allotrope itself, and Comparative Examples 3 to 5 contain the carbon allotropes fullerene, carbon nanotubes or graphene, but contain graphite. did not exist.
  • graphite has, for example, (1) weaker force acting between layers and easier to cleave than mica, talc, etc., and (2) the number of layers that can be cleaved when compared with particles of the same thickness. It has the characteristic of being many. Therefore, it is presumed that the examples containing the component (D) (graphite) had better releasability than Comparative Examples 1 to 5 not containing the component (D). In particular, Example 1 showed excellent releasability even when the content of the component (D) was only 0.1% by mass with respect to the total mass of the components (A) to (D). ..

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Tyre Moulding (AREA)

Abstract

La présente invention a pour objet de réaliser un agent de démoulage pour surfaces internes en caoutchouc, ledit agent de démoulage ayant une aptitude au démoulage élevée, un pouvoir lubrifiant élevé et une excellente fluidité de poudre, tout en permettant à un produit de caoutchouc d'avoir un excellent aspect.　Un agent de démoulage pour surfaces internes de caoutchouc selon la présente invention est caractérisé en ce qu'il contient les composants (A) à (D) décrits ci-dessous, et qu'il contient de 0,1 % en masse à 50 % en masse du composant (D) par rapport à la masse totale des composants (A) à (D). (A) une substance inorganique autre que le composant (D) décrit ci-dessous (B) un silicone hydrophobe (C) un tensioactif (D) du graphite
PCT/JP2021/042422 2020-12-14 2021-11-18 Agent de démoulage pour surfaces internes en caoutchouc, procédé de production d'un agent de démoulage pour surfaces internes en caoutchouc, dispersion aqueuse d'agent de démoulage pour surfaces internes en caoutchouc, procédé de production de produit en caoutchouc, procédé de production de pneu, produit en caoutchouc, et pneu WO2022130890A1 (fr)

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JP2020-206724 2020-12-14
JP2020206724A JP2022093966A (ja) 2020-12-14 2020-12-14 ゴム内面用離型剤、ゴム内面用離型剤の製造方法、ゴム内面用離型剤水分散液、ゴム製品の製造方法、タイヤの製造方法、ゴム製品及びタイヤ

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115368823A (zh) * 2022-09-07 2022-11-22 上海凯陆高分子材料有限公司 一种用于轮胎硫化胶囊表面处理的材料及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04226715A (ja) * 1990-08-02 1992-08-17 Dexter Corp:The 水性スリツプ剤兼離型剤及びタイヤ及び他のゴム製品の成形及び加硫の方法
JPH08323773A (ja) * 1995-05-31 1996-12-10 Nippon Oil & Fats Co Ltd ブラダー用離型剤組成物及びタイヤ成型加硫方法
JP2019188632A (ja) * 2018-04-19 2019-10-31 ライオン・スペシャリティ・ケミカルズ株式会社 タイヤ内面用離型剤、タイヤ内面用離型剤水分散液、タイヤ内面用離型剤の製造方法、タイヤの製造方法およびタイヤ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04226715A (ja) * 1990-08-02 1992-08-17 Dexter Corp:The 水性スリツプ剤兼離型剤及びタイヤ及び他のゴム製品の成形及び加硫の方法
JPH08323773A (ja) * 1995-05-31 1996-12-10 Nippon Oil & Fats Co Ltd ブラダー用離型剤組成物及びタイヤ成型加硫方法
JP2019188632A (ja) * 2018-04-19 2019-10-31 ライオン・スペシャリティ・ケミカルズ株式会社 タイヤ内面用離型剤、タイヤ内面用離型剤水分散液、タイヤ内面用離型剤の製造方法、タイヤの製造方法およびタイヤ

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115368823A (zh) * 2022-09-07 2022-11-22 上海凯陆高分子材料有限公司 一种用于轮胎硫化胶囊表面处理的材料及其制备方法和应用

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