WO2013133207A1 - Agent anti-collant pour caoutchoucs non vulcanisés, et procédé de production de caoutchouc non vulcanisé avec traitement anti-collant - Google Patents

Agent anti-collant pour caoutchoucs non vulcanisés, et procédé de production de caoutchouc non vulcanisé avec traitement anti-collant Download PDF

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WO2013133207A1
WO2013133207A1 PCT/JP2013/055831 JP2013055831W WO2013133207A1 WO 2013133207 A1 WO2013133207 A1 WO 2013133207A1 JP 2013055831 W JP2013055831 W JP 2013055831W WO 2013133207 A1 WO2013133207 A1 WO 2013133207A1
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mass
unvulcanized rubber
adhesion
rubber
agent
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PCT/JP2013/055831
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English (en)
Japanese (ja)
Inventor
石川　浩
友一 小熊
孝介 市橋
栄志 森口
保昌 石原
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一方社油脂工業株式会社
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Priority to CN201380012417.3A priority Critical patent/CN104159961B/zh
Publication of WO2013133207A1 publication Critical patent/WO2013133207A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay

Definitions

  • the present invention relates to an adhesion preventive agent for preventing adhesion between unvulcanized rubbers, and a method for producing an adhesion-treated unvulcanized rubber using the same.
  • unvulcanized rubber molded into a sheet or the like is transferred to the next molding and vulcanization process. In the meantime, they may be stacked or folded for storage. At the time of such storage, for the purpose of preventing the unvulcanized rubber from adhering to each other, an adhesion preventing agent (adhesion preventing agent) is adhered to the surface of the unvulcanized rubber (for example, (See Patent Document 1).
  • an adhesion preventing agent adhered to the surface of the unvulcanized rubber (for example, (See Patent Document 1).
  • the suspension is sprayed with shower equipment on unvulcanized rubber in a high temperature state (for example, 80 to 150 ° C.) after being formed into a sheet or the like, or in a tank containing the suspension.
  • the suspension is attached to the surface of the unvulcanized rubber by dipping the unvulcanized rubber in a high temperature state for a short time. Moisture in the adhering suspension is rapidly evaporated and dried by the heat of the unvulcanized rubber, thereby forming a film of an adhesion-preventing agent on the surface of the unvulcanized rubber.
  • the wet method is in a high temperature state. Under conditions where the suspension is rapidly dried by the heat of the unvulcanized rubber, the suspension is repelled in the drying process, and the adhesion agent is not evenly adhered to the surface of the unvulcanized rubber. It was difficult. If there is uneven adhesion of the anti-adhesive agent, it is difficult to fully exhibit the anti-adhesion performance.
  • the anti-adhesive agents are adhered to the rubber surface by reducing the concentration of the anti-adhesive agent in the suspension. A method of reducing the amount of the agent is taken. Also, since the anti-adhesive agent adhering to the surface of the unvulcanized rubber is kneaded into the rubber in the next step, the amount of the anti-adhesive agent adhering to the unvulcanized rubber is made as small as possible, and the anti-adhesive agent is the rubber. It is preferable not to adversely affect the physical properties.
  • the present invention has been made in view of the above circumstances, and when the anti-adhesive agent is used as an anti-adhesive suspension, the anti-adhesive suspension has good wettability with respect to the surface of the unvulcanized rubber. In addition, when the anti-adhesive agent suspension is dried, the anti-adhesive agent adheres uniformly to the surface of the unvulcanized rubber and exhibits excellent adhesion. It is an object of the present invention to provide an anti-vulcanized rubber anti-adhesive agent that exhibits good anti-adhesion performance even when used as an adhesive.
  • the antivulcanizing agent for unvulcanized rubber according to the present invention contains bentonite (A) containing Na-type montmorillonite in an amount of 60% by mass or more based on the total mass of bentonite with respect to the total mass of the unvulcanized rubber. -90 mass%, an anionic surfactant (B), and a nonionic surfactant (C) represented by the following formula (1), wherein the mass of (B) / the mass of (C) The expressed mass ratio is 0.15 to 0.65.
  • the method for producing an adhesion-treated unvulcanized rubber according to the present invention is characterized by including a step of adhering the adhesion agent for unvulcanized rubber to the surface of the unvulcanized rubber.
  • the anti-curing agent for unvulcanized rubber of the present invention has good wettability with respect to the surface of the unvulcanized rubber when the anti-sticking agent is used as an anti-sticking agent suspension.
  • the anti-adhesive agent suspension is dried, the anti-adhesive agent adheres uniformly to the surface of the unvulcanized rubber. For this reason, even when the suspension is used at a low concentration of the anti-sticking agent, it exhibits good anti-sticking performance.
  • the unvulcanized rubber anti-adhesive agent of the present invention adheres to the surface of the unvulcanized rubber formed into a sheet to form a film, This prevents the sheet-like unvulcanized rubber from adhering to each other during storage.
  • the anti-adhesive agent of the present invention comprises 50 to 90% by mass of bentonite (A) containing Na-type montmorillonite in an amount of 60% by mass or more with respect to the total mass of the bentonite, and an anionic surfactant.
  • C specific nonionic surfactant
  • the bentonite (A) which contains Na type montmorillonite 60 mass% or more with respect to the total mass of bentonite is used as (A) component.
  • the said bentonite (A) is a component which bears the anti-adhesion property of an anti-adhesive agent, Comprising: It is more preferable that content of Na type montmorillonite in bentonite (A) is 90 mass% or more with respect to the total mass of bentonite. preferable.
  • An anti-adhesive agent using bentonite having a Na-type montmorillonite content of less than 60% by mass with respect to the total mass of bentonite has insufficient adhesion to the surface of the unvulcanized rubber. Excellent anti-adhesion performance cannot be imparted.
  • Bentonite (A) contains quartz, cristobalite, feldspar, carbonate minerals, etc. in addition to Na-type montmorillonite. Adhesion decreases when the total mass of these impurities exceeds 40% by mass with respect to the total mass of bentonite. To do.
  • the content of Na-type montmorillonite in bentonite (A) is a value measured by X-ray diffraction.
  • composition (B) In the present invention, an anionic surfactant is used as the component (B).
  • the anionic surfactant (B) effectively adsorbs to the Na-type montmorillonite in the bentonite (A) when the anti-vulcanized rubber anti-adhesive agent of the present invention is used as an anti-adhesive suspension.
  • the type montmorillonite is uniformly dispersed in the form of flakes in the anti-adhesive agent suspension, and the surface tension of the anti-adhesive agent suspension with respect to the surface of the unvulcanized rubber is reduced, whereby the anti-adhesive agent suspension It is surmised that it has the effect of improving the wettability with the surface of the unvulcanized rubber.
  • Carboxylic acid type anionic surfactants such as higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, acylaminocarboxylates
  • Sulfate-type anionic surface activity such as higher alcohol sulfate, polyoxyalkylene higher alcohol sulfate, alkylphenyl ether sulfate, polyoxyalkylene alkylphenyl ether sulfate, glycerin fatty acid ester monosulfate Agent
  • sulfonic acid type anionic surfactants such as alkane sulfonate, ⁇ -olefin sulfonate, linear alkylbenzene sulfonate, ⁇ -sulfo fatty acid ester salt, dialkyl sulfosuccinate, (4) Phosphate ester type
  • the higher fatty acid means a fatty acid having 6 to 20 carbon atoms
  • the higher alcohol means an alcohol having 6 to 20 carbon atoms.
  • the counter ion of the anionic surfactant is preferably an alkali metal such as sodium or potassium, or an alkanolamine such as monoethanolamine or diethanolamine. These may be used alone or in combination of two or more. That is, the salt of the anionic surfactant is preferably a salt with an alkali metal such as sodium or potassium, or a salt with an alkanolamine such as monoethanolamine or diethanolamine.
  • a dialkylsulfosuccinate is preferable, and a dioctylsulfosuccinate Na salt is more preferable because an anti-adhesive suspension excellent in wettability with the surface of the unvulcanized rubber can be obtained.
  • a nonionic surfactant represented by the formula (1) that means a polyoxyalkylene alkyl ether
  • the nonionic surfactant of the formula (1) together with the anionic surfactant which is the component (B), reduces the surface tension of the anti-adhesive agent suspension relative to the surface of the unvulcanized rubber, It is presumed that the effect of effectively increasing the adhesion of the adhesion-preventing agent to the surface of the vulcanized rubber is exhibited.
  • R represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms.
  • the aliphatic hydrocarbon group for R may be linear or branched. Moreover, either saturated or unsaturated may be sufficient.
  • the carbon number of R is preferably 12 to 16 and more preferably 12 to 13 from the viewpoint of excellent dispersibility of the component (A).
  • AO represents an oxyalkylene group having 2 to 4 carbon atoms
  • n is the average added mole number of AO.
  • n is preferably 1 to 8, and more preferably 1 to 5.
  • n is less than 1, the surface activity decreases, and the dispersibility of component (A) decreases.
  • n is in the range of 1 to 8, the dispersibility of component (A) is improved, and adhesion is improved by giving sufficient viscoelasticity to the coating even when the hydrophobicity of the unvulcanized rubber surface is high. It is considered a thing.
  • n exceeds 8 the hydrophilicity becomes too high and lacks suitability.
  • the oxyalkylene group having 2 to 4 carbon atoms is a group formed by adding an alkylene oxide having 2 to 4 carbon atoms, and is formed by adding an oxyethylene group (EO) formed by adding ethylene oxide or propylene oxide.
  • EO oxyethylene group
  • PO oxypropylene groups
  • BO oxybutylene groups
  • AO n contains at least an oxyethylene group.
  • n contains an oxyethylene group (EO) and an oxypropylene group (PO) and / or an oxybutylene group (BO), these groups are randomly arranged even if they are arranged in a block shape. It may be arranged.
  • Preferable (AO) n consists of only an oxyethylene group (EO) from the viewpoint of excellent balance between hydrophilicity and hydrophobicity.
  • nonionic surfactant (C) As such nonionic surfactant (C), the following are mentioned, for example.
  • a nonionic surfactant (hereinafter referred to as C13EO3) in which R in the formula (1) is a branched and saturated aliphatic hydrocarbon group having 13 carbon atoms, n is 3, and AO is EO. May be indicated.)
  • -Nonion in which R in formula (1) is a branched and saturated aliphatic hydrocarbon group having 13 carbon atoms, n is 3, and 2 mol of EO and 1 mol of PO are added as AO Surfactant (hereinafter sometimes referred to as C13EO2 / PO1).
  • nonionic surfactant (C) there is “Finesurf TDP-0201R (100% purity)” manufactured by Aoki Oil & Fat Co., Ltd.
  • C18EO5 A nonionic surfactant (hereinafter referred to as C18EO5) in which R in the formula (1) is a linear and saturated aliphatic hydrocarbon group having 18 carbon atoms, n is 5, and AO is EO. May be written.)
  • As such a nonionic surfactant (C) there is “Brownon SR-705 (purity 100%)” manufactured by Aoki Oil & Fat Co., Ltd.).
  • C13EO3 and C13EO2 / PO1 are more preferable.
  • the anti-adhesive agent of the present invention may contain additives such as antifoaming agents, wettability aids, lubricants (sliding agents), and viscosity aids as necessary. May be included as an optional component.
  • additives such as antifoaming agents, wettability aids, lubricants (sliding agents), and viscosity aids as necessary. May be included as an optional component.
  • oil-based antifoaming agents such as castor oil, sesame oil, linseed oil, animal and vegetable oils; isoamyl stearate, distearyl succinate, ethylene glycol distearate, butyl stearate, etc.
  • Fatty acid ester antifoaming agents such as polyoxyalkylene monohydric alcohol di-t-amylphenoxyethanol, 3-heptanol, 2-ethylhexanol; di-t-amylphenoxyethanol, 3-heptylcellosolve, Ether-based antifoaming agents such as nonyl cellosolve and 3-heptylcarbitol; phosphate ester-based antifoaming agents such as tributyl osphate and tris (butoxyethyl) phosphate; amine-based antifoaming agents such as diamylamine; Acylate polyami Amide-based defoaming agent and the like; mineral oils; silicone oil; and the like.
  • alcohol defoaming agents such as polyoxyalkylene monohydric alcohol di-t-amylphenoxyethanol, 3-heptanol, 2-ethylhexanol; di-t-amylphenoxyethanol, 3-hepty
  • Examples of the wettability aid include alcohols, and are not particularly limited.
  • alcohols for example, methanol, ethanol, hexanol, glycerin, 1,3-butanediol, propylene glycol, dipropylene glycol, pentylene glycol, hexylene glycol,
  • examples thereof include polyethylene glycol, saltol, maltitol, sucrose, erythritol, xylitol and the like, and one or more kinds can be used.
  • Examples of the lubricant include metal soaps, and are not particularly limited.
  • the metal soaps described here are water-insoluble salts and generally do not correspond to anionic surfactants.
  • the lubricant for example, carbonates such as calcium carbonate, magnesium carbonate, barium carbonate; silicates such as kaolin, aluminum silicate, calcium silicate, clay, talc, mica, sericite; calcium sulfate, sulfuric acid Sulfates such as barium; metal oxides such as silica, alumina, magnesium oxide, antimony trioxide, titanium oxide, white carbon and iron oxide; metal hydroxides such as aluminum hydroxide, magnesium hydroxide and iron hydroxide; bengara Carbon black; inorganic powders such as graphite are also included, and one or more kinds can be used.
  • the viscosity auxiliary agent examples include water-soluble polymers and are not particularly limited.
  • Examples include natural water-soluble polymers such as seed gum, tragacanth gum, gum arabic, carrageenan, rhamzan gum, succinoglycan, tara gum, gellan gum, karaya gum, pectin, alginic acid derivatives, and cellulose ethers.
  • the anti-adhesive agent may contain water for the purpose of suppressing the powder flow.
  • the content of water is, for example, about 2 to 3% by mass relative to the total mass of the adhesion-preventing agent.
  • the anti-adhesive agent of the present invention comprises 50 to 90% by mass of bentonite (A) containing Na-type montmorillonite in an amount of 60% by mass or more with respect to the total mass of the bentonite, and an anionic surfactant. (B) and the nonionic surfactant (C) represented by Formula (1) are contained. Since bentonite (A) is a component responsible for adhesion, the adhesion is reduced when the content in the adhesion is less than 50% by mass relative to the total mass of the adhesion.
  • a more preferable content of bentonite (A) in the anti-adhesive agent is 60 to 80% by mass with respect to the total mass of the anti-adhesive agent.
  • some bentonite circulates in a state containing water, but in the present specification, when the content of bentonite (A) is referred to, the content is a value not including the amount of water.
  • the mass ratio (B) / (C) of the mass of the component (B) to the mass of the component (C) in the anti-adhesive agent is preferably 0.15 to 0.65.
  • the anti-adhesive agent of the present invention when used as an anti-adhesive suspension, the anti-adhesive suspension exhibits good wettability with respect to the surface of the unvulcanized rubber. And when the anti-adhesive suspension is dehydrated and dried on the surface of the unvulcanized rubber in a high temperature state, the anti-adhesive suspension is removed from the surface of the unvulcanized rubber. And an excellent anti-adhesive that adheres uniformly to the surface.
  • the mass ratio (B) / (C) is preferably 0.20 to 0.50.
  • the mass ratio ((B) + (C)) / (A) of the total mass of the component (B) and the component (C) to the mass of the component (A) in the anti-adhesive agent is preferably 0.05 or more, More preferably, it is 0.15 to 0.30.
  • the mass ratio is less than the above lower limit, the wettability between the surface of the anti-adhesive agent suspension and the unvulcanized rubber, the adhesion of the anti-adhesive agent to the surface of the unvulcanized rubber is insufficient, There is a tendency that it is impossible to impart good adhesion performance.
  • the mass ratio ((B) + (C)) / (A) is preferably 0.30 or less.
  • the anti-adhesive agent of the present invention can be produced by mixing the components (A) to (C) and optional components blended as necessary.
  • an apparatus used for mixing an apparatus having a configuration in which a stirring blade is provided in a container can be used.
  • Specific examples include a powder mixer that can perform rocking stirring or stirring, such as a ribbon-type mixer and a vertical screw-type mixer.
  • a super mixer manufactured by Kawata Co., Ltd.
  • a high speed mixer manufactured by Fukae Co., Ltd.
  • a new gram machine manufactured by Seishin Enterprise Co., Ltd.
  • an SV mixer manufactured by Shinko Environmental Solution Co., Ltd.
  • Multifunctional powder mixers such as can also be used.
  • 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. Good.
  • a spray device for spraying or spraying the liquid component on a mixture other than the liquid component, You may use a shower apparatus etc. together.
  • the method for producing an adhesion-treated unvulcanized rubber according to the present invention includes a step of adhering the above-mentioned adhesion preventing agent to the surface of the unvulcanized rubber. Even if the non-vulcanized rubber that has been subjected to the adhesion treatment manufactured in this way is stored by being stacked or folded, the unvulcanized rubber does not adhere to each other.
  • the adhesion process includes a suspension adhesion process in which an anti-adhesive suspension in which an anti-adhesive is dispersed in water is adhered to the surface of the unvulcanized rubber, and an anti-adhesive suspension on the surface of the unvulcanized rubber.
  • a step having a drying step of drying the liquid and forming a film made of an anti-adhesive agent on the surface of the unvulcanized rubber is preferable. Such a process is sometimes called a wet method.
  • the anti-adhesive agent suspension it is preferable to adhere the anti-adhesive agent suspension to the unvulcanized rubber at a high temperature of, for example, about 80 to 150 ° C. by heat when it is formed into a sheet or the like.
  • Specific methods of the suspension adhesion step include, for example, a method of spraying the anti-adhesive suspension on the unvulcanized rubber with a shower device, and a short method of unvulcanized rubber in the tank containing the anti-adhesive suspension. There is a dipping method in which the immersion is performed for a time. Moreover, the method of apply
  • coating apparatus may be employ
  • the anti-adhesive agent of the present invention contains Na-type montmorillonite in an amount of 60% by mass or more with respect to the total mass of bentonite, and bentonite (A) having excellent adhesiveness with respect to the total mass of the anti-adhesive agent.
  • the anionic surfactant (B) and the nonionic surfactant (C) represented by the formula (1) are included.
  • the mass ratio (B) / (C) of the content of the anionic surfactant (B) to the content of the nonionic surfactant (C) is preferably 0.15 to 0.65.
  • the concentration of the antiadhesive is as low as 1.0 to 1.5% by mass relative to the total mass of the antiadhesive suspension. It can be used at a low concentration, and even when used at the low concentration, it can form a uniform film composed of the anti-adhesive agent on the surface of the unvulcanized rubber, and has excellent anti-adhesion performance against the unvulcanized rubber. Give.
  • the reason why the anti-adhesive agent of the present invention has such an effect can be presumed as follows.
  • the anionic surfactant of the component (B) constituting the anti-adhesive agent is effectively adsorbed on Na-type montmorillonite in bentonite (A) when the anti-adhesive agent is used as an anti-adhesive suspension, It is considered that Na-type montmorillonite is uniformly dispersed in the form of flakes in the above-mentioned anti-adhesive suspension, and the surface tension of the above-mentioned anti-adhesive suspension with respect to the surface of the unvulcanized rubber is reduced.
  • the anti-sticking agent suspension prepared from the anti-sticking agent of the present invention containing the component (B) is not only excellent in wettability with the surface of the unvulcanized rubber, but also in a highly dispersed state of Na-type montmorillonite. It is considered that the surface of the unvulcanized rubber can be efficiently covered.
  • the nonionic surfactant of component (C) that constitutes the anti-adhesive agent acts together with the anionic surfactant as the component (B), and the surface of the anti-adhesive suspension with respect to the surface of the unvulcanized rubber.
  • the dispersion of the bentonite component (A) in the above-described anti-adhesive suspension is controlled, and the anti-adhesive suspension covering the surface of the unvulcanized rubber is dried and dehydrated.
  • the adhesion of the adhesion preventing agent to the unvulcanized rubber surface is effectively enhanced by increasing the viscoelasticity of the adhesion preventing agent suspension.
  • the anti-adhesive agent in the anti-adhesive suspension covering the surface of the unvulcanized rubber does not repel the surface of the unvulcanized rubber during the drying process after adhering to the surface. It is thought that it adheres and forms a uniform film.
  • the depositing agent of the present invention is as described above.
  • An anionic surfactant (B) and a nonionic surfactant (C) that exhibit a specific action are contained in a specific ratio.
  • the anti-adhesive agent of the present invention when used as an anti-adhesive suspension, the anti-adhesive agent suspension exhibits good wettability with respect to the surface of the unvulcanized rubber, and When the adhesive suspension is dried, the anti-adhesive agent adheres to the surface of the unvulcanized rubber evenly and exhibits excellent adhesion. Therefore, even when the suspension is used with a low concentration of the anti-adhesive agent, Good adhesion performance can be imparted to unvulcanized rubber.
  • the type of rubber to which the adhesion-preventing agent of the present invention can be applied is an unvulcanized rubber.
  • rubber types include natural rubber (NR), butadiene rubber (BR), styrene butadiene rubber (SBR), IIR (butyl rubber), EPDM (ethylene propylene rubber), and a mixture of these.
  • NR natural rubber
  • BR butadiene rubber
  • SBR styrene butadiene rubber
  • IIR butyl rubber
  • EPDM ethylene propylene rubber
  • the rubber which was made is mentioned.
  • the unvulcanized rubber to which the adhesion-preventing agent is applied is a vulcanizing agent (sulfur etc.) and various additives generally used for rubber (anti-aging agent, vulcanization accelerator, carbon black, etc.). ) And the like.
  • One aspect of the present invention is that the bentonite (A) containing Na-type montmorillonite in an amount of 60% by mass or more with respect to the total mass of bentonite is 50 to 90% by mass with respect to the total mass of the composition, B) and the nonionic surfactant (C) represented by the formula (1), and the mass ratio represented by the mass of the (B) / the mass of the (C) is 0.15 to Relates to the composition being 0.65.
  • the bentonite (A) containing Na-type montmorillonite in an amount of 60% by mass or more based on the total mass of bentonite is 50 to 90% by mass based on the total mass of the composition;
  • an anionic surfactant (B) which is a dioctylsulfosuccinate Na salt; represented by the formula (1), wherein R in the formula (1) is a branched and saturated aliphatic group having 13 carbon atoms.
  • the present invention relates to a composition in which the mass ratio represented by the mass of B) / the mass of (C) is 0.15 to 0.65.
  • Another aspect of the present invention is any one of the above aspects, further comprising at least one additive selected from the group consisting of an antifoaming agent, a wettability aid, a lubricant (slipper), and a viscosity aid. Relates to one composition. Yet another aspect of the present invention relates to the use of any one of the above aspects for the prevention of unvulcanized rubber.
  • Bentonite (A-1) (“Kunipia-F” manufactured by Kunimine Kogyo Co., Ltd., Na-type montmorillonite content: 98.5% by mass (Kunipia F product) so that the Na-type montmorillonite content is as shown in Table 1. 6) Bentonite (A-2) to (A-6) with different contents of Na-type montmorillonite mixed with bentonite sub-mineral prepared by the following method. ) was prepared as component (A).
  • the powder thus obtained was designated as “bentonite secondary mineral”.
  • the analysis conditions for X-ray diffraction when the Na-type montmorillonite content (residual amount) is quantified are as follows.
  • X-ray diffraction analysis conditions / measurement device X'Pert PRO MRD (manufactured by PANalytical) ⁇ Target: Cu ⁇ Tube voltage: 45kV ⁇ Tube current: 40 mA ⁇ Scan axis: Goniometer ⁇ Scan range: 5 ° -60 ° ⁇ Step size: 0.03 ° ⁇ Step time: 12.7 seconds ⁇ Divergent slit: 1/2 ° ⁇ Scatter slit: 1 ° ⁇ Reception slit: None
  • Examples 1 to 18, Comparative Examples 1 to 9 The components (A) to (C) and calcium stearate (optional component: manufactured by NOF Corporation, calcium stearate (purity 100%)) as a lubricant are kneaded at a mass ratio shown in Tables 2 to 4.
  • an anti-adhesive agent comprising a uniform powder was prepared.
  • each obtained anti-adhesive was added to tap water, stirring, and prepared the anti-adhesive suspension whose density
  • concentration of an anti-adhesive is 1 mass% with respect to the total mass of an anti-adhesive suspension.
  • concentration 1% by mass was 1 mass% with respect to the total mass of an anti-adhesive suspension.
  • B-1 Dioctyl sulfosuccinate Na salt (manufactured by Nippon Cytec Industries, Ltd., “Aerosol GPG (purity 70%)”)
  • B-2 Alkylbenzenesulfonic acid sodium salt whose alkyl group has 12 to 20 carbon atoms (“Liporan PB (purity 95%)” manufactured by Lion Corporation)
  • B-3 Na stearate (manufactured by Dainichi Chemical Co., Ltd., “Die Wax NA (purity 100%))
  • C-1 “Leocor TD-30 (100% purity)” manufactured by Lion Corporation
  • C-2 “Finesurf TDP-0201R (purity 100%)” manufactured by Aoki Oil & Fat Co., Ltd.
  • C-3 “Brownon SR-705 (100% purity)” manufactured by Aoki Oil & Fat Co., Ltd.
  • Unvulcanized NR / BR rubber For a total of 100 parts by mass of 70 parts by mass of NR (RSS # 3) and 30 parts by mass of BR (manufactured by JSR Co., Ltd., “BR-01”), White Carbon (Tosoh Silica Co., Ltd., “Nip Seal VN -3 ”) 10 parts by mass, ISAF black (manufactured by Tokai Carbon Co., Ltd.,” Seast 6 "), 30 parts by mass, JSRARAMA (process oil) (Nihon Sun Sekiyu Co., Ltd.,” Aroma 790 ”) 15 parts by mass Parts, 3 parts by weight of zinc white (Hakusuitec Co., Ltd., 2 types of zinc white), 1 part by weight of stearic acid (manufactured by NOF Corporation, cocoon), 6PPD (manufactured by Ou).
  • the unvulcanized rubber (unvulcanized NR / BR rubber) is kneaded with an open roll at a temperature of 80 to 120 ° C. to obtain a rubber sheet (thickness: 5 to 8 mm, 60 cm ⁇ 15 cm).
  • the rubber sheet immediately after kneading was immersed in 1 L of an anti-adhesive suspension (temperature 40 ° C.) obtained in each example for about 1 second. Thereafter, the rubber sheet was quickly pulled up vertically and allowed to stand at room temperature. After about 3 seconds, the surface of the rubber sheet was photographed.
  • 0% coating area 2 The coating area exceeds 0 and less than 40% 3: The coating area is 40% or more and less than 70% 4: The coating area is 70% or more and less than 100%, and the coating is not vertically striped or madrid It is a film (pass). 5: The coating area is 100%, and the coating is a homogeneous coating that is not vertically striped or madrid (pass).
  • the rubber is immersed in the anti-adhesive agent suspension for a very short time (about 1 second).
  • the anti-adhesive agent can be applied in a uniform thin film state with no unevenness such as vertical stripes and madras. The state that can remain on the rubber surface was regarded as a passing score.
  • Unvulcanized rubber (unvulcanized NR / BR rubber) is kneaded with an open roll at a temperature of 80 to 120 ° C. to give a rubber sheet (thickness: 5 to 8 mm, 60 cm ⁇ 15 cm)
  • the rubber sheet immediately after being kneaded was immersed in 1 L of the anti-adhesive suspension (temperature 40 ° C.) obtained in each example for about 1 second. Thereafter, the rubber sheet was quickly pulled up vertically, allowed to stand in a vertical state at room temperature, and naturally dried. Thereafter, the rubber sheet was cut into 6 cm ⁇ 15 cm, and the two sheets were laminated to form a laminated state.
  • a load of 1 t / m 2 was applied to the test piece in the laminated state in the vertical direction from one surface, and 60 It was left at 12 ° C. for 12 hours. Thereafter, the test piece was returned to room temperature, a 180 ° peel test was performed using a tensile tester [AGS-500D type, SHIMADZU], and peel resistance (N / cm) was measured at a pulling speed of 300 mm / min. The measured peel resistance values are listed in Tables 2-4.
  • the peel resistance When the peel resistance is 2.0 N / cm or less, the rubber sheet can be peeled off without a large load, and it can be judged that the adhesion prevention performance is good. When the peel resistance is more than 2.0 N / cm, it can be determined that the load when peeling the rubber sheet is large and the adhesion prevention performance is poor. Furthermore, when the peeling resistance is more than 3.0 N / cm, the rubber sheet is in close contact, and it can be judged that peeling at a normal work site is difficult.
  • the blending amount (mass ratio%) of each component in the table is a value calculated in terms of pure content.
  • each of the anti-sticking agent suspensions obtained in Examples 1 to 18 has both wettability and adhesion to the surface of the unvulcanized rubber in a high temperature state. It was a passing score of 4 points or more and was excellent. Specifically, according to each of the anti-sticking agent suspensions obtained in Examples 1 to 18, the rubber having the surface heated at 80 to 120 ° C. and having a high temperature is removed for a very short time (about 1 sec) shows excellent wettability immediately after pulling up, and even if moisture rapidly evaporates from the adhered suspension of adhesion, unevenness such as vertical stripes and madras A uniform thin film of the anti-adhesive agent dried film having no area could be formed on the rubber surface at a high area ratio.
  • the unvulcanized rubber treated with the anti-adhesive agent suspensions of Examples 1 to 18 having excellent wettability and adhesion as described above has a peel resistance even after being overlaid and loaded. All of them were as low as 2 N / cm or less, and high adhesion performance was imparted. From the above, it has been clarified that having both good wettability and adhesion leads to the provision of excellent anti-adhesion performance.
  • each of the anti-sticking agent suspensions obtained in Comparative Examples 1 to 9 is not good because at least one of wettability and adhesion is 3 points or less. Therefore, the result was that the adhesion preventing performance was not good.
  • Comparative Examples 1 and 2 using bentonite (A) having a low Na-type montmorillonite content wettability and adhesion were poor.
  • Comparative Example 3 since the amount of bentonite (A) is small, the wettability is good but the adhesion is poor.
  • Comparative Example 4 the amount of bentonite (A) is excessive, and the anionic surfactant (B) and the nonionic surfactant Since there was little (C), wettability was bad and adhesiveness was also bad. Further, in Comparative Example 5 using a nonionic surfactant having a large average added mole number of oxyalkylene groups, the nonionic surfactant (C) has high hydrophilicity and insufficient wettability and adhesion. It was. In Comparative Example 6 containing no nonionic surfactant (C), the wettability was excellent, but the adhesion was poor.
  • Comparative Example 7 not containing the anionic surfactant (B), wettability and adhesion were extremely poor, and therefore, in the evaluation of the anti-adhesion performance, the two rubber sheets constituting the test piece were in close contact with each other. In the 180 ° peel test under the above conditions, the test piece could not be peeled off, and the test piece was also broken. Further, Comparative Example 8 having a small (B) / (C) had poor wettability, and Comparative Example 9 having a large (B) / (C) had particularly poor adhesion. In addition, regarding the adhesion, in Comparative Example 3 and Comparative Example 6, the ratio of the area of the portion covered with the dry film is high, but vertical striped unevenness is observed.
  • the dry film is In addition to the low area ratio of the covered part, spotted irregularities were observed.
  • the suspensions of Examples 1 to 18 were prepared by using bentonite (A) containing 60% by mass or more of Na-type montmorillonite, an anionic surfactant (B), and a specific nonion as the deposition inhibitor.
  • a surfactant (C) and a mass ratio represented by (B) / (C) of 0.15 to 0.65 is used. It exhibits good wettability and exhibits excellent adhesion that adheres to the surface of the unvulcanized rubber evenly when dried. Therefore, even if the concentration of the anti-sticking agent in the suspension is as low as 1% by mass, It was clear that good adhesion performance could be imparted to the vulcanized rubber.
  • NR / BR rubber is used as the rubber of the unvulcanized rubber.
  • rubber such as general NR, SBR, BR, IIR, EPDM is used, the above embodiment and Results similar to those of the comparative example are obtained.
  • the anti-curing agent for unvulcanized rubber according to the present invention when the anti-sticking agent is used as an anti-sticking agent suspension, the unvulcanized rubber is used even if the anti-sticking agent concentration of the suspension is lowered. Excellent adhesion performance.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne un agent anti-collant pour caoutchoucs non vulcanisés, qui comprend une bentonite (A) dans une quantité de 50 à 90 % en masse par rapport à la quantité totale de l'agent anti-collant pour caoutchoucs non vulcanisés, un tensioactif anionique (B) et un tensioactif non ionique (C) représentés par la formule (1). La bentonite (A) contient de la montmorillonite de type Na dans une quantité de 60 % en masse ou plus par rapport à la quantité totale de la bentonite et le rapport de la teneur de l'agent tensioactif anionique (B) sur la teneur de l'agent tensioactif non ionique (C) (à savoir B/C) est de 0,15 à 0,65 en masse. R(AO)nH (1) Dans la formule, R représente un groupe hydrocarbure aliphatique ayant 8 à 18 atomes de carbone ; AO représente un groupe oxyalkylène ayant 2 à 4 atomes de carbone ; n désigne le nombre molaire moyen de groupes AO ajoutés et représente une valeur numérique de 1 à 8 ; et (AO)n contient au moins un groupe oxyéthylène.
PCT/JP2013/055831 2012-03-06 2013-03-04 Agent anti-collant pour caoutchoucs non vulcanisés, et procédé de production de caoutchouc non vulcanisé avec traitement anti-collant WO2013133207A1 (fr)

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JP2017008233A (ja) * 2015-06-24 2017-01-12 横浜ゴム株式会社 ゴム組成物および空気入りタイヤ
WO2018207939A1 (fr) * 2017-05-12 2018-11-15 ライオン・スペシャリティ・ケミカルズ株式会社 Agent anti-adhésivité pour caoutchoucs non vulcanisés et dispersion aqueuse d'agent anti-adhésivité pour caoutchoucs non vulcanisés
WO2019050027A1 (fr) * 2017-09-11 2019-03-14 ライオン・スペシャリティ・ケミカルズ株式会社 Agent anti-collant en caoutchouc non vulcanisé, procédé de production de liquide anti-collant et dispositif de production de liquide anti-collant
WO2019098171A1 (fr) * 2017-11-16 2019-05-23 ライオン・スペシャリティ・ケミカルズ株式会社 Agent antistatique pour caoutchouc non vulcanisé et dispersion aqueuse dudit agent antistatique pour caoutchouc non vulcanisé
JP2020041089A (ja) * 2018-09-12 2020-03-19 ライオン・スペシャリティ・ケミカルズ株式会社 未加硫ゴム用防着剤および未加硫ゴム用防着剤水分散液

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EP3434719A4 (fr) * 2016-03-24 2019-12-04 Lion Specialty Chemicals Co., Ltd. Agent anti-collant pour caoutchouc non vulcanisé et dispersion aqueuse d'agent anti-collant pour caoutchouc non vulcanisé
JP7012014B2 (ja) * 2016-08-09 2022-01-27 ライオン・スペシャリティ・ケミカルズ株式会社 未加硫ゴム用防着剤組成物
JP7262630B2 (ja) * 2017-05-12 2023-04-21 ライオン・スペシャリティ・ケミカルズ株式会社 未加硫ゴム用防着剤および未加硫ゴム用防着剤水分散液
JP7377594B2 (ja) * 2017-08-30 2023-11-10 ライオン・スペシャリティ・ケミカルズ株式会社 未加硫ゴム用防着剤および未加硫ゴム用防着剤水分散液
CN109988336B (zh) * 2019-04-09 2020-10-16 江西广源化工有限责任公司 一种蒙脱石改性纳米氢氧化铝复合无机阻燃剂的制备方法
CN112300694A (zh) * 2020-09-25 2021-02-02 广东华声电器实业有限公司 一种环保线缆防粘剂及其制备方法和应用
CN114672248A (zh) * 2022-04-18 2022-06-28 江苏洪海轮胎科技有限公司 一种防粘剂、制备方法及内表面防粘的自修复轮胎

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017008233A (ja) * 2015-06-24 2017-01-12 横浜ゴム株式会社 ゴム組成物および空気入りタイヤ
WO2018207939A1 (fr) * 2017-05-12 2018-11-15 ライオン・スペシャリティ・ケミカルズ株式会社 Agent anti-adhésivité pour caoutchoucs non vulcanisés et dispersion aqueuse d'agent anti-adhésivité pour caoutchoucs non vulcanisés
WO2019050027A1 (fr) * 2017-09-11 2019-03-14 ライオン・スペシャリティ・ケミカルズ株式会社 Agent anti-collant en caoutchouc non vulcanisé, procédé de production de liquide anti-collant et dispositif de production de liquide anti-collant
WO2019098171A1 (fr) * 2017-11-16 2019-05-23 ライオン・スペシャリティ・ケミカルズ株式会社 Agent antistatique pour caoutchouc non vulcanisé et dispersion aqueuse dudit agent antistatique pour caoutchouc non vulcanisé
JP2019089970A (ja) * 2017-11-16 2019-06-13 ライオン・スペシャリティ・ケミカルズ株式会社 未加硫ゴム用防着剤および未加硫ゴム用防着剤水分散液
JP7037921B2 (ja) 2017-11-16 2022-03-17 ライオン・スペシャリティ・ケミカルズ株式会社 未加硫ゴム用防着剤および未加硫ゴム用防着剤水分散液
JP2020041089A (ja) * 2018-09-12 2020-03-19 ライオン・スペシャリティ・ケミカルズ株式会社 未加硫ゴム用防着剤および未加硫ゴム用防着剤水分散液

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