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WO2009119445A1 - Agent antiadhésif - Google Patents

Agent antiadhésif Download PDF

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Publication number
WO2009119445A1
WO2009119445A1 PCT/JP2009/055445 JP2009055445W WO2009119445A1 WO 2009119445 A1 WO2009119445 A1 WO 2009119445A1 JP 2009055445 W JP2009055445 W JP 2009055445W WO 2009119445 A1 WO2009119445 A1 WO 2009119445A1
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WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
atom
release agent
mold release
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PCT/JP2009/055445
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English (en)
Japanese (ja)
Inventor
晃之 福田
尚志 三橋
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Daikin Industries Ltd
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Daikin Industries Ltd
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Filing date
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Publication of WO2009119445A1 publication Critical patent/WO2009119445A1/fr
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    • 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

Definitions

  • the present invention relates to a mold release agent, and more particularly, to a mold release agent used by being applied to a mold for molding a synthetic resin or rubber.
  • the present invention relates to a release agent (release agent composition), and more particularly to a mold release agent suitable for use in molding a molded body such as a synthetic resin or a synthetic rubber.
  • a release agent is applied to the inner surface of the molding die.
  • wax-type mold release agents such as paraffin wax, higher fatty acid ester wax, polyethylene wax and the like are known. These wax-based release agents are widely used since they are available at low cost and the surface state of the resulting molded article is good.
  • the wax-based mold release agent is inferior in mold release force, it is sufficient to apply it thickly to the mold, especially when molding a molded body using a material having strong adhesive force such as epoxy resin or urethane resin. Therefore, there is a problem that the inside of the molding die is contaminated as the number of molding steps is repeated. This problem also adversely affects the dimensional accuracy of the molded body.
  • the wax-type mold release agent is also inferior in the adhesive force with respect to a shaping
  • a fluorine-based mold release agent [a copolymer of a polyfluoroalkyl ester of (meth) acrylic acid and a substituted vinyl compound] is known (Japanese Patent Laid-Open No. 59-101319). No. and JP-A-60-255404). Since these fluorine-based mold release agents are excellent in mold release force, a sufficient mold release effect can be obtained only by forming a thin film. Moreover, since it is excellent also in the adhesive force with respect to a shaping
  • Japanese Patent Publication No. 3-8245 discloses a release agent comprising a copolymer obtained by polymerizing a perfluoroalkyl group-containing vinyl monomer, a phosphoric acid-containing vinyl monomer and a hydrocarbon vinyl monomer.
  • Patent Nos. 0940355 and 0940356 disclose a mold release agent comprising a perfluoroalkyl group phosphate ester.
  • a resin or rubber accompanied by a reaction at the time of molding processing, particularly a urethane resin inhibits the curing reaction, resulting in a molded article resulting from this.
  • the appearance of the surface is poor.
  • the problem of mold contamination arises by reaction with a mold release agent and a molded object.
  • Japanese Patent Publication No. 3-8245 and Japanese Patent Publication No. 5-517288 there is also known a release agent obtained by blending a polyfluoroalkyl group-containing copolymer with silicone oil and silicone resin.
  • silicone since silicone is blended, stickiness is generated on the surface of the molded body and the secondary processability is poor. Silicone also causes work environment contamination.
  • the silicone-based release agent has a problem that when it is transferred to the surface of the molded body, the surface of the molded body becomes sticky or the secondary workability to the surface of the molded body is inferior. Further, when these fluorine-based mold release agents are dispersed in water, a large amount of an emulsifier is required.
  • telomers can produce PFOA by degradation or metabolism (telomers mean long chain fluoroalkyl groups). We also announced that telomers are used in many products such as foam, water- and oil-repellent and antifouling foams, care products, cleaning products, carpets, textiles, paper and leather. Yes.
  • the Rf group carbon number of the fluorine-containing copolymer mentioned above is 8 or more, there is a concern that it may contain PFOA and PFOA analogs that have bioaccumulation potential, and the carbon number is 6 or less as soon as possible.
  • PFOA and PFOA analogs that have bioaccumulation potential
  • the carbon number is 6 or less as soon as possible.
  • An object of the present invention is to provide a mold release agent comprising a fluoropolymer having a sufficiently high water-solubility and having good appearance on the surface of the molded body, good maintainability to the surface of the molded body. .
  • the present invention comprises (A) a repeating unit derived from a fluorine-containing acrylate monomer, and (B) a fluorine-containing polymer having a repeating unit derived from an amino group-containing monomer, which is water-soluble.
  • a mold release agent containing is provided.
  • the release agent of the present invention is characterized in that the fluoropolymer has a short-chain fluoroalkyl group having 7 or less carbon atoms, particularly 6 or less, so that sufficient solubility in water can be obtained. . Since the fluoropolymer of the present invention has a sufficiently high water solubility, it does not require a large amount of emulsifier, so there is no appearance defect on the surface of the molded body, and the maintainability to the surface of the molded body is good. It has an excellent releasability. In particular, the surface state of the molded body is good, there are no holes on the surface, and the surface is fine.
  • the “acrylate monomer” includes not only an acrylate having a hydrogen atom at the ⁇ -position but also an acrylate in which the hydrogen atom at the ⁇ -position is substituted with a substituent such as a methyl group or a halogen atom.
  • examples of the fluorine-containing acrylate monomer (A) include at least one fluorine-containing group selected from the group consisting of a fluoroalkyl group, a fluoroalkenyl group and a fluoroether group (hereinafter referred to as “fluorine-containing group”).
  • X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group (where X 1 and X 2 is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, A substituted or unsubstituted phenyl group. ] It is a monomer which has an unsaturated group represented by these.
  • Examples of the acrylate monomer having a fluorine-containing group include a formula: [Wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms (for example, 1 to 6)), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group.
  • X 1 and X 2 are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituent Or an unsubstituted benzyl group, a substituted or unsubstituted phenyl group, Y represents a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group.
  • R 1 represents an alkyl group having 1 to 4 carbon atoms
  • Y 1 is a hydrogen atom or an acetyl group.
  • Rf represents a linear or branched fluoroalkyl group having 1 to 7 carbon atoms, a fluoroalkenyl group having 2 to 7 carbon atoms, or repeating units: —C 3 F 6 O—, —C 2 F 4 O— and —
  • a fluoroether group having a total number of 1 to 200 of at least one repeating unit selected from the group consisting of CF 2 O—.
  • Rf group when the Rf group is a fluoroalkyl group, it is preferably a perfluoroalkyl group.
  • Rf groups are -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ).
  • Rf group is a fluoroalkyl group
  • the number of carbons in the Rf group should be 1 to 7, for example 2 to 6, especially 4 to 6, especially 6 from the viewpoints of PFOA and functions described above. Is preferred.
  • Rf may be linear.
  • Rf group is a fluoroalkenyl group
  • the Rf group is a fluoroalkenyl group
  • the Rf group preferably has 2 to 7 carbon atoms, particularly 3 to 6 carbon atoms, especially 6 carbon atoms.
  • the fluoroether group is at least one repeating unit selected from the group consisting of —C 3 F 6 O—, —C 2 F 4 O—, and —CF 2 O— (oxypar group). Fluoroalkylene group).
  • —C 3 F 6 O— is —CF 2 CF 2 CF 2 O— or —CF 2 C (CF 3 ) FO—.
  • —C 2 F 4 O— is generally —CF 2 CF 2 O—.
  • the total number of oxyperfluoroalkylene repeating units is 1 to 200, for example 1 to 100, in particular 5 to 50.
  • the fluoroether group has a terminal group that is directly bonded to the oxyperfluoroalkylene repeat unit.
  • the fluoroether group may have a C1-C10 fluoroalkylene group, particularly a perfluoroalkylene group, in addition to the oxyperfluoroalkylene repeating unit and the terminal group. Examples of the fluoroalkylene group having 1 to 10 carbon atoms are —CF 2 — and —CF 2 CF 2 —.
  • fluoroether groups that are examples of Rf groups are as follows.
  • F- (CF 2 CF 2 CF 2 O) n -CF 2 CF 2- (n is 1 to 200)
  • F- (CF 2 C (CF 3 ) FO) n -CF 2 CF 2- (n is 1 to 200)
  • F- (CF 2 C (CF 3 ) FO) n- (CF 2 O) m -CF 2 CF 2- (total of n and m is 1 to 200)
  • F- (CF 2 CF 2 O) n- (CF 2 O) m -CF 2 CF 2- total of n and m is 1 to 200)
  • Y represents a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group.
  • An aliphatic group a —CH 2 CH 2 N (R 1 ) SO 2 — group (where R 1 is an alkyl group having 1 to 4 carbon atoms) or a —CH 2 CH (OY 1 ) CH 2 — group ( However, Y ⁇ 1 > is a hydrogen atom or an acetyl group.).
  • the aliphatic group is preferably an alkylene group (particularly having 1 to 4 carbon atoms, such as 1 or 2).
  • the aromatic group and the cycloaliphatic group may be either substituted or unsubstituted.
  • X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (where X 1 and X 2 are hydrogen atoms) Atom, fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted Of the phenyl group.
  • X may be a hydrogen atom or a methyl group, but the ⁇ -position may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or the like.
  • fluorine-containing acrylate monomer examples include as follows.
  • 2 OCOCH CH 2 Rf-SO 2 N (C 2 H 5)
  • Rf is a linear or branched fluoroalkyl group having 1 to 7 carbon atoms, a fluoroalkenyl group having 2 to 7 carbon atoms, or a repeating unit: —C 3 F 6 O—, —C 2 F 4 A fluoroether group having a total number of 1 to 200 of at least one repeating unit selected from the group consisting of O— and —CF 2 O—.
  • the amino group-containing monomer (B) is a compound having an amino group and a carbon-carbon double bond.
  • Examples of amino group-containing monomers (B) have the formula: [Wherein R 11 , R 12 and R 21 are the same or different and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y 11 is an oxygen atom or NH, and Z is 1 to 4 carbon atoms] 21 (for example, 1 to 10) branched or straight chain alkylene groups. R 11 and R 12 may be bonded to each other to form a ring together with the adjacent nitrogen atom. ] It is shown by. Since the copolymer includes an amino group, for example, when a salt is formed with a protonic acid, the copolymer is dissociated when dissolved in water and becomes cationic.
  • R 11 , R 12 and R 21 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, butyl, etc.).
  • R 21 is preferably a hydrogen atom or a methyl group.
  • R 11 and R 12 are preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms (that is, methyl, ethyl).
  • R 11 and R 12 may be bonded through a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom.
  • Examples of the ring formed by combining R 11 and R 12 together with the adjacent nitrogen atom include an aziridine ring, pyrrolidine ring, piperidine ring, piperazine ring, morpholine A ring etc. are mentioned.
  • Examples of the alkylene group represented by Z include linear or branched C1-C21 such as methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene groups (for example, 1-10, preferably 1-4 C1). In particular, 1 to 3) alkylene groups are mentioned.
  • amino group-containing monomer (B) examples include chemical formulas (II) such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate.
  • compound Y 11 is an oxygen atom in; dimethylaminoethyl (meth) acrylamide, Y 11 in dimethylaminopropyl (meth) formula of acrylamide (II) and the like compounds wherein NH.
  • the amino group-containing monomer (B) can be used alone or in combination of two or more.
  • the monomer constituting the fluoropolymer may contain a hydrophilic non-fluorine monomer (C) in addition to the monomers (A) and (B).
  • the hydrophilic non-fluorine monomer (C) has hydrophilicity and does not contain a fluorine atom.
  • An example of a hydrophilic group is an oxyalkylene group.
  • the hydrophilic non-fluorine monomer (C) may be a monomer having a hydrophilic group which is an oxyalkylene group (2 to 6 carbon atoms of an alkylene group) and a carbon-carbon double bond.
  • the hydrophilic group which is an oxyalkylene group is nonionic.
  • the number of oxyalkylene groups in the hydrophilic non-fluorine monomer (C) may be 2 to 200, for example 3 to 50.
  • the hydrophilic non-fluorine monomer (C) may be polyalkylene glycol mono (meth) acrylate and / or polyalkylene glycol di (meth) acrylate.
  • the molecular weight of the hydrophilic non-fluorine monomer (C) may be 100 or more, such as 150 or more, particularly 200 or more, particularly 250 to 3000.
  • R in the general formula (III) is particularly preferably an ethylene group.
  • R in the general formula (III) may be a combination of two or more alkylene groups. In that case, at least one of R is preferably an ethylene group. Examples of the combination of R include an ethylene group / propylene group combination and an ethylene group / butylene group combination.
  • the hydrophilic non-fluorine monomer (C) may be a mixture of two or more. In that case, at least one of the hydrophilic non-fluorine monomers (C) preferably has R in the general formula (III) as an ethylene group.
  • hydrophilic non-fluorine monomer (C) examples include, for example, the following, but are not limited thereto.
  • C 4 H 9 CH 2 CX 1 COO- (CH 2 CH 2 O) 23 -OOC (
  • the monomer constituting the fluoropolymer may contain another monomer (D) as required in addition to the monomers (A), (B), (C).
  • the other monomer (D) is preferably a non-fluorine monomer.
  • the other monomer (D) include hydrocarbon group-containing monomers, ethylene, vinyl acetate, vinyl halide (eg, vinyl chloride), vinylidene halide (eg, vinylidene chloride), acrylonitrile, 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, vinyl alkyl ketone, vinyl alkyl Examples include, but are not limited to, ether, isoprene, chloroprene, butadiene and the like.
  • the other monomer (D) includes a monomer having a silane group.
  • the monomer having a silane group is preferably a compound having a silane group (particularly a terminal silane group) and a carbon-carbon double bond.
  • the monomer having a silane group may be a terminal silane coupling agent or a monomer having a silane coupling agent in the side chain. Specific examples of the monomer having a silane group are as follows.
  • the weight average molecular weight of the fluoropolymer may be, for example, from 1,000 to 1,000,000, in particular from 2,000 to 100,000, especially from 4,000 to 20,000.
  • the weight average molecular weight of the fluoropolymer is determined by GPC (gel permeation chromatography) (polystyrene conversion).
  • the fluoropolymer is soluble in water.
  • the solubility of the fluoropolymer (the amount of the fluoropolymer that can be dissolved in 100 g of water at 25 ° C.) may be 5 g or more, for example, 10 g or more, particularly 20 g or more.
  • the upper limit of solubility may be 500 g, for example 200 g.
  • the fluorine-containing polymer may be composed of a combination of repeating units derived from the following monomers. (1) Monomer (A) + Monomer (B) (2) Monomer (A) + Monomer (B) + Monomer (C) (3) Monomer (A) + Monomer (B) + Monomer (D) (4) Monomer (A) + Monomer (B) + Monomer (C) + Monomer (D)
  • the amount of monomer (B) is 1 to 500 parts by weight, for example 2 to 100 parts by weight, in particular 3 to 80 parts by weight, especially 5 to 70 parts by weight,
  • the amount of the monomer (C) is 0 to 10 parts by weight, for example 1 to 5 parts by weight
  • the amount of the monomer (D) is 0 to 10 parts by weight, for example 1 to 5 parts by weight, It may be.
  • the fluoropolymer in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected.
  • Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization. In particular, solution polymerization is preferable.
  • a method is adopted in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, for example, is heated and stirred in the range of 50 to 120 ° C. for 1 to 10 hours.
  • the polymerization initiator include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, Examples include diisopropyl peroxydicarbonate.
  • the polymerization initiator may be used in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the monomer.
  • Organic solvents are those that are inert to the monomers and dissolve them, such as pentane, hexane, heptane, octane, isooctane, cyclohexane, benzene, toluene, xylene, petroleum ether, commercial petroleum solvents (ExxonMobil).
  • EXXSOL D40, ISOPER E, etc. tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, t-butyl acetate, isopropanol, propylene glycol methyl ether acetate, p- Examples include chlorobenzotrifluoride, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like.
  • the organic solvent may be used in the range of 50 to 1000 parts by weight with respect to 100 parts by weight of the total amount of monomers.
  • an aqueous solution of the polymer can be obtained by adding water to the reaction mixture and removing the organic solvent (by distillation or the like).
  • the release agent comprises (1) a fluoropolymer and (2) a liquid medium, that is, water or a mixture of water and a water-soluble organic solvent.
  • water-soluble organic solvents are alcohols such as methanol, ethanol, n-propanol, isopropanol; ketones such as acetone.
  • the amount of the water-soluble organic solvent may be 50% by weight or less, for example, 1 to 30% by weight with respect to the mixture (the sum of water and the water-soluble organic solvent).
  • the release agent is in the form of a solution (aqueous solution) of a fluoropolymer.
  • the amount of the fluorine-containing polymer is not particularly limited and may be appropriately selected from a range in which it can be uniformly dissolved. For example, it may be 0.1 to 50% by weight, for example 0.2 to 20% by weight, in particular 0.5 to 10% by weight, based on the release agent.
  • the release agent of the present invention may contain (3) an additive in addition to (1) the fluoropolymer and (2) the liquid medium.
  • the additive (3) are silicon-containing compounds, waxes, acrylic emulsions and the like.
  • the silicon-containing compound is preferably a compound having at least one siloxane bond.
  • the silicon-containing compound is a compound excluding a compound having a silane group.
  • Examples of silicon-containing compounds include alkyl silicates and siliconates.
  • alkyl silicates include the following general formula (I): [Wherein R 1n represents an alkyl group having 1 to 18 carbon atoms, and when nn is 2 or more, they may be the same or different.
  • R 2n represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be the same or different when nn is 2 or more.
  • nn represents an integer of 1 to 20.
  • the alkyl group having 1 to 18 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and hexyl.
  • the alkyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and these are linear. Alternatively, it may be branched.
  • the nn is an integer of 1 to 20, for example, 1 to 10.
  • the alkyl silicate includes, for example, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethyl.
  • dimers and the like of silicon-containing compounds can also be used as silicon-containing compounds, and examples thereof include those having nn of 2 or 3 in the above general formula (I). Furthermore, nn may be an integer up to 20.
  • Siliconates are for example represented by the formula: R 1 a Si (OR 2 ) b (OM) c is a compound represented by c .
  • a is an integer of 0 or more (preferably 1)
  • b is an integer of 0 or more (preferably 2)
  • R 1 may be the same or different and represents a hydrocarbon group having 1 to 18 carbon atoms.
  • R 2 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
  • M may be the same or different and represents an alkali metal.
  • the hydrocarbon group is, for example, an aliphatic hydrocarbon group (for example, an alkyl group), an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or an araliphatic hydrocarbon group.
  • R 1 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, and n-hexyl.
  • a methyl group, an ethyl group, and a propyl group are preferable, and a methyl group is particularly preferable.
  • R 2 include a hydrogen atom and the same group as R 1 . Among these, a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen atom is particularly preferable.
  • M include Li, Na, K and the like, and Na is particularly preferable.
  • Specific examples of the alkyl siliconate are sodium methyl siliconate [CH 3 Si (OH) 2 (ONa)] and potassium ethyl siliconate [C 2 H 5 Si (OH) 2 (OK)].
  • the amount of the additive (3) may be 0 to 200 parts by weight, for example 0 to 50 parts by weight, for example, 0.1 to 50 parts by weight with respect to 100 parts by weight of the fluoropolymer (1). .
  • the treating agent may contain other water repellents, other oil repellents, drying rate adjusting agents, cross-linking agents, film-forming aids, compatibilizing agents, Surfactant, antifreezing agent, viscosity modifier, UV absorber, antioxidant, pH adjuster, antifoam agent, slipperiness adjuster, antistatic agent, hydrophilizing agent, antibacterial agent, antiseptic, insecticide, You may contain a fragrance
  • a mold release agent is apply
  • the releasable composition of the present invention can be applied to the surface of a mold by a method such as brush coating, roll coating, spray coating, knife coating or dip coating. It may be applied to the surface of the unvulcanized rubber, transferred to the surface of the mold and cured.
  • the mold may be made of metal (for example, steel, aluminum).
  • the releasable composition of the present invention is useful for releasing a rubber (for example, an elastomer) and a resin (for example, a thermosetting resin or a thermoplastic resin).
  • a rubber for example, an elastomer
  • a resin for example, a thermosetting resin or a thermoplastic resin.
  • the material to be molded include polyurethane (soft polyurethane, semi-rigid polyurethane and rigid polyurethane), fluoropolymer (for example, fluororubber), silicone (for example, silicone rubber), and synthetic rubber.
  • IPA isopropanol
  • Comparative Example 1 Instead of the polymer compound, a fluorine-based mold release agent, Die Free ME-810 (manufactured by Daikin Industries, Ltd.) was used and diluted with ion-exchanged water so that the solid content was 1 mass%.
  • Test Example 1 and Comparative Test Example 1 About each release agent shown by the said Example and comparative example, according to the following test method, the mold release property, the frequency
  • the mold release agent composition was uniformly applied by spraying only on one surface of a mold having a length of 20 cm, a width of 5 cm, and a depth of 3 cm. Next, the molded product was blended and molded under the conditions shown below, and the release property was evaluated. Evaluation of releasability is based on the following criteria. ⁇ : Release with a light force, ⁇ : Release with a little force, ⁇ : Release when a strong force is applied, ⁇ : Do not release.
  • the number of times of mold release was such that after the release agent was applied once, the mold release properties deteriorated without further application. That is, it indicates the number of times that the molded product can be taken out completely. Moreover, the surface state after shaping
  • the following molded products 1 to 4 were used as molded products.
  • Molded item 1 Urethane resin (a) Composition Liquid A polyol Sumifene 3900 90 parts [Sumitomo Bayer Urethane Co., Ltd.] Water (foaming agent) 1.6 parts Triethanolamine 3 parts Triethylamine 0.5 parts Kaorizer 0.5 part [manufactured by Kao Corporation] B liquid isocyanate Sumijoule 44V20 41.3 parts [Sumitomo Bayer Urethane Co., Ltd.]
  • Molding 2 Fluoro rubber (a) Compound composition Daiel G740 100 parts [Daikin Industries, Ltd.] Kyowamag 150 3 parts [Kyowa Chemical Industry Co., Ltd.] Caldic 2000 6th part [Omi Chemical Industry Co., Ltd.] 20 parts of MT carbon black [manufactured by RTVanderblit Co Inc]
  • Vulcanization conditions The above compound is sufficiently mixed with a rubber roll and vulcanized under the following conditions.
  • Vulcanization pressure 150Kg / cm 2 Vulcanization temperature 170 ° C
  • Molding 3 Silicone rubber (a) Composition KE-551-U 100 parts [Shin-Etsu Chemical Co., Ltd.] C-8B 1st [Shin-Etsu Chemical Co., Ltd.]
  • Vulcanization conditions The above compound is sufficiently mixed with a rubber roll and vulcanized under the following conditions.
  • Molding 4 Synthetic rubber (a) Composition IR 2000 55 parts [manufactured by JSR Corporation] SBR TUFDENE2003 30 parts [Asahi Kasei Corporation] BR 150 15 parts [Ube Industries, Ltd.] 55 parts of White Carbon Toxeal 255G [manufactured by Lianji Chemical Industry]
  • Vulcanization conditions The above compound is sufficiently mixed with a rubber roll and vulcanized under the following conditions.
  • the release agent of the present invention has sufficiently high water solubility, is excellent in releasability, and gives a good surface state to a molded article of a polymer substance.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention porte sur un agent antiadhésif comprenant un polymère fluoré, qui ne provoque pas d'aspect médiocre dans une surface de produit moulé, qui peut être bien maintenu et appliqué sur la surface du produit moulé et qui a une solubilité élevée satisfaisante dans l'eau. L'agent anti-adhésif comprend un polymère fluoré qui comprend (A) une unité de répétition issue d'un monomère fluoroacrylate et (B) une unité de répétition issue d'un monomère contenant un groupe amino, et qui est soluble dans l'eau. Le monomère contenant un groupe amino (B) est, de préférence, représenté par la formule :  Formule (II) dans laquelle R11, R12 et R21, qui peuvent être identiques ou différents, représentent un atome d'hydrogène ou un groupe alkyle ayant 1 à 4 atomes de carbone ; Y11 représente un atome d'oxygène ou NH ; Z représente un groupe alkylène à chaîne droite ou ramifiée ayant 1 à 10 atomes de carbone ; et R11 et R12 peuvent se combiner entre eux, et, avec un atome d'azote adjacent, former un noyau.
PCT/JP2009/055445 2008-03-24 2009-03-19 Agent antiadhésif Ceased WO2009119445A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008075194 2008-03-24
JP2008-075194 2008-03-24

Publications (1)

Publication Number Publication Date
WO2009119445A1 true WO2009119445A1 (fr) 2009-10-01

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PCT/JP2009/055445 Ceased WO2009119445A1 (fr) 2008-03-24 2009-03-19 Agent antiadhésif

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WO (1) WO2009119445A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102329497A (zh) * 2011-07-12 2012-01-25 苏州斯迪克电子胶粘材料有限公司 一种雾面离型剂
JP2014136381A (ja) * 2013-01-17 2014-07-28 Sumitomo Rubber Ind Ltd ゴム又は樹脂成型用離型剤
JP2017177401A (ja) * 2016-03-29 2017-10-05 三菱マテリアル電子化成株式会社 離型用液組成物
WO2018174190A1 (fr) 2017-03-23 2018-09-27 株式会社ネオス Agent de traitement de surface et procédé pour sa production
CN109517204A (zh) * 2018-11-27 2019-03-26 威高集团有限公司 一种超滑抗菌材料及其制备方法和超滑抗菌导管

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JPS5353608A (en) * 1976-10-23 1978-05-16 Neos Kk Hexafluoropropene oligomer derivatives
JPS6221512A (ja) * 1985-07-23 1987-01-29 Asahi Glass Co Ltd 離型剤組成物
JPS63104804A (ja) * 1986-10-22 1988-05-10 Daikin Ind Ltd 離型剤
JPH09277271A (ja) * 1996-04-10 1997-10-28 Sumitomo Chem Co Ltd 離型剤およびその塗布物
JP2004114620A (ja) * 2002-09-27 2004-04-15 Nof Corp 離型用コーティング剤及び離型フィルム
JP2009057530A (ja) * 2007-08-30 2009-03-19 Ft-Net Co Ltd フッ素系表面改質組成物

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JPS5353608A (en) * 1976-10-23 1978-05-16 Neos Kk Hexafluoropropene oligomer derivatives
JPS6221512A (ja) * 1985-07-23 1987-01-29 Asahi Glass Co Ltd 離型剤組成物
JPS63104804A (ja) * 1986-10-22 1988-05-10 Daikin Ind Ltd 離型剤
JPH09277271A (ja) * 1996-04-10 1997-10-28 Sumitomo Chem Co Ltd 離型剤およびその塗布物
JP2004114620A (ja) * 2002-09-27 2004-04-15 Nof Corp 離型用コーティング剤及び離型フィルム
JP2009057530A (ja) * 2007-08-30 2009-03-19 Ft-Net Co Ltd フッ素系表面改質組成物

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102329497A (zh) * 2011-07-12 2012-01-25 苏州斯迪克电子胶粘材料有限公司 一种雾面离型剂
CN102329497B (zh) * 2011-07-12 2012-11-21 苏州斯迪克新材料科技股份有限公司 一种雾面离型剂
JP2014136381A (ja) * 2013-01-17 2014-07-28 Sumitomo Rubber Ind Ltd ゴム又は樹脂成型用離型剤
JP2017177401A (ja) * 2016-03-29 2017-10-05 三菱マテリアル電子化成株式会社 離型用液組成物
WO2018174190A1 (fr) 2017-03-23 2018-09-27 株式会社ネオス Agent de traitement de surface et procédé pour sa production
KR20190129078A (ko) 2017-03-23 2019-11-19 네오스 컴파니 리미티드 표면 처리제 및 그 제조 방법
JPWO2018174190A1 (ja) * 2017-03-23 2020-01-23 株式会社ネオス 表面処理剤及びその製造方法
JP7117286B2 (ja) 2017-03-23 2022-08-12 株式会社ネオス 表面処理剤及びその製造方法
CN109517204A (zh) * 2018-11-27 2019-03-26 威高集团有限公司 一种超滑抗菌材料及其制备方法和超滑抗菌导管
CN109517204B (zh) * 2018-11-27 2021-04-30 威高集团有限公司 一种超滑抗菌材料及其制备方法和超滑抗菌导管

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